WO2014193089A1 - Method for preparation of carbon quantum dots - Google Patents

Method for preparation of carbon quantum dots Download PDF

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WO2014193089A1
WO2014193089A1 PCT/KR2014/003998 KR2014003998W WO2014193089A1 WO 2014193089 A1 WO2014193089 A1 WO 2014193089A1 KR 2014003998 W KR2014003998 W KR 2014003998W WO 2014193089 A1 WO2014193089 A1 WO 2014193089A1
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solution
carbon quantum
reaction
fluorescence
synthesized
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PCT/KR2014/003998
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French (fr)
Korean (ko)
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문병기
정중현
최병춘
유영문
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부경대학교 산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/03—Pressure vessels, or vacuum vessels, having closure members or seals specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0038—Manufacturing processes for forming specific nanostructures not provided for in groups B82B3/0014 - B82B3/0033
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors

Definitions

  • the present invention relates to a carbon quantum dot production method and a carbon quantum dot produced thereby, more specifically Organic compounds such as sugar, starch, vitamin C, glucose, tartaric acid, citric acid, oleic acid, glutamine, glutamic acid, urea, benzene, acetylacetone, acetophenone and acetic acid, and reaction accelerators such as oxidizing agents, reducing agents, and catalysts include water, methanol, ethanol, Carbon quantum dot production method and carbon quantum dot produced by mixing in a solvent such as 2-propanol, hydrogen peroxide, n-propanol, chlorobenzene and reacted at a temperature of 230 °C or more to produce a carbon quantum dot will be.
  • Organic compounds such as sugar, starch, vitamin C, glucose, tartaric acid, citric acid, oleic acid, glutamine, glutamic acid, urea, benzene, acetylacetone, acetophenone and acetic
  • carbon nanotubes CNT
  • purerine graphene
  • graphene graphene
  • Carbon quantum dots are not pure carbon crystals, but have physical properties of quantum effects among nano-sized carbon compounds, and are well known for their applicability in various fields.
  • Carbon quantum dot is based on graphite nanoparticles, and is known to have a structure in which chemical groups such as epoxides, hydroxyl groups, and carboxyl groups are bonded to the surface, and carbon nanoparticles and graphene oxides. Also called nanoparticles.
  • the main component of the carbon quantum dot is carbon (graphite nanoparticles), and it is called carbon quantum dot because it has the characteristics of quantum dots.
  • the size of the carbon quantum dots is several nm. It has the characteristics of a typical quantum dot that has a different color depending on the particle size and the fluorescence wavelength varies depending on the particle size.
  • carbon quantum dots are bio-friendly carbon compounds and can be applied to sensors that can be injected into the human body.
  • carbon quantum dots have applicability in many fields, chemical synthesis methods for mass production are not well known. Stripping graphite one by one produces graphene, and grinding graphite into nanoparticles results in carbon quantum dots.
  • the method of making carbon quantum dots by peeling or pulverizing graphite is called a top-down method and is the most common method of synthesizing carbon quantum dots.
  • the method of manufacturing carbon quantum dots by the top-down method has low production efficiency, and it is very difficult to artificially control the size, surface state, and the like of the particles.
  • the present invention for overcoming various problems of the existing method for synthesizing carbon quantum dots as described above is a new synthesis technology, a bottom-up method, that is, through the reaction of decomposition, carbonization, and crystallization of organic compounds.
  • the purpose is to enable the production of carbon quantum dots.
  • the present invention can synthesize a carbon quantum dot from all kinds of organic materials, it is possible to control the size, efficiency of the product and to synthesize in large quantities.
  • the object as described above is to prepare a solution by mixing an organic compound, a solvent, an accelerator; And it is achieved by the carbon quantum dot manufacturing method comprising the step of heating the solution.
  • the accelerator is characterized in that any one or more of an oxidizing agent, a reducing agent, a catalyst.
  • the oxidizing agent is characterized in that any one or more of nitric acid, sulfuric acid, hydrogen peroxide.
  • the reducing agent is characterized in that potassium borohydride.
  • the catalyst is characterized in that the Fe 2 O 3 nanoparticles.
  • the solvent is characterized in that any one or more of water, methanol, ethanol, 2-propanol, n-propanol, hydrogen peroxide, chlorobenzene.
  • the organic compound is any one of sugar, starch, vitamin C, glucose, tartaric acid, citric acid, oleic acid, glutamine, glutamic acid, urea, benzene, acetylacetone, acetophenone, acetic acid It is characterized by one or more.
  • the solution is characterized in that the heating to a temperature of 220 to 290 °C or more.
  • the present invention is a method for synthesizing carbon quantum dots, by introducing a new synthetic method borrowing a natural environment in which coal or graphite is generated from organic matter, the efficiency and productivity are higher than the existing method, carbon Quantum dots can be produced in large quantities.
  • the present invention can control the size, synthesis efficiency of the carbon quantum dot simply by changing the synthesis conditions, such as solvent, temperature.
  • the present invention can synthesize carbon quantum dots from almost all kinds of organic matter, and can be synthesized from inexpensive food compounds such as flour, starch, sugar and the like.
  • the present invention synthesizes a carbon quantum dot only with a solvent, an accelerator, and an organic material, thereby obtaining a carbon quantum dot from a synthesized product without undergoing a complicated purification process.
  • the present invention includes a crystallization process, the size of the product can be adjusted according to the concentration of the organic matter in the crystallization process, the higher the concentration of the organic matter is produced, the smaller particles are produced at a lower concentration.
  • the present invention synthesizes carbon quantum dots by a bottom-up method of decomposing organic compounds to synthesize carbon quantum dots, thereby increasing efficiency and economic efficiency, easily controlling particle sizes, and uniform particle size of carbon quantum dots. As a result, the physical properties are uniform.
  • Coal, graphite and diamond are carbon allotrope.
  • Diamond is a carbon crystal produced under high temperature and high pressure, and is mainly found in igneous rock layers.
  • Graphite is mainly found in metamorphic rocks and sometimes in igneous rocks.
  • Coal, an amorphous carbon is found mainly in sedimentary rock layers, and it is known that the sedimentary layers of organic matter in plants and animals become carbon through oxidation and carbonization.
  • Diamonds, graphite, and coal, all made in nature, are all produced from organic matter under constant pressure and temperature.
  • Amorphous coal is produced in the sedimentary layers with low pressure and temperature, and graphite of layered structure is produced in the metamorphic rock layers with medium pressure and temperature, and diamonds with high hardness are produced in the high-temperature and high-pressure igneous rock layers.
  • the carbon quantum point has a lower degree of crystallinity than graphite, which is a lumped crystal, and a higher degree of crystallinity than non-crystalline coal. It is thought that carbon quantum dots, which are low-crystallinity carbon materials, can be created by creating an environment with a temperature and pressure that is intermediate between that of coal and graphite. In this environment of temperature and pressure, when organic matter is decomposed, carbonized and crystallized into nanoparticles, carbon quantum dots are generated.
  • a hydrothermal method or a similar solvothermal method can be used.
  • a closed vessel of water is heated to generate temperature and pressure, and single crystals such as quartz, emerald, and ZnO can be grown.
  • Solvent thermal synthesis method is a method for producing a temperature and pressure by synthesizing a closed container containing an organic solvent, such as alcohol, benzene is used for the reaction that requires an organic solvent.
  • Organic matter (carbon compounds) buried in the ground is slowly decomposed and carbonized to produce coal.
  • the natural process of producing coal requires not only heat and pressure to decompose and carbonize organics, but also a long time.
  • an active method for decomposing the organic matter is required.
  • the decomposition of the organic matter is promoted using an oxidizing agent, a reducing agent, a catalyst, and the like.
  • Oxidizers used as accelerators include nitric acid, sulfuric acid, hydrogen peroxide, potassium permanganate, and reducing agents include NaBH 4 , potassium borohydride (KBH 4 ), LiAlH 4 , and N 2 H 4 . , Ni, TiO 2 , Fe 2 O 3 nanoparticles and the like.
  • Coal, graphite, and the like are produced by decomposing and carbonizing organic substances, which are the remains of plants and animals.
  • a general organic compound is used as a starting material for synthesizing carbon quantum dots.
  • Carbon quantum dots can be synthesized from all kinds of organic materials. All of these organics are clear liquids or white powders. When synthesized by the method of the present invention using a transparent or white organic material as a starting material, a liquid having a color unique to carbon quantum dots becomes a black liquid when the concentration of carbon quantum dots is high.
  • solvent thermal crystal growth it is possible to control the rate and form of crystal growth according to the polarity of the solvent.
  • the shape of the carbon crystals was adjusted according to the dielectric constant of the solvent.
  • Water a highly polar solvent, is easy to synthesize low concentrations of carbon quantum dots.
  • a high concentration of carbon quantum dots can be synthesized, thereby increasing the efficiency of the synthesis.
  • solvents such as water, methanol (methyl alcohol), ethanol (ethyl alcohol), 2-propanol (isopropyl alcohol), n-propanol (n-propyl alcohol), hydrogen peroxide, chlorobenzene, and the like are used. To synthesize a carbon quantum dot.
  • a method of synthesizing carbon quantum dots by decomposing, carbonizing, and crystallizing an organic substance was developed.
  • the flowchart of the method is as follows.
  • carbon quantum dots can be synthesized by decomposing all kinds of organic substances.
  • the synthesis efficiency of the carbon quantum dot is high, there is an advantage that can be adjusted in size.
  • Carbon homogenates such as coal, graphite, and diamond are produced under heat and pressure in the earth's crust.
  • the raw materials of coal and graphite are organic substances, and organic compounds buried in the earth's crust are decomposed, and carbon isomers are produced through carbonization and crystallization.
  • the present invention borrows the principle that such carbon homogenates are naturally produced, and has developed a new synthesis method for synthesizing carbon quantum dots. This synthesis process consists of decomposing organic compounds dissolved in sealed containers using accelerators, carbonizing and crystallizing the decomposed organic compounds by applying pressure and heat.
  • This synthesis method uses (i) a high pressure reactor capable of maintaining high temperature and high pressure, (ii) various organic compounds as raw materials, (iii) accelerators for decomposing organic matters and promoting reactions, and (iv) Solvent was used to control the reaction.
  • a high pressure reactor capable of maintaining high temperature and high pressure
  • various organic compounds as raw materials
  • accelerators for decomposing organic matters and promoting reactions and
  • Solvent was used to control the reaction.
  • the high pressure reactor used in the synthesis of the present invention is composed of an inner container and an outer container as in Patent No. 1007694210000, and the inner container is made of Teflon that does not react with chemicals, and the outer container for maintaining pressure is made of stainless steel. It was. A thermostat and a magnetic stirrer were attached to the high pressure reactor. The temperature of the chemical reaction was automatically controlled using a temperature controller, and the solution was kept homogeneous during the reaction using a magnetic stirrer. There are two types of high pressure reactors used in the reaction, and the volume of each inner container is 1,200cc and 60cc.
  • carbon quantum dots were synthesized from various organic compounds. Oleic acid, acetylacetone, acetophenone, acetic acid, acetone, benzene and sugar, starch, vitamin C, glucose, tartaric acid, citric acid, glutamine, glutamic acid, and the like.
  • the greatest advantage of the synthesis method in the present invention is that it is possible to synthesize carbon quantum dots from almost all kinds of organic materials by decomposing and carbonizing crystallization of commonly encountered organic compounds.
  • Compounds synthesized by the method of the present invention include organic substances such as solvents, carbon quantum dots, aromatic oils, and precipitates, and these were purified to evaluate physical and chemical properties.
  • Carbon quantum dots are readily soluble in water and are several nm in size.
  • the aromatic oil is filtered by the filter, and the carbon quantum dot and the solvent are permeated.
  • the permeated solution was diluted with water and passed through a hydrophilic membrane filter with a pore size of 0.1 ⁇ m to obtain a carbon quantum dot solution.
  • the carbon quantum dot solution which had been removed with impurities, was uniform, and had excellent dispersion in water such that no precipitation occurred after 3 months at room temperature.
  • carbon quantum dots such as XRD patterns, FT-IR absorption spectra, particle size measurement by TEM, fluorescence characteristics, and light absorption characteristics.
  • the biggest feature of carbon quantum dot is carbon material that emits fluorescence.
  • four fluorescence measurements are shown for one synthesis example. Two pictures of fluorescence emitted from the bottom of the vial containing the solution and two fluorescence spectra measured with a fluorophotometer. Two fluorescence spectra were measured by irradiating light at 365 nm and 400 nm, respectively, and color coordinates (CIE1931) of fluorescence were calculated from the measured fluorescence spectra.
  • the main component of the carbon quantum dot is carbon, so it absorbs light in all wavelength ranges of visible light.
  • the solution containing the carbon quantum dot was extracted from the composite and placed in a cuvette having a transmission length of 10 mm to measure light absorption spectra of 300 nm to 700 nm.
  • the absorption efficiency of 500 nm was expressed in optical density (OD) in the measured light absorption spectrum, and the synthesis efficiency of carbon quantum dots was compared.
  • the synthesized conditions and the absorbance of the compound are shown in Tables 1 and 2.
  • the type and amount of organic matter, reaction accelerator, temperature, and the like were maintained under the same conditions, and the amount of carbon quantum dots generated when the solvent was changed increased in the order of water, methanol, and ethanol.
  • the water absorption was OD of 0.185 when the solvent was used.
  • the absorbance of the solvent was 1.94 and ethanol was synthesized as the solvent.
  • Tables 1 and 2 it can be seen that the concentration of carbon quantum dots synthesized in ethanol is several orders of magnitude higher than the carbon quantum dots synthesized using water as a solvent. 5 cc of the solution synthesized in Synthesis Example 31 was diluted with water to obtain 500 cc of carbon quantum dot solution having the same concentration as the solution of Synthesis Example 2.
  • the synthesis efficiency was low mainly by using hydrothermal synthesis method using water as a solvent.
  • the synthesis efficiency of synthesizing carbon quantum dots by using organic solvents such as methanol and ethanol has been increased, and the synthesis method can produce carbon quantum dots in large quantities by decomposing almost all kinds of organic substances by facilitating the reaction using accelerators.
  • Examples of synthesizing carbon quantum dots are summarized in Tables 1 and 2 below.
  • the organic materials, reaction accelerators and solvents used for synthesizing carbon quantum dots were shown, and the reaction temperature and duration were also shown.
  • the synthesis example when the amount of solvent was less than 60cc, the synthesis was carried out using a high pressure reactor with an internal volume of 60cc, and the synthesis with the amount of the solvent was greater than 400cc using a high pressure reactor with an internal volume of 1200cc.
  • the absorbance of the solution after the reaction was measured to compare the relative concentration of the carbon quantum dot produced.
  • FIGS. 1 to 54 show results of various examples synthesized by the methods of ⁇ Synthesis Example 1> to ⁇ Synthesis Example 54>, as shown in Tables 1 and 2.
  • FIGS. 1A to 1I show the characteristics of Synthesis Example 1 of the carbon quantum dots synthesized by the method of the present invention.
  • the mixture was placed in a high pressure reactor having an internal volume of 1200 cc and maintained at 250 ° C. for 35 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in (a) of FIG.
  • (a) of FIG. 1 there is absorption in all wavelength ranges of visible light, and the intensity of absorption gradually increases as the wavelength becomes shorter.
  • the peak of the absorption curve appears at 261 nm, which is an optical band, one of the characteristics of carbon quantum dots.
  • the absorption coefficient of the synthetic solution at 500 nm is 0.194.
  • Figure 1 (b) is an excitation spectrum when the fluorescence wavelength is 428nm, it can be seen that there is also an optical band of the same wavelength as the absorption spectrum in this excitation spectrum. When irradiated with excitation light of 365 nm, the fluorescence spectrum is as shown in FIG.
  • carbon quantum dots One characteristic of carbon quantum dots is that the fluorescence spectrum varies depending on the excitation wavelength.
  • the wavelength of the excitation light is 335 nm, 365 nm, 435 nm, 470 nm, and 500 nm, as shown in FIG. 1D
  • the fluorescence spectrum is the same as that of FIG.
  • the photograph of the solution containing the synthesized solution is shown in (d-1) of FIG. 1, and the photo of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the vial containing the solution is shown in FIG. 2), and the photo taken with blue LED (460 nm) for fluorescence is (d-3) of FIG. 1.
  • the FT-IR spectrum of the synthesized solution is as shown in FIG.
  • the synthesized solution is dried, it becomes a sticky black gel, and the x-ray diffraction pattern of the gel is shown in FIG.
  • FIG. 1 (g)-(p) A photograph of the synthesized solution measured by a transmission electron microscope (TEM) is shown in FIG. 1 (g)-(p), and the size, shape, crystal lattice, and the like of the carbon quantum dots included in the solution were confirmed.
  • Figure 1 (g) and (i) the size of the carbon quantum dot was measured.
  • the size distribution of the carbon quantum dots is shown in (q) of FIG. 1, and the average size of the carbon quantum dots is about 2.64 nm.
  • (H) and (j) of FIG. 1 are enlarged TEM photographs of (g) and (i) of FIG. 1, and the crystal surface patterns of carbon quantum dots appear as shown in the photograph.
  • FIG. 1 (g)-(p)-(p) A photograph of the synthesized solution measured by a transmission electron microscope (TEM) is shown in FIG. 1 (g)-(p), and the size, shape, crystal lattice, and the like of the carbon quantum dots included in the solution were confirmed.
  • 1 (k) is a carbon quantum dot photograph having a clear crystal surface pattern, and the diffraction pattern of the crystal surface pattern is (l) of FIG. 1.
  • the diffraction point of (l) of FIG. 1 has hexagonal symmetry and is the same as that of c-plane of graphite.
  • the diffraction pattern of the crystal plane pattern and the hexagonal symmetry can be seen.
  • 1 (o) and (p) photographs were compared with the crystal plane of graphite by measuring the spacing of the crystal plane pattern.
  • FIG. 2 shows the results of Synthesis Example 2 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 2 of Table 1 distilled water 37.5cc, acetylacetone 3g, and 1g nitric acid were mixed to obtain an internal volume of 60cc.
  • the reaction mixture was placed in a phosphorous autoclave and maintained at 250 ° C. for 35 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 2 (a), the absorption coefficient is 0.185 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 2B and 2C, respectively, and the color coordinates of fluorescence are (0.1667, 0.1464) and (0.1883, 0.2455), respectively.
  • 2 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the vial containing the solution is shown in Figure 2 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 2 (f).
  • FIG. 3 shows the results of Synthesis Example 3 of the carbon quantum dots synthesized by the method of the present invention.
  • 500 cc of distilled water, 36 g of citric acid, and 12 g of nitric acid were mixed to obtain a high pressure of 1200 cc.
  • the reaction was carried out while keeping in the reactor for 30 hours at 250 °C.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 3 (a), the absorption coefficient is 0.937 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 3B and 3C, respectively, and the color coordinates of fluorescence are (0.1811, 0.1901) and (0.2006, 0.2883), respectively.
  • 3 (d) is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 3 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 3 (f). to be.
  • FIG. 4 shows the results of Synthesis Example 4 of the carbon quantum dots synthesized by the method of the present invention.
  • the synthesis example 4 of Table 1 40 cc of distilled water, 3 g of citric acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor at 250 ° C. The reaction was maintained at 35 hours at. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 4 (a), the absorption coefficient is 0.0304 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 4B and 4C, respectively, and the color coordinates of fluorescence are (0.1677, 0.1462) and (0.2001, 0.2668), respectively.
  • 4 (d) is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 4 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 4 (f). to be.
  • FIG. 5 shows the results of Synthesis Example 5 of the carbon quantum dots synthesized by the method of the present invention.
  • distilled water 37.5cc, glucose 1g, and nitric acid 3g were mixed and placed in a high pressure reactor.
  • the reaction was maintained at 30 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction.
  • the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 5 (a), the absorption coefficient is 0.0096 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 5B and 5C, respectively, and the color coordinates of fluorescence are (0.1716, 0.1200) and (0.2841, 0.2670), respectively.
  • 5 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 5 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 5 ( f).
  • FIG. 6 shows the results of Synthesis Example 6 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 6 of Table 1 37.5 cc of distilled water, 1.2 g of glucose, and 2 g of nitric acid were mixed to a high pressure reactor. The reaction was carried out while maintaining at 245 °C for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 6 (a), the absorption coefficient is 0.117 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 6B and 6C, respectively, and the color coordinates of fluorescence are (0.1659, 0.1590) and (0.1812, 0.2772), respectively.
  • 6 (d) is a test tube photograph containing the synthesized solution.
  • the photo of fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 6 (e)
  • the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 6 ( f).
  • FIG. 7 shows the results of Synthesis Example 7 of the carbon quantum dots synthesized by the method of the present invention.
  • distilled water 37.5 cc, sugar 1 g, and nitric acid 3 g were mixed and placed in a high pressure reactor.
  • the reaction was maintained at 30 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction.
  • the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 7 (a), the absorption coefficient is 0.130 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 7B and 7C, respectively, and the color coordinates of fluorescence are (0.1641, 0.1479) and (0.1777, 0.2546), respectively.
  • 7 (d) is a test tube photograph containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 7 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 7 ( f).
  • FIG. 8 shows the results of Synthesis Example 8 of the carbon quantum dots synthesized by the method of the present invention.
  • synthesis example 8 of Table 1 37.5 cc of distilled water, 3 g of sugar, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 8 (a), the absorption coefficient is 0.564 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 8B and 8C, respectively, and the color coordinates of fluorescence are (0.1827, 0.1922) and (0.1843, 0.2843), respectively.
  • (D) of FIG. 8 is a test tube photograph containing the synthesized solution.
  • the photo of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 8 (e)
  • the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 8 ( f).
  • FIG. 9 shows the results of Synthesis Example 9 of the carbon quantum dots synthesized by the method of the present invention.
  • the reaction was maintained at 30 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 9 (a), the absorption coefficient is 0.410 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 9B and 9C, respectively, and the color coordinates of fluorescence are (0.1724, 0.1692) and (0.1826, 0.2729), respectively.
  • 9 (d) is a test tube photograph containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 9 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 9 ( f).
  • FIG. 10 shows the results of Synthesis Example 10 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 10 of Table 1 37.5 cc of distilled water, 3 g of acetic acid, and 2 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 24 ° C. for 24 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 10 (a), the absorption coefficient is 0.00475 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 10B and 10C, respectively.
  • the color coordinates of (b) of FIG. 10 are (0.1769, 0.1340), and (c) of FIG. 10 corresponds to a case where the fluorescence is very weak. Therefore, the color coordinates are not calculated.
  • 10 (d) is a photograph of a test tube containing a synthesized solution.
  • FIG. 11 shows the results of Synthesis Example 11 of the carbon quantum dots synthesized by the method of the present invention.
  • distilled water 37.5cc, tartaric acid and 2g nitric acid were mixed and placed in a high pressure reactor at 245 ° C. The reaction was maintained for 30 hours at. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 11 (a), the absorption coefficient is 0.0787 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 11B and 11C, respectively, and the color coordinates of fluorescence are (0.1682, 0.1450) and (0.0.1906, 0.2529), respectively.
  • 11 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 11 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 11 ( f).
  • FIG. 12 shows the results of Synthesis Example 12 of the carbon quantum dots synthesized by the method of the present invention.
  • distilled water 37.5cc, urea 3g, and 1g nitric acid were mixed and placed in a high pressure reactor.
  • the reaction was maintained at 30 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction.
  • the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is as shown in Figure 12 (a), the absorption coefficient is 0.00147 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 12B and 12C, respectively, and the color coordinates of fluorescence are (0.1637, 0.1167) and (0.1899, 0.2526), respectively.
  • 12 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 12 (e), the photo taken with fluorescence by the blue LED (460 nm) is shown in Figure 12 ( f).
  • FIG. 13 shows the results of Synthesis Example 13 of the carbon quantum dots synthesized by the method of the present invention.
  • synthesis example 13 of Table 1 37.5 cc of distilled water, 1 g of glutamic acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 13 (a), the absorption coefficient is 0.123 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 13B and 13C, respectively, and the color coordinates of fluorescence are (0.1653, 0.1215) and (0.2062, 0.2454), respectively.
  • (D) of FIG. 13 is a test tube photograph containing the synthesized solution.
  • the photo of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 13 (e)
  • the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 13 ( f).
  • FIG. 14 shows the results of Synthesis Example 14 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 14 of Table 1 37.5 cc of distilled water, 3 g of oleic acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 14 (a), the absorption coefficient is 0.0384 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 14B and 14C, respectively, and the color coordinates of fluorescence are (0.1622, 0.1136) and (0.0.1740, 0.1967), respectively.
  • Figure 14 (d) is a test tube picture containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 14 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 14 ( f).
  • FIG. 15 shows the results of Synthesis Example 15 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 15 of Table 1 37.5 cc of distilled water, 3 g of acetphenone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 15 (a), the absorption coefficient is 0.111 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 15B and 15C, respectively. The color coordinates of (b) of FIG. 15 are (0.2401, 0.2271), and (c) of FIG. 15 corresponds to a case where the fluorescence is very weak. Therefore, the color coordinates are not calculated.
  • Figure 15 (d) is a photograph of the test tube containing the synthesized solution.
  • FIG. 16 shows the results of Synthesis Example 16 of the carbon quantum dots synthesized by the method of the present invention.
  • the synthesis example 16 of Table 1 37.5 cc of hydrogen peroxide and 3 g of acetylacetone were mixed and placed in a high pressure reactor at 245 ° C.
  • FIG. The reaction was maintained for 30 hours.
  • Hydrogen peroxide, the oxidant in this synthesis is both a solvent and an accelerator to decompose acetylacetone to promote the reaction.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 16 (a), the absorption coefficient at 500nm is 0.197.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 16B and 16C, respectively, and the color coordinates of fluorescence are (0.1684, 0.1393) and (0.1854, 0.2287), respectively.
  • (D) of FIG. 16 is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 16 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 16 (f). to be.
  • FIG. 17 shows the results of Synthesis Example 17 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 17 of Table 1 37.5 cc of distilled water, 3 g of glucose, and 1 g of sulfuric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 17 (a), the absorption coefficient is 0.170 at 500nm. Fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 17B and 17C, respectively, and the color coordinates of fluorescence are (0.1685, 1425) and (0.2144, 0.3331), respectively.
  • Figure 17 (d) is a test tube picture containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 17 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 17 ( f).
  • FIG. 18 shows the results of Synthesis Example 18 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 18 of Table 1 37.5 cc of distilled water, 3 g of acetylacetone, and potassium borohydride (KBH 4 ) 1g was mixed and placed in a high pressure reactor, and reacted at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 18 (a), the absorption coefficient is 0.480 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 18B and 18C, respectively, and the color coordinates of fluorescence are (0.1910, 0.1899) and (0.2109, 0.3193), respectively.
  • 18 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 18 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 18 ( f).
  • FIGS. 19A to 19D show results of Synthesis Example 19 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 19 of Table 1 500 cc of methanol, 36 g of acetylacetone, and 12 g of nitric acid were used. The mixture was placed in a high pressure reactor having an internal volume of 1200 cc and maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 19 (a) The UV-Vis absorption spectrum of the diluted solution of the synthetic solution at 1/15 ratio is shown in FIG. 19 (a), and the absorption coefficient at 0.2 nm is 0.241. According to the diluted ratio, the absorption coefficient of the synthetic solution is 3.62. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 19B and 19C, respectively, and the color coordinates of fluorescence are (0.1776, 0.1763) and (0.1964, 0.2739), respectively.
  • 19 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 19 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
  • TEM photograph of the synthetic solution is shown in (g) of FIG.
  • TEM images measured on a 50 nm scale show quantum dot particles dispersed and not aggregated, and crystal lattice planes were clear in five photographs in which each particle was enlarged.
  • the average size of the quantum dot particles measured in the TEM image is 4.15nm, the distribution according to the size is shown in Figure 19 (h).
  • FIG. 20 shows the results of Synthesis Example 20 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 20 of Table 1 37.5 cc of methanol, 3 g of acetylacetone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 20 (a) The UV-Vis absorption spectrum of the solution diluted by the 1/15 ratio of the synthetic solution is shown in FIG. 20 (a), and the absorption coefficient at 500 nm is 0.129. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.94. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 20B and 20C, respectively, and the color coordinates of fluorescence are (0.1768, 0.1754) and (0.1939, 0.2716), respectively.
  • (D) of FIG. 20 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 20 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
  • FIG. 21 is a result of synthesizing the properties of Synthesis Example 21 of the carbon quantum dot synthesized by the method of the present invention.
  • Synthesis Example 21 of Table 1 20 cc of methanol, 20 cc of distilled water, 3 g of acetylacetone, and 1 g of nitric acid were mixed. And reacted while maintaining at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 21 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/5 is shown in FIG. 21 (a), and the absorption coefficient at 500 nm is 0.136. According to the diluted ratio, the absorption coefficient of the synthetic solution is 0.679. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 21B and 21C, respectively, and the color coordinates of fluorescence are (0.1708, 0.1534) and (0.1962, 0.2784), respectively.
  • 21 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 21 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at 1/5 ratio. Is Fig. 21 (f).
  • FIG. 22 shows the results of Synthesis Example 22 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 22 of Table 1 37.5 cc of methanol, 3 g of acetone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 22 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a 1/10 ratio is shown in FIG. 22 (a), and the absorption coefficient at 500 nm is 0.152. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 1.52. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 22B and 22C, respectively, and the color coordinates of fluorescence are (0.1722, 0.1671) and (0.1848, 0.2632), respectively.
  • (D) of FIG. 22 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG.
  • FIG. 23 shows the properties of Synthesis Example 23 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 23 of Table 1 37.5 cc of methanol, 3 g of acetophenone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 23 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/7 is shown in FIG. 23 (a), and the absorption coefficient at 500 nm is 0.144. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.01. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 23B and 23C, respectively, and the color coordinates of fluorescence are (0.1689, 0.1111) and (0.2016, 0.2659), respectively.
  • Figure 23 (d) is a test tube picture containing the synthesized solution. Photograph (e) of FIG.
  • FIG. 24 shows the results of Synthesis Example 24 of the carbon quantum dots synthesized by the method of the present invention.
  • synthesis example 24 of Table 1 37.5 cc of methanol, 3 g of oleic acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 24 (a), the absorption coefficient is 0.254 at 500nm. Fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 24B and 24C, respectively, and the color coordinates of fluorescence are (0.1836, 0.1137) and (0.2038, 0.2861), respectively.
  • 24 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 24 (e) irradiated with an ultraviolet LED (380 nm) emitted from the bottom of a glass bottle containing a solution diluted at a ratio of 1/7 is (e), and photographed with a blue LED (460 nm). Is (f) of FIG.
  • the UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a 1/20 ratio is shown in FIG. 25 (a), and the absorption coefficient at 0.2 nm is 0.263. According to the diluted ratio, the absorption coefficient of the synthetic solution is 5.25. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 25B and 25C, respectively, and the color coordinates of fluorescence are (0.1772, 0.1111) and (0.1955, 0.2759), respectively. 25 (d) is a test tube photograph containing the synthesized solution.
  • the photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/20 is (e) of FIG. 25, the photo was taken by fluorescence by the blue LED (460 nm). Is (f) of FIG.
  • the X-ray diffraction pattern measured by drying the permeate liquid is shown in FIG. 25 (h).
  • FIG. 25 is an enlarged photograph of part of FIG. 25 (i-1), and is a CQD in which the crystal lattice plane is clearly visible.
  • the diffraction pattern obtained by Fourier transforming the crystal lattice of one particle in FIG. 25 (i-2) is shown in FIG. 25 (i-3). The diffraction pattern formed a crushed hexagon.
  • 25 (j-1) and (j-2) are carbon quantum points in which crystal lattice planes are clearly measured, and the measured lattice distances and surface indices are indicated.
  • 25 (j-2) shows a diffraction pattern obtained by Fourier transforming a crystal lattice.
  • Figure 25 (k) shows the size distribution of carbon quantum dot particles measured by TEM, the average size is about 4.40nm.
  • FIG. 26 shows the results of Synthesis Example 26 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 26 of Table 1 45 cc of ethanol, 3 g of acetylacetone, and 0.45 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 26 (a) The UV-Vis absorption spectrum of the solution diluted by the 1/15 ratio of the synthetic solution is shown in FIG. 26 (a), and the absorption coefficient at 500 nm is 0.148. According to the diluted ratio, the absorption coefficient of the synthetic solution is 2.23. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 26B and 26C, respectively, and the color coordinates of fluorescence are (0.1747, 0.1694) and (0.1887, 0.2590), respectively.
  • (D) of FIG. 26 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 26 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
  • FIG. 27 shows the results of Synthesis Example 27 of the carbon quantum dots synthesized by the method of the present invention.
  • the synthesis example 27 of Table 1 45 cc of ethanol, 3 g of acetylacetone, and 0.45 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 230 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 27A The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/5 is shown in FIG. 27A, and the absorption coefficient at 0.2 nm is 0.233. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.16.
  • the fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 27B and 27C, respectively, and the color coordinates of fluorescence are (0.1711, 0.1608) and (0.1857, 0.2573), respectively.
  • Figure 27 is a test tube picture containing the synthesized solution. Photograph (e) of FIG.
  • FIG. 28 shows the results of Synthesis Example 28 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 28 of Table 2 45 cc of ethanol, 3 g of acetylacetone, and 0.45 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 280 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 28 (a) The UV-Vis absorption spectrum of the diluted solution of the synthetic solution at 1/15 ratio is shown in FIG. 28 (a), and the absorption coefficient at 500 nm is 0.0875. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.31. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 28B and 28C, respectively, and the color coordinates of fluorescence are (0.1809, 0.1794) and (0.2035, 0.3331), respectively.
  • Figure 28 (d) is a test tube picture containing the synthesized solution. Photograph (e) of FIG. 28 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
  • synthesis example 29 is a summary of the characteristics of the synthesis example 29 of the carbon quantum dot synthesized by the method of the present invention, in the case of the synthesis example 29 of Table 2, ethanol 37.5cc, acetylacetone 3g, 1g nitric acid were mixed and placed in a high pressure reactor The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 29 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/36 is shown in FIG. 29 (a), and the absorption coefficient at 500 nm is 0.173. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 6.24. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 29B and 29C, respectively, and the color coordinates of fluorescence are (0.1808, 0.1770) and (0.1978, 0.2777), respectively.
  • (D) of FIG. 29 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 29 is a photo of fluorescence emitted by ultraviolet LED (380 nm) emitted from the bottom of a glass bottle containing a solution diluted at 1/36 ratio. Is (f) of FIG.
  • Synthesis Example 30 is a summary of the characteristics of Synthesis Example 30 of the carbon quantum dot synthesized by the method of the present invention, in the case of Synthesis Example 30 of Table 2, 20cc of ethanol, 9g of acetylacetone, 3g of nitric acid were mixed and placed in a high pressure reactor 250 The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 30 The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a ratio of 1/500 is shown in FIG. 30 (a), and the absorption coefficient at 500 nm is 0.117. In terms of dilution ratio, the absorption coefficient of permeate is 58.6. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 30B and 30C, respectively, and the color coordinates of fluorescence are (0.1973, 0.2186) and (0.2219, 0.3130), respectively.
  • D of FIG. 30 is a photograph of a test tube containing the synthesized solution. Photograph (e) of FIG.
  • Synthesis Example 31 is a summary of the characteristics of Synthesis Example 31 of the carbon quantum dot synthesized by the method of the present invention, in the case of Synthesis Example 31 of Table 1, 20cc of ethanol, 15g of acetylacetone, 5g of nitric acid were mixed into a high pressure reactor 250 The reaction was maintained at 20 ° C. for 20 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 31 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a 1/200 ratio is shown in FIG. 31 (a), and the absorption coefficient at 0.3 nm is 0.376. In terms of the diluted ratio, the absorption coefficient of the permeate is 75.1. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 31B and 31C, respectively, and the color coordinates of fluorescence are (0.1870, 0.1943) and (0.2086, 0.2942), respectively.
  • (D) of FIG. 31 is a photograph of a test tube containing a synthesized solution. Photograph (e) of FIG. 31 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/200. Is Fig. 31 (f).
  • synthesis example 32 is a summary of the characteristics of the synthesis example 32 of the carbon quantum dots synthesized by the method of the present invention, in the case of the synthesis example 32 of Table 2, ethanol 45cc, 3g citric acid, 0.45g nitric acid was mixed and put into a high pressure reactor 250 The reaction was maintained at 35 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 32 (a), the absorption coefficient is 0.345 at 500nm.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 32B and 32C, respectively, and the color coordinates of fluorescence are (0.1809, 0.1811) and (0.1949, 0.2645), respectively.
  • (D) of FIG. 32 is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 32 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 32 (f). to be.
  • FIG. 33 shows the results of Synthesis Example 33 of the carbon quantum dots synthesized by the method of the present invention.
  • ethanol 40cc, vitamin C 3g, and nitric acid 1g were mixed and placed in a high pressure reactor. The reaction was maintained at 35 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 33 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/100 is shown in FIG. 33 (a), and the absorption coefficient at 500 nm is 0.256. According to the diluted ratio, the absorption coefficient of the synthetic solution is 25.6.
  • the fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 33B and 33C, respectively, and the color coordinates of fluorescence are (0.1931, 0.2127) and (0.2143, 0.3034), respectively.
  • 33 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 33 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the 1/100 ratio. Is (f) of FIG.
  • FIG. 34 shows the results of Synthesis Example 34 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 34 of Table 2 20 cc of ethanol, 9 g of vitamin C, and 3.24 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 34 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at 1/100 ratio is shown in FIG. 34 (a), and the absorption coefficient at 0.3 nm is 0.363. According to the diluted ratio, the absorption coefficient of permeate solution is 36.3. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 34B and 34C, respectively, and the color coordinates of fluorescence are (0.1795, 0.1834) and (0.1997, 0.2888), respectively.
  • 34 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 34 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the 1/100 ratio. Is Fig. 34 (f).
  • FIG. 35 shows the results of Synthesis Example 35 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 35 of Table 2 37.5 cc of ethanol, 3 g of glutamine, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 35 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a ratio of 1/31 is shown in FIG. 35 (a), and the absorption coefficient at 0.2 nm is 0.210. According to the diluted ratio, the absorption coefficient of the permeate solution is 6.51. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 35B and 35C, respectively, and the color coordinates of fluorescence are (0.1816, 0.1790) and (0.1994, 0.2777), respectively.
  • 35 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 35 shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/31. Is (f) of FIG.
  • Synthesis Example 36 shows the results of Synthesis Example 36 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 36 of Table 2 37.5 cc of ethanol, 1 g of glucose, and 3 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 36 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/81 is shown in FIG. 36 (a), and the absorption coefficient at 0.3 nm is 0.320. According to the diluted ratio, the absorption coefficient of the synthetic solution is 25.9. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 36B and 36C, respectively, and the color coordinates of fluorescence are (0.1931, 0.2300) and (0.2079, 0.3019), respectively. 36 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG.
  • Synthesis Example 37 shows the properties of Synthesis Example 37 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 36 of Table 2 37.5 cc of ethanol, 1 g of white sugar, and 3 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 37 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a ratio of 1/81 is shown in FIG. 37 (a), and the absorption coefficient at 0.3 nm is 0.339. According to the diluted ratio, the absorption coefficient of the permeate solution is 27.5. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 37B and 37C, respectively, and the color coordinates of fluorescence are (0.1958, 0.2317) and (0.2206, 0.3368), respectively.
  • 37 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 37 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/81. Is (f) of FIG.
  • Synthesis Example 38 shows the characteristics of Synthesis Example 38 of the carbon quantum dots synthesized by the method of the present invention.
  • 20 cc of ethanol, 15 g of white sugar, and 5 g of nitric acid were mixed and placed in a high pressure reactor.
  • the reaction was maintained at 30 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • the UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/81 is shown in FIG. 38 (a), and the absorption coefficient at 0.2 nm is 0.248. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 20.1. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 38 (b) and 38 (c), respectively, and the color coordinates of fluorescence are (0.1916, 0.2133) and (0.2232, 0.3121), respectively. 38 (d) is a test tube photograph containing the synthesized solution.
  • the photo of fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/81 is (e) of FIG. 38, and the photo was taken by fluorescence by the blue LED (460 nm). Is (f) of FIG.
  • FIG. 39 shows the results of Synthesis Example 39 of the carbon quantum dots synthesized by the method of the present invention.
  • the reaction was maintained at 245 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 39 (a) The UV-Vis absorption spectrum of the diluted solution of the synthesis solution at 1/111 ratio is shown in FIG. 39 (a), and the absorption coefficient at 0.2 nm is 0.201. Converted according to the diluted ratio, the absorption coefficient of the synthetic solution is 22.4. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 39B and 39C, respectively, and the color coordinates of fluorescence are (0.2146, 0.2467) and (0.2505, 0.3324), respectively.
  • 39 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 39 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/111. Is (f) of FIG.
  • Synthesis Example 40 shows the characteristics of Synthesis Example 40 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 40 of Table 2 37.5 cc of ethanol, 3 g of tartaric acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 40 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a 1/11 ratio is shown in FIG. 40 (a), and the absorption coefficient at 0.3 nm is 0.391. According to the diluted ratio, the absorption coefficient of the permeate is 4.30. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 40B and 40C, respectively, and the color coordinates of fluorescence are (0.1945, 0.2139) and (0.2187, 0.2951), respectively.
  • 40 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 40 shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/11. Is (f) of FIG.
  • FIG. 41 shows the characteristics of Synthesis Example 41 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 41 of Table 2 45 cc of ethanol, 3 g of urea, and 3 g of nitric acid were mixed and placed in a high pressure reactor at 245 ° C. The reaction was maintained for 30 hours at. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the solution diluted with the synthesis solution at 1/13 ratio is shown in Figure 41 (a), the absorption coefficient is 0.128 at 500nm. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.66. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 41B and 41C, respectively, and the color coordinates of fluorescence are (0.1749, 0.1496) and (0.0.2060, 0.2565), respectively.
  • 41 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 41 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/13. Is Fig. 41 (f).
  • FIG. 42 shows the results of Synthesis Example 42 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 42 of Table 2 37.5 cc of ethanol, 3 g of acetone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 42 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/10 is shown in FIG. 42 (a), and the absorption coefficient at 500 nm is 0.156. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.56. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 42B and 42C, respectively, and the color coordinates of fluorescence are (0.1692, 0.1439) and (0.0.1884, 0.2437), respectively. 42 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 42 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/10. Is (f) of FIG.
  • Synthesis Example 43 shows the characteristics of Synthesis Example 43 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 43 of Table 2 37.5 cc of ethanol, 3 g of ethylene glycol, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • the UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a ratio of 1/15 is shown in FIG. 43 (a), and the absorption coefficient at 0.25 nm is 0.252. According to the diluted ratio, the absorption coefficient of the permeate solution is 3.78.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 43B and 43C, respectively, and the color coordinates of fluorescence are (0.1951, 0.2402) and (0.2221, 0.3180), respectively.
  • 43 (d) is a test tube photograph containing the synthesized solution.
  • Photograph (e) of Figure 43 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing a solution diluted at a ratio of 1/15, and was taken by fluorescence by blue LED (460 nm).
  • FIG. 44 shows the results of Synthesis Example 44 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 44 of Table 2 37.5 cc of ethanol, 3 g of starch, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 44 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at 1/56 ratio is shown in FIG. 44 (a), and the absorption coefficient at 0.6 nm is 0.699. According to the diluted ratio, the absorption coefficient of permeate solution is 39.1. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 44B and 44C, respectively, and the color coordinates of fluorescence are (0.2084, 0.2464) and (0.2402, 0.3322), respectively. 44 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 44 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/56. Is (f) of FIG.
  • FIG. 45 shows the results of Synthesis Example 45 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 45 of Table 2 45 cc of ethanol, 3 g of oleic acid, and 0.16 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 45 (a), the absorption coefficient is 0.650 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 45B and 45C, respectively, and the color coordinates of fluorescence are (0.1801, 0.1885) and (0.1951, 2838), respectively.
  • 45 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution is shown in Figure 45 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 45 (f). to be.
  • FIG. 46 shows the results of Synthesis Example 46 of the carbon quantum dots synthesized by the method of the present invention.
  • the reaction was carried out while maintaining at 250 °C for 35 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • the UV-Vis absorption spectrum of the solution diluted by the 1/20 ratio of the synthetic solution is shown in FIG. 46 (a), and the absorption coefficient at 0.2 nm is 0.214. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 4.27. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 46B and 46C, respectively, and the color coordinates of fluorescence are (0.1778, 0.1724) and (0.1956, 0.2712), respectively. 46 (d) is a test tube photograph containing the synthesized solution.
  • FIG. 47 is a result of synthesizing the properties of Synthesis Example 47 of the carbon quantum dots synthesized by the method of the present invention. And reacted while maintaining at 250 °C for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • the UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/36 is shown in FIG. 47 (a), and the absorption coefficient at 500 nm is 0.147. Converted according to the diluted ratio, the absorption coefficient of the synthetic solution is 5.28. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 47B and 47C, respectively, and the color coordinates of fluorescence are (0.1796, 0.1714) and (0.2039, 0.2648), respectively. 47 is a test tube photograph containing the synthesized solution.
  • FIG. 48 shows the results of Synthesis Example 48 of the carbon quantum dots synthesized by the method of the present invention.
  • synthesis example 48 of Table 2 37.5 cc of chlorobenzene, 3 g of acetylacetone, and 1 g of nitric acid were mixed to the high pressure reactor. The reaction was carried out while maintaining at 245 °C for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 48 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a 1/46 ratio is shown in FIG. 48 (a), and the absorption coefficient at 0.4 nm is 0.446. According to the diluted ratio, the absorption coefficient of the permeate solution is 20.5. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 48B and 48C, respectively, and the color coordinates of fluorescence are (0.1893, 0.2005) and (0.2165, 0.2884), respectively.
  • 48 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 48 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the diluted solution at 1/46 ratio. Is (f) of FIG.
  • FIG. 49 shows the results of Synthesis Example 49 of the carbon quantum dots synthesized by the method of the present invention.
  • synthesis example 49 of Table 2 37.5 cc of ethanol, 3 g of glucose, and 1 g of sulfuric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 49 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a ratio of 1/36 is shown in FIG. 49 (a), and the absorption coefficient at 500 nm is 0.039. According to the diluted ratio, the absorption coefficient of the permeate is 1.42. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 49B and 49C, respectively, and the color coordinates of fluorescence are (0.1795, 0.1848) and (0.2148, 0.2917), respectively. 49 (d) is a test tube photograph containing the synthesized solution.
  • FIG. 50 shows the properties of Synthesis Example 50 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 50 of Table 2 ethanol 40 cc, white sugar 1 g, potassium borohydride (KBH 4 ) 1 g
  • the mixture was put into a high pressure reactor and reacted while maintaining at 245 °C for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction.
  • the high pressure reactor was naturally cooled.
  • the composite was filtered through a membrane filter with a pore size of 0.2 ⁇ m to separate black permeate.
  • FIG. 50 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a 1/36 ratio is shown in FIG. 50 (a), and the absorption coefficient at 0.2 nm is 0.294. According to the diluted ratio, the absorption coefficient of the permeate is 10.6. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 50B and 50C, respectively, and the color coordinates of fluorescence are (0.2051, 0.2260) and (0.2416, 0.3150), respectively.
  • 50 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 50 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at 1/36 ratio. Is (f) of FIG.
  • Fig. 51 shows the results of Synthesis Example 51 of the carbon quantum dots synthesized by the method of the present invention.
  • Synthesis Example 51 of Table 2 ethanol 40cc, acetylacetone 3g, potassium borohydride (KBH 4 ) 1g
  • the mixture was put into a high pressure reactor and reacted while maintaining at 245 °C for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • the UV-Vis absorption spectrum of the diluted solution of the synthesis solution at 1/13 ratio is shown in FIG. 51 (a), and the absorption coefficient at 0.3 nm is 0.303. According to the diluted ratio, the absorption coefficient of the synthetic solution is 3.94.
  • Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 51B and 51C, respectively, and the color coordinates of fluorescence are (0.2286, 0.2540) and (0.2667, 0.3235), respectively.
  • 51 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG.
  • Synthesis Example 52 is a result of synthesizing the properties of Synthesis Example 52 of the carbon quantum dot synthesized by the method of the present invention; in the Synthesis Example 52 of Table 2, 37.5 cc of ethanol, 3 g of benzene, and potassium borohydride (KBH 4 ) 0.69
  • the mixture was mixed and placed in a high pressure reactor to react at 245 ° C. for 30 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • FIG. 52 (a) The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a 1/11 ratio is shown in FIG. 52 (a), and the absorption coefficient at 500 nm is 0.142. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.56. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIG. 52 (c), respectively, and the color coordinates of fluorescence are (0.1853, 0.1906) and (0.2199, 0.2992), respectively. (D) of FIG. 52 is a test tube photograph containing the synthesized solution.
  • Photograph (e) of Figure 52 shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/11 is a photo taken by the blue LED (460 nm).
  • FIG. 53 shows the results of Synthesis Example 53 of the carbon quantum dots synthesized by the method of the present invention.
  • the synthesis example 53 of Table 2 45 cc of ethanol, 3 g of acetylacetone, and 0.3 g of Fe 2 O 3 nanoparticles were mixed.
  • the reaction mixture was placed in a high pressure reactor and maintained at 250 ° C. for 35 hours.
  • the mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 53 (a), the absorption coefficient is 0.047 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 53B and 53C, respectively, and the color coordinates of fluorescence are (0.1781, 0.1751) and (0.2045, 0.2750), respectively.
  • Figure 53 (d) is a test tube picture containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution is shown in Figure 53 (e), the fluorescence emitted by the blue LED (460 nm) is shown in Figure 53 (f). to be.
  • FIG. 54 shows the results of Synthesis Example 54 of the carbon quantum dots synthesized by the method of the present invention.
  • the synthesis example 54 of Table 2 42.5 cc of ethanol, 3 g of acetylacetone, and 0.5 cc of acetic acid were mixed. The reaction was carried out while maintaining at 250 °C for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
  • UV-Vis absorption spectrum of the synthetic solution is shown in Figure 54 (a), the absorption coefficient is 0.0173 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 54B and 54C, respectively, and the color coordinates of fluorescence are (0.1745, 0.1637) and (0.1988, 0.2505), respectively.
  • 54 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution is shown in Figure 54 (e), the fluorescence emitted by the blue LED (460 nm) is shown in Figure 54 (f). to be.

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Abstract

A carbon quantum dot is a carbon nanoparticle showing quantum effects, which is chemically stable and has no biological toxicity, and thus can substitute for a semiconductor quantum dot. According to the present invention, a method for synthesizing carbon quantum dots by creating a condition similar to a natural environment where coal and graphite are produced has been developed, and it is possible to synthesize carbon quantum dots by degrading any type of organic matter using a promoter. Further, the present invention suggests a method for mass synthesis of carbon quantum dots by improving the synthesis efficiency of carbon quantum dots several tens of times using an organic solvent. By using the method of the present invention, the sizes of the carbon quantum dots can be easily adjusted and the synthesized carbon quantum dots show excellent fluorescence characteristics and high water dispersibility.

Description

탄소양자점의 제조방법Manufacturing method of carbon quantum dot
본 발명은 탄소양자점 제조방법과 이에 의해 제조된 탄소양자점에 관한 것으로서, 더욱 상세하게는 설탕, 전분, 비타민C, 글루코스, 주석산, 구연산, 올레익산, 글루타민, 글루타민산, 요소, 벤젠, 아세틸아세톤, 아세토페논, 초산 등 유기화합물과 산화제, 환원제, 촉매 등 반응촉진제를 물, 메탄올, 에탄올, 2-프로판올, 과산화수소, n-프로판올, 클로로벤젠 등의 용매에 혼합하고 밀폐용기에 넣어 230℃ 이상의 온도에서 반응하여 탄소양자점을 제조할 수 있도록 하는 탄소양자점 제조방법 및 이에 의해 제조된 탄소양자점에 관한 것이다.The present invention relates to a carbon quantum dot production method and a carbon quantum dot produced thereby, more specifically Organic compounds such as sugar, starch, vitamin C, glucose, tartaric acid, citric acid, oleic acid, glutamine, glutamic acid, urea, benzene, acetylacetone, acetophenone and acetic acid, and reaction accelerators such as oxidizing agents, reducing agents, and catalysts include water, methanol, ethanol, Carbon quantum dot production method and carbon quantum dot produced by mixing in a solvent such as 2-propanol, hydrogen peroxide, n-propanol, chlorobenzene and reacted at a temperature of 230 ℃ or more to produce a carbon quantum dot will be.
고체상태의 탄소는 결정구조에 따라 다이아몬드, 흑연(그래파이트)와 비결정형인 석탄이 자연에 존재한다. 나노크기의 탄소결정으로는 탄소나노튜브(CNT), 퓰레린, 그래핀 등이 잘 알려져 있다. 탄소양자점은 순수한 탄소 결정은 아니나 나노크기의 탄소화합물 중에서 양자효과의 물리적 성질을 가지고 있으며, 다양한 분야에서 응용가능성이 있음이 잘 알려져 있다.In solid carbon, diamond, graphite (graphite) and amorphous coal exist in nature depending on the crystal structure. As nano-sized carbon crystals, carbon nanotubes (CNT), purerine, graphene and the like are well known. Carbon quantum dots are not pure carbon crystals, but have physical properties of quantum effects among nano-sized carbon compounds, and are well known for their applicability in various fields.
탄소양자점(carbon quantum dot, CQD)은 흑연 나노입자를 기반으로 하고, 표면에 에폭사이드, 하이드록실기, 카르복실기 등 화학기가 결합되어 있는 구조로 알려져 있으며, 탄소나노입자(carbon nanoparticle), 그래핀옥사이드 나노입자로도 불리운다. 탄소양자점의 주성분은 탄소(흑연나노입자)이며, 양자점의 특성을 가지고 있으므로 탄소양자점이라 한다. 탄소양자점의 크기는 수 nm이다. 입자크기에 따라 다른 색깔을 띄고, 입자 크기에 따라 형광파장이 달라지는 전형적인 양자점의 특성을 가지고 있다. 또한 여기광의 파장에 따라 다른 파장의 형광을 방출하며, 물에 쉽게 혼합(용해)된다. CdSe 등 독성이 강한 반도체 양자점과 달리 탄소양자점은 생체 친화적인 탄소화합물이므로 인체에 주입할 수 있는 센서 등에 응용할 수 있다. Carbon quantum dot (CQD) is based on graphite nanoparticles, and is known to have a structure in which chemical groups such as epoxides, hydroxyl groups, and carboxyl groups are bonded to the surface, and carbon nanoparticles and graphene oxides. Also called nanoparticles. The main component of the carbon quantum dot is carbon (graphite nanoparticles), and it is called carbon quantum dot because it has the characteristics of quantum dots. The size of the carbon quantum dots is several nm. It has the characteristics of a typical quantum dot that has a different color depending on the particle size and the fluorescence wavelength varies depending on the particle size. In addition, it emits fluorescence of different wavelengths depending on the wavelength of the excitation light, and is easily mixed (dissolved) in water. Unlike semiconductor quantum dots, such as CdSe, which are highly toxic, carbon quantum dots are bio-friendly carbon compounds and can be applied to sensors that can be injected into the human body.
탄소양자점은 많은 분야에 응용가능성이 있음에도 불구하고 대량으로 생산할 수 있는 화학적 합성방법이 잘 알려져 있지 않다. 흑연을 한 층씩 벗겨내면 그래핀이 되며, 흑연을 나노입자로 분쇄하면 탄소양자점이 된다. 흑연을 박리하거나 분쇄하여 탄소양자점을 만드는 방법을 탑-다운(top-down) 방법이라 하며, 탄소양자점을 합성하는 가장 일반적인 방법이다. Although carbon quantum dots have applicability in many fields, chemical synthesis methods for mass production are not well known. Stripping graphite one by one produces graphene, and grinding graphite into nanoparticles results in carbon quantum dots. The method of making carbon quantum dots by peeling or pulverizing graphite is called a top-down method and is the most common method of synthesizing carbon quantum dots.
흑연을 화학적으로 분해하면 탄소양자점이 되며, 레이저 어블레이션(laser ablation), 전기산화(electrooxdizing) 등의 방법을 사용하기도 한다. 그러나 탑-다운(top-down) 방법으로 탄소양자점을 제작하는 방법은 생산효율이 낮으며, 입자의 크기, 표면상태 등을 인위적으로 조절하는 것이 매우 어려운 문제점이 있다.Chemically decomposing graphite becomes a carbon quantum point, and laser ablation and electrooxdizing may be used. However, the method of manufacturing carbon quantum dots by the top-down method has low production efficiency, and it is very difficult to artificially control the size, surface state, and the like of the particles.
따라서, 탄소양자점을 합성하는 기존의 방법이 지닌 여러 가지 단점을 극복할 수 있는 보튼-업(bottom-up) 방법의 새로운 합성기술이 필요하다. Therefore, there is a need for a new synthesis technology of the bottom-up method that can overcome various disadvantages of the existing method of synthesizing carbon quantum dots.
상기한 바와 같은 탄소양자점을 합성하는 기존의 방법이 지닌 여러 가지 문제점을 극복하기 위한 본 발명은 새로운 합성기술인 바텀-업(bottom-up) 방법, 즉 유기화합물을 분해·탄화·결정화하는 반응을 통하여 탄소양자점을 제조할 수 있도록 하는데 그 목적이 있다.The present invention for overcoming various problems of the existing method for synthesizing carbon quantum dots as described above is a new synthesis technology, a bottom-up method, that is, through the reaction of decomposition, carbonization, and crystallization of organic compounds. The purpose is to enable the production of carbon quantum dots.
즉, 본 발명은 모든 종류의 유기물로부터 탄소양자점을 합성할 수 있으며, 생성물의 크기, 효율을 조절할 수 있고 대량으로 합성할 수 있도록 하는데 그 목적이 있다.That is, the present invention can synthesize a carbon quantum dot from all kinds of organic materials, it is possible to control the size, efficiency of the product and to synthesize in large quantities.
상기한 바와 같은 목적은 유기 화합물, 용매, 촉진제를 혼합하여 용액을 만드는 단계; 및 상기 용액을 가열하는 단계를 포함하여 구성되는 탄소양자점 제조방법에 의해 달성된다.The object as described above is to prepare a solution by mixing an organic compound, a solvent, an accelerator; And it is achieved by the carbon quantum dot manufacturing method comprising the step of heating the solution.
또한, 본 발명의 하나의 측면에 의하면, 상기 촉진제가 산화제, 환원제, 촉매 중 어느 하나 이상인 것을 특징으로 한다.In addition, according to one aspect of the invention, the accelerator is characterized in that any one or more of an oxidizing agent, a reducing agent, a catalyst.
또한, 본 발명의 다른 하나의 측면에 의하면, 상기 산화제가 질산, 황산, 과산화수소 중 어느 하나 이상인 것을 특징으로 한다.In addition, according to another aspect of the present invention, the oxidizing agent is characterized in that any one or more of nitric acid, sulfuric acid, hydrogen peroxide.
또한, 본 발명의 또 다른 하나의 측면에 의하면, 상기 환원제가 칼륨보로하이드라이드인 것을 특징으로 한다.In addition, according to another aspect of the present invention, the reducing agent is characterized in that potassium borohydride.
또한, 본 발명의 또 다른 하나의 측면에 의하면, 상기 촉매가 Fe2O3 나노입자인 것을 특징으로 한다.In addition, according to another aspect of the present invention, the catalyst is characterized in that the Fe 2 O 3 nanoparticles.
또한, 본 발명의 또 다른 하나의 측면에 의하면, 상기 용매가 물, 메탄올, 에탄올, 2-프로판올, n- 프로판올, 과산화수소, 클로로벤젠 중 어느 하나 이상인 것을 특징으로 한다.Further, according to another aspect of the present invention, the solvent is characterized in that any one or more of water, methanol, ethanol, 2-propanol, n-propanol, hydrogen peroxide, chlorobenzene.
또한, 본 발명의 또 다른 하나의 측면에 의하면, 상기 유기화합물이 설탕, 전분, 비타민 C, 글루코스, 주석산, 구연산, 올레익산, 글루타민, 글루타민산, 요소, 벤젠, 아세틸아세톤, 아세토페논, 초산 중 어느 하나 이상인 것을 특징으로 한다.According to another aspect of the present invention, the organic compound is any one of sugar, starch, vitamin C, glucose, tartaric acid, citric acid, oleic acid, glutamine, glutamic acid, urea, benzene, acetylacetone, acetophenone, acetic acid It is characterized by one or more.
또한, 본 발명의 또 다른 하나의 측면에 의하면, 상기 용액은 220 내지 290 ℃ 이상의 온도로 가열하는 것을 특징으로 한다.In addition, according to another aspect of the present invention, the solution is characterized in that the heating to a temperature of 220 to 290 ℃ or more.
따라서, 본 발명에 의하면, 본 발명은 탄소양자점을 합성하기 위한 방법으로 유기물에서 석탄이나 흑연이 생성되는 자연적인 환경을 차용한 새로운 합성방법을 도입하여 기존의 방법에 비해서 효율과 생산성이 높으며, 탄소양자점을 대량으로 생산할 수 있다.Therefore, according to the present invention, the present invention is a method for synthesizing carbon quantum dots, by introducing a new synthetic method borrowing a natural environment in which coal or graphite is generated from organic matter, the efficiency and productivity are higher than the existing method, carbon Quantum dots can be produced in large quantities.
또한, 본 발명은 용매, 온도 등 합성조건을 단순히 바꾸면 탄소양자점의 크기, 합성효율을 조절할 수 있다.In addition, the present invention can control the size, synthesis efficiency of the carbon quantum dot simply by changing the synthesis conditions, such as solvent, temperature.
또한, 본 발명은 거의 모든 종류의 유기물로부터 탄소양자점을 합성할 수 있으며, 밀가루, 전분, 설탕 등 저렴한 식품화합물로부터 합성할 수 있다.In addition, the present invention can synthesize carbon quantum dots from almost all kinds of organic matter, and can be synthesized from inexpensive food compounds such as flour, starch, sugar and the like.
또한, 본 발명은 용매, 촉진제, 유기물만으로 탄소양자점을 합성하므로 합성된 생성물로부터 복잡한 정제과정을 거치지 않고 탄소양자점을 얻을 수 있다.In addition, the present invention synthesizes a carbon quantum dot only with a solvent, an accelerator, and an organic material, thereby obtaining a carbon quantum dot from a synthesized product without undergoing a complicated purification process.
또한, 본 발명은 결정화과정을 포함하고 있으며, 결정화과정에서 유기물의 농도에 따라 생성물의 크기를 조절할 수 있으며, 유기물의 농도가 높으면 큰 입자가 생성되며, 낮은 농도에서는 작은 입자가 생성된다. In addition, the present invention includes a crystallization process, the size of the product can be adjusted according to the concentration of the organic matter in the crystallization process, the higher the concentration of the organic matter is produced, the smaller particles are produced at a lower concentration.
또한, 본 발명은 유기화합물을 분해하여 탄소양자점을 합성하는 보튼-업(bottom-up) 방법으로 탄소양자점을 합성함으로써 효율성, 경제성이 높아지고 입자크기의 조절이 용이하며 탄소양자점의 입자크기가 균일하며 이에 따른 물리적 성질이 균일하다는 특징이 있다.In addition, the present invention synthesizes carbon quantum dots by a bottom-up method of decomposing organic compounds to synthesize carbon quantum dots, thereby increasing efficiency and economic efficiency, easily controlling particle sizes, and uniform particle size of carbon quantum dots. As a result, the physical properties are uniform.
도 1 내지 도 54는 본 발명의 방법으로 합성한 탄소양자점의 여러 실시예의 결과특성을 보여주는 도면이다.1 to 54 show results of various embodiments of carbon quantum dots synthesized by the method of the present invention.
이하, 본 발명의 바람직한 실시예를 첨부도면을 참조하여 상세히 설명하기로 한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
가. 자연에서 탄소 동소체의 생성end. Generation of Carbon Allotropes in Nature
석탄, 흑연, 다이아몬드는 탄소 동소체이다. 다이아몬드는 고온과 고압의 조건에서 만들어지는 탄소결정체이며, 화성암층에서 주로 발견된다. 흑연은 변성암층에서 주로 발견되며 화성암층에서도 발견되기도 한다. 무결정의 탄소인 석탄은 퇴적암층에서 주로 발견되며 식물과 동물의 유기물의 퇴적층이 산화, 탄화 반응을 거쳐서 탄소가 되는 것으로 알려져 있다. 자연에서 만들어지는 다이아몬드, 흑연, 석탄 등은 모두 압력과 온도가 일정하게 주어지는 상황에서 유기물로부터 생성된다. 압력과 온도가 낮은 퇴적층에서 무정형의 석탄이 생성되며, 압력과 온도가 중간 크기인 변성암층에서는 층상 구조의 흑연이, 고온·고압의 화성암층에서는 경도가 높은 다이아몬드가 생성된다. Coal, graphite and diamond are carbon allotrope. Diamond is a carbon crystal produced under high temperature and high pressure, and is mainly found in igneous rock layers. Graphite is mainly found in metamorphic rocks and sometimes in igneous rocks. Coal, an amorphous carbon, is found mainly in sedimentary rock layers, and it is known that the sedimentary layers of organic matter in plants and animals become carbon through oxidation and carbonization. Diamonds, graphite, and coal, all made in nature, are all produced from organic matter under constant pressure and temperature. Amorphous coal is produced in the sedimentary layers with low pressure and temperature, and graphite of layered structure is produced in the metamorphic rock layers with medium pressure and temperature, and diamonds with high hardness are produced in the high-temperature and high-pressure igneous rock layers.
나. 탄소나노입자의 결정성장I. Crystal Growth of Carbon Nanoparticles
이와 같이 탄소결정체가 만들어지는 조건을 인위적으로 조성하면 탄소물질을 제작할 수 있을 것으로 판단된다. 탄소양자점은 덩어리 결정인 흑연에 비해 결정화도가 낮고, 무결정인 석탄에 비해 결정화도가 높다. 석탄이 생성되는 환경과 흑연이 생성되는 환경의 중간 정도의 온도와 압력을 가진 환경을 조성하면 결정도가 낮은 탄소물질인 탄소양자점을 만들 수 있을 것으로 생각된다. 이러한 온도와 압력의 환경에서 유기물이 분해하고, 탄화하여 나노입자로 결정화하면 탄소양자점이 생성된다. In this way, it is judged that artificially configuring the conditions under which carbon crystals are made can produce a carbon material. The carbon quantum point has a lower degree of crystallinity than graphite, which is a lumped crystal, and a higher degree of crystallinity than non-crystalline coal. It is thought that carbon quantum dots, which are low-crystallinity carbon materials, can be created by creating an environment with a temperature and pressure that is intermediate between that of coal and graphite. In this environment of temperature and pressure, when organic matter is decomposed, carbonized and crystallized into nanoparticles, carbon quantum dots are generated.
퇴적층과 변성암층이 생성되는 압력과 온도를 조성하기 위해서는 수열합성법(hydrothermal method)이나 이와 유사한 용매열 합성법(solvothermal method)을 사용할 수 있다. 수열합성법에서는 물이 든 밀폐된 용기를 가열하여 온도와 압력을 생성하는 합성방법이며 수정, 에머랄드, ZnO 등 단결정을 성장할 수 있다. 용매열 합성법은 알코올, 벤젠 등 유기용매가 든 밀폐용기를 가열하여 온도와 압력을 생성하여 합성하는 방법으로 유기용매가 필요한 반응에 사용된다. To establish the pressure and temperature at which the sedimentary and metamorphic rocks are formed, a hydrothermal method or a similar solvothermal method can be used. In the hydrothermal synthesis method, a closed vessel of water is heated to generate temperature and pressure, and single crystals such as quartz, emerald, and ZnO can be grown. Solvent thermal synthesis method is a method for producing a temperature and pressure by synthesizing a closed container containing an organic solvent, such as alcohol, benzene is used for the reaction that requires an organic solvent.
다. 촉진제All. accelerant
땅속이 묻힌 유기물(탄소화합물)이 서서히 분해되고 탄화되어 석탄이 생성된다. 석탄이 생성되는 자연적인 과정에서는 유기물을 분해·탄화하기 위한 열과 압력이 필요할 뿐만 아니라 오랜 시간도 필요하다. 그러나, 인위적으로 유기물을 분해하고 탄화하기 위해서는 유기물을 분해하기 위한 적극적인 방법이 필요하며 본 발명에서는 산화제, 환원제, 촉매 등을 사용하여 유기물을 분해하는 것을 촉진하였으며, 이를 촉진제라 한다. 촉진제로 사용되는 산화제에는 질산, 황산, 과산화수소, 과망간산칼륨 등이 있으며, 환원제에는 NaBH4, 칼륨보로하이드라이드(KBH4), LiAlH4, N2H4 등이 있으며, 촉매로는 백금, Pd, Ni, TiO2, Fe2O3 나노입자 등이 있다.Organic matter (carbon compounds) buried in the ground is slowly decomposed and carbonized to produce coal. The natural process of producing coal requires not only heat and pressure to decompose and carbonize organics, but also a long time. However, in order to artificially decompose and carbonize the organic matter, an active method for decomposing the organic matter is required. In the present invention, the decomposition of the organic matter is promoted using an oxidizing agent, a reducing agent, a catalyst, and the like. Oxidizers used as accelerators include nitric acid, sulfuric acid, hydrogen peroxide, potassium permanganate, and reducing agents include NaBH 4 , potassium borohydride (KBH 4 ), LiAlH 4 , and N 2 H 4 . , Ni, TiO 2 , Fe 2 O 3 nanoparticles and the like.
라. 유기물la. Organic matter
석탄, 흑연 등은 동식물의 잔해인 유기물이 분해되고 탄화되어 생성된다. 본 발명에서 탄소양자점을 합성하기 위한 출발물질로 일반적인 유기화합물을 사용한다. 식물에서 추출하는 유기물인 설탕(white sugar), 전분(starch), 비타민C(ascorbic acid), 글루코스(glucose), 주석산(tartaric acid), 구연산(citric acid), 동물지방산인 올레익산(oleic acid), 아미노산인 글루타민(glutamine), 글루타민산(glutamic acid) 및 요소(urea), 벤젠(benzene), 아세틸아세톤(acetylacetone), 아세토페논(C6H5C(O)CH3), 초산(acetic acid) 등 모든 종류의 유기물로부터 탄소양자점을 합성할 수 있다. 이들 유기물은 모두 투명한 액체이거나 흰색의 분말이다. 투명하거나 흰색의 유기물을 출발물질로 하여 본 발명의 방법으로 합성하면 탄소양자점 고유의 색을 띄는 액체가 되며, 탄소양자점의 농도가 높으면 검은색의 액체가 된다.Coal, graphite, and the like are produced by decomposing and carbonizing organic substances, which are the remains of plants and animals. In the present invention, a general organic compound is used as a starting material for synthesizing carbon quantum dots. White sugar, starch, vitamin C (ascorbic acid), glucose, tartaric acid, citric acid, and animal fatty acids oleic acid , Amino acids glutamine, glutamic acid and urea, benzene, acetylacetone, acetophenone (C 6 H 5 C (O) CH 3 ), acetic acid Carbon quantum dots can be synthesized from all kinds of organic materials. All of these organics are clear liquids or white powders. When synthesized by the method of the present invention using a transparent or white organic material as a starting material, a liquid having a color unique to carbon quantum dots becomes a black liquid when the concentration of carbon quantum dots is high.
마. 용매hemp. menstruum
용매열(solvothemal) 결정성장에서는 용매의 극성에 따라 결정성장의 속도와 형태를 조절하는 것이 가능하다. 본 발명에서도 용매의 유전상수에 따라 탄소결정의 형태를 조절하였다. 극성이 큰 용매인 물을 사용하면 낮은 농도의 탄소양자점을 합성하기에 용이하다. 용매의 극성이 낮으면 높은 농도의 탄소양자점을 합성할 수 있어 합성의 효율을 높일 수 있다. 본 발명에서는 물, 메탄올(methyl alcohol), 에탄올(ethyl alcohol), 2-프로판올(isopropyl alcohol), n-프로판올 (n-propyl alcohol), 과산화수소(hydrogen peroxide), 클로로벤젠(chlorobenzene) 등 용매를 사용하여 탄소양자점을 합성하였다.In solvent thermal crystal growth, it is possible to control the rate and form of crystal growth according to the polarity of the solvent. In the present invention, the shape of the carbon crystals was adjusted according to the dielectric constant of the solvent. Water, a highly polar solvent, is easy to synthesize low concentrations of carbon quantum dots. When the polarity of the solvent is low, a high concentration of carbon quantum dots can be synthesized, thereby increasing the efficiency of the synthesis. In the present invention, solvents such as water, methanol (methyl alcohol), ethanol (ethyl alcohol), 2-propanol (isopropyl alcohol), n-propanol (n-propyl alcohol), hydrogen peroxide, chlorobenzene, and the like are used. To synthesize a carbon quantum dot.
본 발명에서는 유기물을 분해·탄화·결정화하여 탄소양자점을 합성하는 방법을 개발하였으며, 이 방법의 흐름도는 아래와 같다. 본 발명의 방법을 통하면 모든 종류의 유기물을 분해하여 탄소양자점을 합성할 수 있다. 또한, 탄소양자점의 합성효율이 높으며, 크기를 조절하는 것이 가능한 장점이 있다. In the present invention, a method of synthesizing carbon quantum dots by decomposing, carbonizing, and crystallizing an organic substance was developed. The flowchart of the method is as follows. Through the method of the present invention, carbon quantum dots can be synthesized by decomposing all kinds of organic substances. In addition, the synthesis efficiency of the carbon quantum dot is high, there is an advantage that can be adjusted in size.
석탄, 흑연, 다이아몬드 등 탄소동종체는 지각속에서 열과 압력을 받아 생성된다. 석탄과 흑연의 원료는 유기물이며, 지각 속에 묻힌 유기화합물이 분해되고, 탄화, 결정화 과정을 거쳐서 탄소동종체가 생성된다. 본 발명에서는 이러한 탄소동종체가 자연적으로 생성되는 원리를 차용하였으며, 탄소양자점을 합성하는 새로운 합성방법을 개발하였다. 이 합성과정에는 밀폐된 용기에서 용해되어 있는 유기화합물을 촉진제를 사용하여 분해하고, 분해된 유기화합물에 압력과 열을 가하여 탄화하고, 결정화하는 과정으로 구성되어 있다. Carbon homogenates such as coal, graphite, and diamond are produced under heat and pressure in the earth's crust. The raw materials of coal and graphite are organic substances, and organic compounds buried in the earth's crust are decomposed, and carbon isomers are produced through carbonization and crystallization. The present invention borrows the principle that such carbon homogenates are naturally produced, and has developed a new synthesis method for synthesizing carbon quantum dots. This synthesis process consists of decomposing organic compounds dissolved in sealed containers using accelerators, carbonizing and crystallizing the decomposed organic compounds by applying pressure and heat.
이 합성방법에는 (i) 고온과 고압의 상태를 유지할 수 있는 고압반응기를 사용하였으며, (ii) 여러 가지 유기화합물을 원료로 하고, (iii) 유기물을 분해하고 반응을 촉진하기 위한 촉진제와 (iv) 반응을 조절하기 위한 용매를 사용하였다. 본 발명의 합성방법을 사용하면 모든 종류의 유기물을 전구체로 하여 탄소양자점을 합성하는 것이 가능하다.This synthesis method uses (i) a high pressure reactor capable of maintaining high temperature and high pressure, (ii) various organic compounds as raw materials, (iii) accelerators for decomposing organic matters and promoting reactions, and (iv) Solvent was used to control the reaction. Using the synthesis method of the present invention, it is possible to synthesize carbon quantum dots using all kinds of organic substances as precursors.
(i) 본 발명의 합성에 사용한 고압반응기는 등록특허 1007694210000와 같이 내부용기와 외부용기로 구성되어 있으며, 내부용기는 화학물과 반응하지 않는 테프론으로 만들었고 압력을 유지하는 외부용기는 스테인레스강으로 제작하였다. 고압반응기에 온도조절 장치와 자석교반장치를 부착하였다. 온도조절장치를 사용하여 화학반응의 온도를 자동으로 조절하였으며, 자석교반장치를 사용하여 반응이 진행되는 동안 용액을 균질하게 유지하였다. 반응에 사용된 고압반응기는 2종류이며 각각의 내부용기의 부피는 1,200cc와 60cc이다.(i) The high pressure reactor used in the synthesis of the present invention is composed of an inner container and an outer container as in Patent No. 1007694210000, and the inner container is made of Teflon that does not react with chemicals, and the outer container for maintaining pressure is made of stainless steel. It was. A thermostat and a magnetic stirrer were attached to the high pressure reactor. The temperature of the chemical reaction was automatically controlled using a temperature controller, and the solution was kept homogeneous during the reaction using a magnetic stirrer. There are two types of high pressure reactors used in the reaction, and the volume of each inner container is 1,200cc and 60cc.
(ii) 본 발명에서는 여러 가지 유기화합물로부터 탄소양자점을 합성하였으며, 발명에서 사용한 유기화합물은 올레익산, 아세틸아세톤, 아세토페논, 초산, 아세톤, 벤젠 및 설탕, 전분, 비타민C, 글루코스, 주석산, 구연산, 글루타민, 글루타민산, 등 식품화합물 등이다. 본 발명에서의 합성방법의 가장 큰 장점은 흔히 접할 수 있는 유기화합물을 분해하고 탄화결정화함으로써 거의 모든 종류의 유기물로부터 탄소양자점을 합성할 수 있다.(ii) In the present invention, carbon quantum dots were synthesized from various organic compounds. Oleic acid, acetylacetone, acetophenone, acetic acid, acetone, benzene and sugar, starch, vitamin C, glucose, tartaric acid, citric acid, glutamine, glutamic acid, and the like. The greatest advantage of the synthesis method in the present invention is that it is possible to synthesize carbon quantum dots from almost all kinds of organic materials by decomposing and carbonizing crystallization of commonly encountered organic compounds.
(iii) 자연에서 유기화합물은 오랜 시간 동안에 걸쳐 서서히 분해된다. 그러나 본 발명에서는 산화제, 환원제, 촉매 등을 화학반응에 첨가하여 유기화합물의 분해를 촉진하였으며 탄소양자점의 합성을 용이하게 하였다. (iii) In nature, organic compounds degrade slowly over time. However, in the present invention, an oxidizing agent, a reducing agent, and a catalyst are added to the chemical reaction to promote decomposition of the organic compound and to facilitate the synthesis of carbon quantum dots.
*(iv) 본 발명에서는 물, 메탄올, 알코올, 프로판올, 클로로벤젠 등 여러 가지 용매를 사용하여 반응을 조절하였다. 물을 용매로 사용하여 합성한 경우에는 탄소양자점의 농도가 낮았다. 용매를 메탄올, 알코올, 프로판올, 클로로벤젠 등으로 하였을 때는 합성된 탄소양자점의 양이 크게 증가하였다. * (iv) In the present invention, various solvents such as water, methanol, alcohol, propanol and chlorobenzene were used to control the reaction. When water was synthesized using a solvent, the concentration of carbon quantum dots was low. When the solvent was methanol, alcohol, propanol, chlorobenzene, or the like, the amount of synthesized carbon quantum dots increased significantly.
바. 합성물의 정제bar. Purification of the Composite
본 발명의 방법으로 합성한 합성물에는 용매, 탄소양자점, 방향족 기름, 침전물 등 유기물이 포함되어 있으며 이들을 정제하여 물리·화학적 특성을 평가하였다. 탄소양자점은 물에 쉽게 용해되고 크기가 수 nm이다. 합성물에서 침전물을 제거하고 친수성의 종이필터로 여러 번 여과하면 방향성 기름 등은 필터에 의해 걸러지고 탄소양자점과 용매는 투과한다. 투과된 용액을 물로 희석하여 포어(pore) 크기가 0.1㎛인 친수성 멤브레인 필터를 통과시켜 탄소양자점 용액을 얻었다. 불순물을 제거하고 정제한 탄소양자점 용액은 균일하였으며, 상온에서 3개월이 지나도 침전이 발생하지 않는 등 물에 대한 분산성이 매우 우수하였다.Compounds synthesized by the method of the present invention include organic substances such as solvents, carbon quantum dots, aromatic oils, and precipitates, and these were purified to evaluate physical and chemical properties. Carbon quantum dots are readily soluble in water and are several nm in size. When the precipitate is removed from the composite and filtered several times with a hydrophilic paper filter, the aromatic oil is filtered by the filter, and the carbon quantum dot and the solvent are permeated. The permeated solution was diluted with water and passed through a hydrophilic membrane filter with a pore size of 0.1 μm to obtain a carbon quantum dot solution. The carbon quantum dot solution, which had been removed with impurities, was uniform, and had excellent dispersion in water such that no precipitation occurred after 3 months at room temperature.
사. 탄소양자점의 평가four. Evaluation of Carbon Quantum Points
탄소양자점에 대한 분석 방법에는 잘 알려진 바와 같이 XRD 패턴, FT-IR 흡수스펙트럼, TEM에 의한 입도 측정, 형광 특성, 광흡수 특성 등 여러 가지 방법이 있다. 탄소양자점의 가장 큰 특징은 형광을 방출하는 탄소물질이다. 본 발명에서는 하나의 합성 예에 대하여 4가지 형광 측정 결과를 나타내었다. 용액이 든 유리병(vial)의 아랫쪽에서 방출하는 형광을 촬영한 사진 2종과 형광광도계로 측정한 2개의 형광스펙트럼이다. 2개의 형광스펙트럼은 각각 365nm, 400nm의 광을 조사하여 측정하였으며, 측정된 형광스펙트럼으로부터 형광의 색좌표(CIE1931)를 계산하였다.As is well known, there are various methods for analyzing carbon quantum dots such as XRD patterns, FT-IR absorption spectra, particle size measurement by TEM, fluorescence characteristics, and light absorption characteristics. The biggest feature of carbon quantum dot is carbon material that emits fluorescence. In the present invention, four fluorescence measurements are shown for one synthesis example. Two pictures of fluorescence emitted from the bottom of the vial containing the solution and two fluorescence spectra measured with a fluorophotometer. Two fluorescence spectra were measured by irradiating light at 365 nm and 400 nm, respectively, and color coordinates (CIE1931) of fluorescence were calculated from the measured fluorescence spectra.
탄소양자점의 주 성분은 탄소이므로 가시광선의 모든 파장영역에서 빛을 흡수한다. 본 발명에서는 유기물의 종류, 양, 합성온도, 시간, 용매의 종류, 촉진제의 종류 등을 달리하여 각기 합성하였으며, 이에 따라 생성된 탄소양자점의 양과 합성효율이 다르다. 합성물에서 탄소양자점이 포함된 용액을 추출하여 투과 길이가 10mm인 큐벳(cuvette)에 담아서 300nm-700nm 영역의 광흡수 스펙트럼을 측정하였다. 측정된 광흡수 스펙트럼에서 500nm의 흡수도(absorbance)를 광학밀도(optical density, OD) 단위로 표현하여 탄소양자점의 합성효율을 상대 비교하였다. The main component of the carbon quantum dot is carbon, so it absorbs light in all wavelength ranges of visible light. In the present invention was synthesized by varying the type, amount, synthesis temperature, time of the organic matter, the type of solvent, the type of accelerator, and the like, the amount and the synthesis efficiency of the carbon quantum dot produced accordingly is different. The solution containing the carbon quantum dot was extracted from the composite and placed in a cuvette having a transmission length of 10 mm to measure light absorption spectra of 300 nm to 700 nm. The absorption efficiency of 500 nm was expressed in optical density (OD) in the measured light absorption spectrum, and the synthesis efficiency of carbon quantum dots was compared.
합성한 조건, 합성물의 흡수도는 표 1, 2와 같다. 유기물의 종류와 양, 반응촉진제, 온도 등 반응의 조건을 동일하게 유지하고, 용매를 달리하였을 때 생성되는 탄소양자점의 양은 물, 메탄올, 에탄올 순으로 증가하였다. <합성 예 2>와 같이 물을 용매로 하였을 때 흡수도는 OD가 0.185이고, <합성 예 20>에서 메탄올을 용매로 하였을 때 흡수도는 OD가 1.94, 에탄올을 용매로 합성한 <합성 예 29>의 흡수도는 OD 6.24이다. 표 1, 2에 정리된 것과 같이 에탄올에서 합성한 탄소양자점의 농도가 물을 용매로 하여 합성한 탄소양자점에 비해 수십배 큼을 알 수 있다. <합성 예 31>의 방법으로 합성한 용액 5cc를 물로 희석하여 <합성 예 2>의 용액과 같은 농도의 탄소양자점 용액 500cc를 얻었다.The synthesized conditions and the absorbance of the compound are shown in Tables 1 and 2. The type and amount of organic matter, reaction accelerator, temperature, and the like were maintained under the same conditions, and the amount of carbon quantum dots generated when the solvent was changed increased in the order of water, methanol, and ethanol. As in <Synthesis Example 2>, the water absorption was OD of 0.185 when the solvent was used. In <Synthesis Example 20>, the absorbance of the solvent was 1.94 and ethanol was synthesized as the solvent. Absorbance of> OD 6.24. As summarized in Tables 1 and 2, it can be seen that the concentration of carbon quantum dots synthesized in ethanol is several orders of magnitude higher than the carbon quantum dots synthesized using water as a solvent. 5 cc of the solution synthesized in Synthesis Example 31 was diluted with water to obtain 500 cc of carbon quantum dot solution having the same concentration as the solution of Synthesis Example 2.
보튼-업(bottom-up) 방법의 탄소양자점 합성에 관하여 보고된 연구논문들에 의하면 주로 물을 용매로 하는 수열합성법을 사용하여 합성효율이 낮았다. 그러나 본 발명에서는 메탄올, 에탄올 등 유기용매를 사용하여 탄소양자점을 합성하는 효율을 높였으며, 촉진제를 사용하여 반응을 용이하게 함으로써 거의 모든 종류의 유기물을 분해하여 탄소양자점을 대량으로 생산할 수 있는 합성방법을 개발하였다.According to the research papers reported on the carbon quantum dot synthesis of the bottom-up method, the synthesis efficiency was low mainly by using hydrothermal synthesis method using water as a solvent. However, in the present invention, the synthesis efficiency of synthesizing carbon quantum dots by using organic solvents such as methanol and ethanol has been increased, and the synthesis method can produce carbon quantum dots in large quantities by decomposing almost all kinds of organic substances by facilitating the reaction using accelerators. Developed.
아. 합성의 예Ah. Synthesis example
탄소양자점을 합성한 실시예를 정리하면, 아래의 표 1, 2와 같다. 탄소양자점을 합성하기 위하여 사용한 유기물, 반응촉진제, 용매의 종류 및 양을 나타내었으며, 반응온도와 지속시간도 나타내었다. 합성 예 중에서 용매의 양이 60cc 보다 적은 경우의 합성은 내부부피가 60cc인 고압반응기를 사용한 것이며, 용매의 양이 400cc 보다 큰 합성은 내부부피가 1200cc인 고압반응기를 사용하여 반응하였다. 또한, 반응이 완료된 용액의 흡수도를 측정하여 생성된 탄소양자점의 상대 농도를 비교하였다.Examples of synthesizing carbon quantum dots are summarized in Tables 1 and 2 below. The organic materials, reaction accelerators and solvents used for synthesizing carbon quantum dots were shown, and the reaction temperature and duration were also shown. In the synthesis example, when the amount of solvent was less than 60cc, the synthesis was carried out using a high pressure reactor with an internal volume of 60cc, and the synthesis with the amount of the solvent was greater than 400cc using a high pressure reactor with an internal volume of 1200cc. In addition, the absorbance of the solution after the reaction was measured to compare the relative concentration of the carbon quantum dot produced.
표 1
합성예 유기물/g 용매/cc 촉진제/g 온도/℃ 시간/hr 흡수도/OD　
1 acetylacetone/36 H2O/500 HNO3/12 250 30 0.194
2 acetylacetone/3 H2O/37.5 HNO3/1 250 35 0.185
3 citric acid/36 H2O/500 HNO3/12 250 30 0.939
4 citric acid/3 H2O/40 HNO3/1 250 35 0.0304
5 glucose/1 H2O/37.5 HNO3/3 245 30 0.0096
6 glucose/1.2 H2O/37.5 HNO3/2 245 30 0.117
7 sugar/1.4 H2O/37.5 HNO3/3 250 30 0.130
8 sugar/3 H2O/37.5 HNO3/1 245 30 0.564
9 starch/3 H2O/37.5 HNO3/1 250 30 0.410
10 acetic acid/3 H2O/37.5 HNO3/2 245 24 0.00475
11 tartar acid/2 H2O/37.5 HNO3/2 245 30 0.0789
12 urea/3 H2O/37.5 HNO3/1.3 245 30 0.00147
13 glutamic acid/1 H2O/37.5 HNO3/1 245 30 0.123
14 oleic acid/3 H2O/37.5 HNO3/1 250 30 0.0385
15 acetophenone/3 H2O/37.5 HNO3/1 245 30 0.111
16 acetylacetone/3 H2O2/37.5 　- 245 30 0.197
17 glucose/3 H2O/37.5 H2SO4/1 245 30 0.170
18 acetylacetone/3 H2O/37.5 KBH4/1 245 30 0.480
19 acetylacetone/36 MeOH/500 HNO3/12 250 30 3.62
20 acetylacetone/3 MeOH/ 37.5 HNO3/1 250 35 1.94
21 acetylacetone/3 H2O/20MeOH/20 HNO3/1 250 35 0.679
22 acetone/3 MeOH/37.5 HNO3/1 250 30 1.52
23 acetophenone/3 MeOH/37.5 HNO3/1 250 30 1.01
24 oleic acid/3 MeOH/37.5 HNO3/1 250 30 0.254
25 acetylacetone/36 EtOH/550 HNO3/12 250 35 5.25
26 acetylacetone/3 EtOH/45 HNO3/0.451 250 35 2.22
27 acetylacetone/3 EtOH/45 HNO3/0.452 230 35 1.16
Table 1
Synthesis Example Organic matter / g Solvent / cc Accelerator / g Temperature / ℃ Hour / hr Absorbance / OD
One acetylacetone / 36 H 2 O / 500 HNO 3/12 250 30 0.194
2 acetylacetone / 3 H 2 O / 37.5 HNO 3/1 250 35 0.185
3 citric acid / 36 H 2 O / 500 HNO 3/12 250 30 0.939
4 citric acid / 3 H 2 O / 40 HNO 3/1 250 35 0.0304
5 glucose / 1 H 2 O / 37.5 HNO 3/3 245 30 0.0096
6 glucose / 1.2 H 2 O / 37.5 HNO 3/2 245 30 0.117
7 sugar / 1.4 H 2 O / 37.5 HNO 3/3 250 30 0.130
8 sugar / 3 H 2 O / 37.5 HNO 3/1 245 30 0.564
9 starch / 3 H 2 O / 37.5 HNO 3/1 250 30 0.410
10 acetic acid / 3 H 2 O / 37.5 HNO 3/2 245 24 0.00475
11 tartar acid / 2 H 2 O / 37.5 HNO 3/2 245 30 0.0789
12 urea / 3 H 2 O / 37.5 HNO 3 /1.3 245 30 0.00147
13 glutamic acid / 1 H 2 O / 37.5 HNO 3/1 245 30 0.123
14 oleic acid / 3 H 2 O / 37.5 HNO 3/1 250 30 0.0385
15 acetophenone / 3 H 2 O / 37.5 HNO 3/1 245 30 0.111
16 acetylacetone / 3 H 2 O 2 /37.5 - 245 30 0.197
17 glucose / 3 H 2 O / 37.5 H 2 SO 4/1 245 30 0.170
18 acetylacetone / 3 H 2 O / 37.5 KBH 4/1 245 30 0.480
19 acetylacetone / 36 MeOH / 500 HNO 3/12 250 30 3.62
20 acetylacetone / 3 MeOH / 37.5 HNO 3/1 250 35 1.94
21 acetylacetone / 3 H 2 O / 20 MeOH / 20 HNO 3/1 250 35 0.679
22 acetone / 3 MeOH / 37.5 HNO 3/1 250 30 1.52
23 acetophenone / 3 MeOH / 37.5 HNO 3/1 250 30 1.01
24 oleic acid / 3 MeOH / 37.5 HNO 3/1 250 30 0.254
25 acetylacetone / 36 EtOH / 550 HNO 3/12 250 35 5.25
26 acetylacetone / 3 EtOH / 45 HNO 3 /0.451 250 35 2.22
27 acetylacetone / 3 EtOH / 45 HNO 3 /0.452 230 35 1.16
표 2
합성예 유기물/g 용매 /cc 촉진제/g 온도/℃ 시간/hr 흡수도/OD　　
28 acetylacetone/3 EtOH/53 HNO3/0.454 280 35 1.31
29 acetylacetone/3 EtOH/37.5 HNO3/1 250 35 6.24
30 acetylacetone/9 EtOH/20 HNO3/3 250 30 58.6
31 acetylacetone/15 EtOH/20 HNO3/5 250 20 75.1
32 acetylacetone/3 EtOH/45 HNO3/0.45 250 35 0.345
33 ascorbic acid/3 EtOH/40 HNO3/1 250 35 25.6
34 ascorbic acid/9 EtOH/20 HNO3/3.24 250 30 36.3
35 glutamine/3 EtOH/37.5 HNO3/1 250 30 6.51
36 glucose/1 EtOH/37.5 HNO3/3 245 30 25.9
37 sugar/1 EtOH/37.5 HNO3/3 250 30 27.5
38 sugar/15 EtOH/20 HNO3/5 245 30 20.1
39 sugar/3 EtOH/37.5 HNO3/1 245 30 22.4
40 tartar acid/3 EtOH/37.5 HNO3/1 245 30 4.30
41 urea/3 EtOH/45 HNO3/1 245 30 1.66
42 acetone/3 EtOH/37.5 HNO3/1 245 30 1.56
43 ethyleneglycole/3 EtOH/37.5 HNO3/1 245 30 3.78
44 starch/3 EtOH/37.5 HNO3/1 250 30 39.1
45 oleic acid/3 EtOH/45 HNO3/0.157 250 35 0.650
46 acetylacetone/3 2-PrOH/40 HNO3/3 250 35 4.27
47 acetylacetone/3 n-PrOH/37.5 HNO3/1 250 30 5.28
48 acetylacetone/3 chlorobenzene/37.5 HNO3/1 245 30 20.5
49 glucose/3 EtOH/37.5 H2SO4/1 245 30 1.423
50 sugar/1 EtOH/40 KBH4/1 245 30 10.6
51 acetylacetone/3 EtOH/37.5 KBH4/1 245 30 3.94
52 benzene/3 EtOH/37.5 KBH4/0.685 245 30 1.56
53 acetylacetone/3 EtOH/45 Fe2O3/0.3 250 35 0.0467
54 acetylacetone/3 EtOH/42.5 CH3COOH/ 0.5 250 35 0.0173
TABLE 2
Synthesis Example Organic matter / g Solvent / cc Accelerator / g Temperature / ℃ Hour / hr Absorbance / OD
28 acetylacetone / 3 EtOH / 53 HNO 3 /0.454 280 35 1.31
29 acetylacetone / 3 EtOH / 37.5 HNO 3/1 250 35 6.24
30 acetylacetone / 9 EtOH / 20 HNO 3/3 250 30 58.6
31 acetylacetone / 15 EtOH / 20 HNO 3/5 250 20 75.1
32 acetylacetone / 3 EtOH / 45 HNO 3 /0.45 250 35 0.345
33 ascorbic acid / 3 EtOH / 40 HNO 3/1 250 35 25.6
34 ascorbic acid / 9 EtOH / 20 HNO 3 /3.24 250 30 36.3
35 glutamine / 3 EtOH / 37.5 HNO 3/1 250 30 6.51
36 glucose / 1 EtOH / 37.5 HNO 3/3 245 30 25.9
37 sugar / 1 EtOH / 37.5 HNO 3/3 250 30 27.5
38 sugar / 15 EtOH / 20 HNO 3/5 245 30 20.1
39 sugar / 3 EtOH / 37.5 HNO 3/1 245 30 22.4
40 tartar acid / 3 EtOH / 37.5 HNO 3/1 245 30 4.30
41 urea / 3 EtOH / 45 HNO 3/1 245 30 1.66
42 acetone / 3 EtOH / 37.5 HNO 3/1 245 30 1.56
43 ethyleneglycole / 3 EtOH / 37.5 HNO 3/1 245 30 3.78
44 starch / 3 EtOH / 37.5 HNO 3/1 250 30 39.1
45 oleic acid / 3 EtOH / 45 HNO 3 /0.157 250 35 0.650
46 acetylacetone / 3 2-PrOH / 40 HNO 3/3 250 35 4.27
47 acetylacetone / 3 n-PrOH / 37.5 HNO 3/1 250 30 5.28
48 acetylacetone / 3 chlorobenzene / 37.5 HNO 3/1 245 30 20.5
49 glucose / 3 EtOH / 37.5 H 2 SO 4/1 245 30 1.423
50 sugar / 1 EtOH / 40 KBH 4/1 245 30 10.6
51 acetylacetone / 3 EtOH / 37.5 KBH 4/1 245 30 3.94
52 benzene / 3 EtOH / 37.5 KBH 4 /0.685 245 30 1.56
53 acetylacetone / 3 EtOH / 45 Fe 2 O 3 /0.3 250 35 0.0467
54 acetylacetone / 3 EtOH / 42.5 CH 3 COOH / 0.5 250 35 0.0173
자. 합성 및 분석결과의 그림 설명character. Pictorial explanation of synthesis and analysis results
본 발명의 방법으로 합성한 탄소양자점의 여러 실시예의 특성을 정리한 결과는 도 1 내지 도 54와 같다. 도 1 내지 도 54는 표 1, 2에서와 같이 <합성 예 1> 내지 <합성 예 54>의 방법으로 합성한 여러 실시예의 결과특성을 보여준다.The results of various examples of the carbon quantum dots synthesized by the method of the present invention are shown in FIGS. 1 to 54. 1 to 54 show results of various examples synthesized by the methods of <Synthesis Example 1> to <Synthesis Example 54>, as shown in Tables 1 and 2.
[실시예 1]Example 1
도 1, 즉 도 1a 내지 도 1i는 본 발명의 방법으로 합성한 탄소양자점의 합성예 1의 특성을 정리한 결과로서, 표 1의 합성 예 1의 경우, 증류수 500cc, 아세틸아세톤 36g, 질산 12g을 혼합하여 내부부피가 1200cc인 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 1, that is, FIGS. 1A to 1I show the characteristics of Synthesis Example 1 of the carbon quantum dots synthesized by the method of the present invention. The mixture was placed in a high pressure reactor having an internal volume of 1200 cc and maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 1의 (a)이다. 도 1의 (a)에서와 같이 가시광의 모든 파장영역에서 흡수가 있으며 파장이 짧아질수록 흡수의 세기가 점차 증가한다. 261nm에서 흡수곡선의 피크가 나타나며, 이는 탄소양자점의 특징 중 하나인 광학밴드(optical band)이다. 500nm에서 합성용액의 흡수계수는 0.194이다. 도 1의 (b)는 형광파장이 428nm일 때 여기 스펙트럼이며, 이 여기 스펙트럼에서도 흡수 스펙트럼과 같은 파장의 광학밴드가 있음을 알 수 있다. 365nm의 여기광으로 조사했을 때 형광스펙트럼은 도 1의 (c)와 같다. UV-Vis absorption spectrum of the synthetic solution is shown in (a) of FIG. As shown in (a) of FIG. 1, there is absorption in all wavelength ranges of visible light, and the intensity of absorption gradually increases as the wavelength becomes shorter. The peak of the absorption curve appears at 261 nm, which is an optical band, one of the characteristics of carbon quantum dots. The absorption coefficient of the synthetic solution at 500 nm is 0.194. Figure 1 (b) is an excitation spectrum when the fluorescence wavelength is 428nm, it can be seen that there is also an optical band of the same wavelength as the absorption spectrum in this excitation spectrum. When irradiated with excitation light of 365 nm, the fluorescence spectrum is as shown in FIG.
탄소양자점의 특징 중 하나는 여기 파장에 따라 형광스펙트럼이 달라진다. 도 1의 (d)와 같이 여기광의 파장이 각각 335nm, 365nm, 435nm, 470nm, 500nm일 때 형광스펙트럼은 도 1의 (d)와 같다. 합성한 용액이 담긴 용액의 사진은 도 1의 (d-1)과 같으며, 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 1의 (d-2)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 1의 (d-3)이다.One characteristic of carbon quantum dots is that the fluorescence spectrum varies depending on the excitation wavelength. When the wavelength of the excitation light is 335 nm, 365 nm, 435 nm, 470 nm, and 500 nm, as shown in FIG. 1D, the fluorescence spectrum is the same as that of FIG. The photograph of the solution containing the synthesized solution is shown in (d-1) of FIG. 1, and the photo of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the vial containing the solution is shown in FIG. 2), and the photo taken with blue LED (460 nm) for fluorescence is (d-3) of FIG. 1.
합성한 용액의 FT-IR 스펙트럼은 도 1의 (e)와 같다. IR스펙트럼에서 O-H, C-H, C=O, C-O, C-O-C 결합에 의한 흡수 피크들을 확인할 수 있으며, 이들 흡수피크로 부터 탄소양자점의 표면에 -COOH, -OH, =O 등의 화학기가 붙어있음을 추정할 수 있다. 합성한 용액을 건조하면 끈적끈적한 검은 색의 젤이 되며, 이 젤의 x-선 회절패턴은 도 1의 (f)와 같다. The FT-IR spectrum of the synthesized solution is as shown in FIG. In the IR spectrum, absorption peaks by OH, CH, C = O, CO, and COC bonds can be identified, and chemical absorption groups such as -COOH, -OH, and = O are attached to the surface of the carbon quantum dot from these absorption peaks. can do. When the synthesized solution is dried, it becomes a sticky black gel, and the x-ray diffraction pattern of the gel is shown in FIG.
합성한 용액을 투과전자현미경(TEM)으로 측정한 사진은 도 1의 (g)-(p)와 같으며, 용액 속에 포함된 탄소양자점의 크기, 형태, 결정격자 등을 확인하였다. 도 1의 (g)와 (i) 사진에서 탄소양자점의 크기를 측정하였다. 탄소양자점의 크기분포는 도 1의 (q)와 같으며, 탄소양자점의 평균크기는 약 2.64nm이다. 도 1의 (h)와 (j)는 도 1의 (g)와 (i)를 부분 확대한 TEM 사진이며, 사진에서와 같이 탄소양자점의 결정면 무늬가 나타난다. 도 1의 (k)는 결정면 무늬가 뚜렷한 탄소양자점 사진이며 결정면 무늬의 회절무늬는 도 1의 (l)이다. 도 1의 (l)의 회절점은 6각 대칭성을 가지고 있으며 흑연의 c-면이 가지는 대칭성과 같다. 도 1의 (m) 사진과 (n) 사진에서도 결정면 무늬와 6각 대칭성의 회절패턴을 볼 수 있다. 도 1의 (o)와 (p) 사진은 결정면 무늬의 간격을 측정하여 흑연의 결정면과 비교하였다.A photograph of the synthesized solution measured by a transmission electron microscope (TEM) is shown in FIG. 1 (g)-(p), and the size, shape, crystal lattice, and the like of the carbon quantum dots included in the solution were confirmed. In Figure 1 (g) and (i) the size of the carbon quantum dot was measured. The size distribution of the carbon quantum dots is shown in (q) of FIG. 1, and the average size of the carbon quantum dots is about 2.64 nm. (H) and (j) of FIG. 1 are enlarged TEM photographs of (g) and (i) of FIG. 1, and the crystal surface patterns of carbon quantum dots appear as shown in the photograph. FIG. 1 (k) is a carbon quantum dot photograph having a clear crystal surface pattern, and the diffraction pattern of the crystal surface pattern is (l) of FIG. 1. The diffraction point of (l) of FIG. 1 has hexagonal symmetry and is the same as that of c-plane of graphite. In (m) and (n) of FIG. 1, the diffraction pattern of the crystal plane pattern and the hexagonal symmetry can be seen. 1 (o) and (p) photographs were compared with the crystal plane of graphite by measuring the spacing of the crystal plane pattern.
도 1의 (a)-(p)의 결과를 정리하면, 합성 예 1의 방법으로 합성한 입자는 평균크기가 2.64nm인 흑연입자이고, 입자의 표면에 -COOH, -OH, =O 기가 부착되어 있으며 양자점의 형광특성을 나타내는 탄소양자점임을 알 수 있다.1 (a)-(p) summarized, the particles synthesized by the method of Synthesis Example 1 are graphite particles having an average size of 2.64 nm, and -COOH, -OH, = O groups adhere to the surface of the particles. It can be seen that it is a carbon quantum dot showing the fluorescent characteristics of the quantum dot.
[실시예 2]Example 2
도 2는 본 발명의 방법으로 합성한 탄소양자점의 합성예 2의 특성을 정리한 결과로서, 표 1의 합성 예 2의 경우, 증류수 37.5cc, 아세틸아세톤 3g, 질산 1g을 혼합하여 내부부피가 60cc인 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 2 shows the results of Synthesis Example 2 of the carbon quantum dots synthesized by the method of the present invention.In the Synthesis Example 2 of Table 1, distilled water 37.5cc, acetylacetone 3g, and 1g nitric acid were mixed to obtain an internal volume of 60cc. The reaction mixture was placed in a phosphorous autoclave and maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 2의 (a)와 같으며, 500nm에서 흡수계수는 0.185이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 2의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1667, 0.1464)와 (0.1883, 0.2455)이다. 도 2의 (d)는 합성한 용액이 담긴 시험관 사진이다. 용액이 든 유리병(vial)의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 2의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 2의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 2 (a), the absorption coefficient is 0.185 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 2B and 2C, respectively, and the color coordinates of fluorescence are (0.1667, 0.1464) and (0.1883, 0.2455), respectively. 2 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the vial containing the solution is shown in Figure 2 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 2 (f).
[실시예 3]Example 3
도 3은 본 발명의 방법으로 합성한 탄소양자점의 합성예 3의 특성을 정리한 결과로서, 표 1의 합성 예 3의 경우, 증류수 500cc, 구연산 36g, 질산 12g을 혼합하여 내부부피가 1200cc인 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 3 shows the results of Synthesis Example 3 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 3 of Table 1, 500 cc of distilled water, 36 g of citric acid, and 12 g of nitric acid were mixed to obtain a high pressure of 1200 cc. The reaction was carried out while keeping in the reactor for 30 hours at 250 ℃. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 3의 (a)와 같으며, 500nm에서 흡수계수는 0.937이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 3의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1811, 0.1901)와 (0.2006, 0.2883)이다. 도 3의 (d)는 합성한 용액이 담긴 시험관의 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 3의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 3의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 3 (a), the absorption coefficient is 0.937 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 3B and 3C, respectively, and the color coordinates of fluorescence are (0.1811, 0.1901) and (0.2006, 0.2883), respectively. 3 (d) is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 3 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 3 (f). to be.
[실시예 4]Example 4
도 4는 본 발명의 방법으로 합성한 탄소양자점의 합성예 4의 특성을 정리한 결과로서, 표 1의 합성 예 4의 경우, 증류수 40cc, 구연산 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 4 shows the results of Synthesis Example 4 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 4 of Table 1, 40 cc of distilled water, 3 g of citric acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor at 250 ° C. The reaction was maintained at 35 hours at. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 4의 (a)와 같으며, 500nm에서 흡수계수는 0.0304이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 4의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1677, 0.1462)와 (0.2001, 0.2668)이다. 도 4의 (d)는 합성한 용액이 담긴 시험관의 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 4의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 4의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 4 (a), the absorption coefficient is 0.0304 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 4B and 4C, respectively, and the color coordinates of fluorescence are (0.1677, 0.1462) and (0.2001, 0.2668), respectively. 4 (d) is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 4 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 4 (f). to be.
[실시예 5]Example 5
도 5는 본 발명의 방법으로 합성한 탄소양자점의 합성예 5의 특성을 정리한 결과로서, 표 1의 합성 예 5의 경우, 증류수 37.5cc, 글루코스 1g, 질산 3g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 5 shows the results of Synthesis Example 5 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 5 of Table 1, distilled water 37.5cc, glucose 1g, and nitric acid 3g were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 5의 (a)와 같으며, 500nm에서 흡수계수는 0.0096이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 5의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1716, 0.1200)와 (0.2841, 0.2670)이다. 도 5의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 5의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 5의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 5 (a), the absorption coefficient is 0.0096 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 5B and 5C, respectively, and the color coordinates of fluorescence are (0.1716, 0.1200) and (0.2841, 0.2670), respectively. 5 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 5 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 5 ( f).
[실시예 6]Example 6
*도 6은 본 발명의 방법으로 합성한 탄소양자점의 합성예 6의 특성을 정리한 결과로서, 표 1의 합성 예 6의 경우, 증류수 37.5cc, 글루코스 1.2g, 질산 2g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 6 shows the results of Synthesis Example 6 of the carbon quantum dots synthesized by the method of the present invention. In Synthesis Example 6 of Table 1, 37.5 cc of distilled water, 1.2 g of glucose, and 2 g of nitric acid were mixed to a high pressure reactor. The reaction was carried out while maintaining at 245 ℃ for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 6의 (a)와 같으며, 500nm에서 흡수계수는 0.117이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 6의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1659, 0.1590)와 (0.1812, 0.2772)이다. 도 6의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 6의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 6의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 6 (a), the absorption coefficient is 0.117 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 6B and 6C, respectively, and the color coordinates of fluorescence are (0.1659, 0.1590) and (0.1812, 0.2772), respectively. 6 (d) is a test tube photograph containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 6 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 6 ( f).
[실시예 7]Example 7
도 7은 본 발명의 방법으로 합성한 탄소양자점의 합성예 7의 특성을 정리한 결과로서, 표 1의 합성 예 7의 경우, 증류수 37.5cc, 설탕 1g, 질산 3g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 7 shows the results of Synthesis Example 7 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 7 of Table 1, distilled water 37.5 cc, sugar 1 g, and nitric acid 3 g were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 7의 (a)와 같으며, 500nm에서 흡수계수는 0.130이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 7의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1641, 0.1479)와 (0.1777, 0.2546)이다. 도 7의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 7의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 7의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 7 (a), the absorption coefficient is 0.130 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 7B and 7C, respectively, and the color coordinates of fluorescence are (0.1641, 0.1479) and (0.1777, 0.2546), respectively. 7 (d) is a test tube photograph containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 7 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 7 ( f).
[실시예 8]Example 8
도 8은 본 발명의 방법으로 합성한 탄소양자점의 합성예 8의 특성을 정리한 결과로서, 표 1의 합성 예 8의 경우, 증류수 37.5cc, 설탕 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 8 shows the results of Synthesis Example 8 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 8 of Table 1, 37.5 cc of distilled water, 3 g of sugar, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 8의 (a)와 같으며, 500nm에서 흡수계수는 0.564이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 8의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1827, 0.1922)와 (0.1843, 0.2843)이다. 도 8의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 8의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 8의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 8 (a), the absorption coefficient is 0.564 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 8B and 8C, respectively, and the color coordinates of fluorescence are (0.1827, 0.1922) and (0.1843, 0.2843), respectively. (D) of FIG. 8 is a test tube photograph containing the synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 8 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 8 ( f).
[실시예 9]Example 9
도 9는 본 발명의 방법으로 합성한 탄소양자점의 합성예 9의 특성을 정리한 결과로서, 표 1의 합성 예 9의 경우, 증류수 37.5cc, 전분 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 9 shows the results of Synthesis Example 9 of the carbon quantum dots synthesized by the method of the present invention. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 9의 (a)와 같으며, 500nm에서 흡수계수는 0.410이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 9의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1724, 0.1692)와 (0.1826, 0.2729) 이다. 도 9의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 9의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 9의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 9 (a), the absorption coefficient is 0.410 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 9B and 9C, respectively, and the color coordinates of fluorescence are (0.1724, 0.1692) and (0.1826, 0.2729), respectively. 9 (d) is a test tube photograph containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 9 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 9 ( f).
[실시예 10]Example 10
도 10은 본 발명의 방법으로 합성한 탄소양자점의 합성예 10의 특성을 정리한 결과로서, 표 1의 합성 예 10의 경우, 증류수 37.5cc, 초산 3g, 질산 2g을 혼합하여 고압반응기에 넣고 245℃에서 24시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 10 shows the results of Synthesis Example 10 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 10 of Table 1, 37.5 cc of distilled water, 3 g of acetic acid, and 2 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 24 ° C. for 24 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 10의 (a)와 같으며, 500nm에서 흡수계수는 0.00475이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 10의 (b), (c)와 같다. 도 10의 (b)의 색좌표는 (0.1769, 0.1340)이며, 도 10의 (c)는 형광이 아주 약한 경우에 해당하므로 색좌표를 계산하지 않았다. 도 10의 (d)는 합성한 용액이 담긴 시험관의 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 10의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 10의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 10 (a), the absorption coefficient is 0.00475 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 10B and 10C, respectively. The color coordinates of (b) of FIG. 10 are (0.1769, 0.1340), and (c) of FIG. 10 corresponds to a case where the fluorescence is very weak. Therefore, the color coordinates are not calculated. 10 (d) is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 10 (e), the photo taken with the blue LED (460nm) fluorescence is shown in Figure 10 (f) to be.
[실시예 11]Example 11
도 11은 본 발명의 방법으로 합성한 탄소양자점의 합성예 11의 특성을 정리한 결과로서 표 1의 합성 예 11의 경우, 증류수 37.5cc, 주석산 2g, 질산 2g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 11 shows the results of Synthesis Example 11 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 11 of Table 1, distilled water 37.5cc, tartaric acid and 2g nitric acid were mixed and placed in a high pressure reactor at 245 ° C. The reaction was maintained for 30 hours at. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 11의 (a)와 같으며, 500nm에서 흡수계수는 0.0787이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 11의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1682, 0.1450)와 (0.0.1906, 0.2529) 이다. 도 11의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 11의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 11의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 11 (a), the absorption coefficient is 0.0787 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 11B and 11C, respectively, and the color coordinates of fluorescence are (0.1682, 0.1450) and (0.0.1906, 0.2529), respectively. 11 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 11 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 11 ( f).
[실시예 12]Example 12
도 12는 본 발명의 방법으로 합성한 탄소양자점의 합성예 12의 특성을 정리한 결과로서, 표 1의 합성 예 12의 경우, 증류수 37.5cc, 요소 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 12 shows the results of Synthesis Example 12 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 12 of Table 1, distilled water 37.5cc, urea 3g, and 1g nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
*합성용액의 UV-Vis 흡수스펙트럼은 도 12의 (a)와 같으며, 500nm에서 흡수계수는 0.00147이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 12의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1637, 0.1167)와 (0.1899, 0.2526) 이다. 도 12의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 12의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 12의 (f)이다.* UV-Vis absorption spectrum of the synthetic solution is as shown in Figure 12 (a), the absorption coefficient is 0.00147 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 12B and 12C, respectively, and the color coordinates of fluorescence are (0.1637, 0.1167) and (0.1899, 0.2526), respectively. 12 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 12 (e), the photo taken with fluorescence by the blue LED (460 nm) is shown in Figure 12 ( f).
[실시예 13]Example 13
도 13은 본 발명의 방법으로 합성한 탄소양자점의 합성예 13의 특성을 정리한 결과로서, 표 1의 합성 예 13의 경우, 증류수 37.5cc, 글루타민산 1g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 13 shows the results of Synthesis Example 13 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 13 of Table 1, 37.5 cc of distilled water, 1 g of glutamic acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 13의 (a)와 같으며, 500nm에서 흡수계수는 0.123이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 13의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1653, 0.1215)와 (0.2062, 0.2454) 이다. 도 13의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 13의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 13의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 13 (a), the absorption coefficient is 0.123 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 13B and 13C, respectively, and the color coordinates of fluorescence are (0.1653, 0.1215) and (0.2062, 0.2454), respectively. (D) of FIG. 13 is a test tube photograph containing the synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 13 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 13 ( f).
[실시예 14]Example 14
도 14는 본 발명의 방법으로 합성한 탄소양자점의 합성예 14의 특성을 정리한 결과로서, 표 1의 합성 예 14의 경우, 증류수 37.5cc, 올레익산 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 14 shows the results of Synthesis Example 14 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 14 of Table 1, 37.5 cc of distilled water, 3 g of oleic acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 14의 (a)와 같으며, 500nm에서 흡수계수는 0.0384이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 14의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1622, 0.1136)와 (0.0.1740, 0.1967) 이다. 도 14의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 14의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 14의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 14 (a), the absorption coefficient is 0.0384 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 14B and 14C, respectively, and the color coordinates of fluorescence are (0.1622, 0.1136) and (0.0.1740, 0.1967), respectively. Figure 14 (d) is a test tube picture containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 14 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 14 ( f).
[실시예 15]Example 15
도 15는 본 발명의 방법으로 합성한 탄소양자점의 합성예 15의 특성을 정리한 결과로서, 표 1의 합성 예 15의 경우, 증류수 37.5cc, 아세트페논 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 15 shows the results of Synthesis Example 15 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 15 of Table 1, 37.5 cc of distilled water, 3 g of acetphenone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 15의 (a)와 같으며, 500nm에서 흡수계수는 0.111이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 15의 (b), (c)와 같다. 도 15의 (b)의 색좌표는 (0.2401, 0.2271)이며, 도 15의 (c)는 형광이 아주 약한 경우에 해당하므로 색좌표를 계산하지 않았다. 도 15의 (d)는 합성한 용액이 담긴 시험관의 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 15의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 15의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 15 (a), the absorption coefficient is 0.111 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 15B and 15C, respectively. The color coordinates of (b) of FIG. 15 are (0.2401, 0.2271), and (c) of FIG. 15 corresponds to a case where the fluorescence is very weak. Therefore, the color coordinates are not calculated. Figure 15 (d) is a photograph of the test tube containing the synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the vial containing the solution is shown in Figure 15 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 15 (f). to be.
[실시예 16]Example 16
도 16은 본 발명의 방법으로 합성한 탄소양자점의 합성예 16의 특성을 정리한 결과로서, 표 1의 합성 예 16의 경우, 과산화수소 37.5cc, 아세틸아세톤 3g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 이 합성에서 산화제인 과산화수소는 용매이기도 하며 아세틸아세톤을 분해하여 반응을 촉진하는 촉진제이다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 16 shows the results of Synthesis Example 16 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 16 of Table 1, 37.5 cc of hydrogen peroxide and 3 g of acetylacetone were mixed and placed in a high pressure reactor at 245 ° C. FIG. The reaction was maintained for 30 hours. Hydrogen peroxide, the oxidant in this synthesis, is both a solvent and an accelerator to decompose acetylacetone to promote the reaction. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 16의 (a)와 같으며, 500nm에서 흡수계수는 0.197이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 16의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1684, 0.1393)와 (0.1854, 0.2287)이다. 도 16의 (d)는 합성한 용액이 담긴 시험관의 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 16의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 16의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 16 (a), the absorption coefficient at 500nm is 0.197. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 16B and 16C, respectively, and the color coordinates of fluorescence are (0.1684, 0.1393) and (0.1854, 0.2287), respectively. (D) of FIG. 16 is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 16 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 16 (f). to be.
[실시예 17]Example 17
도 17은 본 발명의 방법으로 합성한 탄소양자점의 합성예 17의 특성을 정리한 결과로서, 표 1의 합성 예 17의 경우, 증류수 37.5cc, 글루코스 3g, 황산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 17 shows the results of Synthesis Example 17 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 17 of Table 1, 37.5 cc of distilled water, 3 g of glucose, and 1 g of sulfuric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 17의 (a)와 같으며, 500nm에서 흡수계수는 0.170이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 17의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1685, 1425)와 (0.2144, 0.3331) 이다. 도 17의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 17의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 17의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 17 (a), the absorption coefficient is 0.170 at 500nm. Fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 17B and 17C, respectively, and the color coordinates of fluorescence are (0.1685, 1425) and (0.2144, 0.3331), respectively. Figure 17 (d) is a test tube picture containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 17 (e), the photo taken by the blue LED (460 nm) fluorescence is shown in Figure 17 ( f).
[실시예 18]Example 18
도 18은 본 발명의 방법으로 합성한 탄소양자점의 합성예 18의 특성을 정리한 결과로서, 표 1의 합성 예 18의 경우, 증류수 37.5cc, 아세틸아세톤 3g, 칼륨보로하이드라이드(KBH4) 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 18 shows the results of Synthesis Example 18 of the carbon quantum dots synthesized by the method of the present invention. For Synthesis Example 18 of Table 1, 37.5 cc of distilled water, 3 g of acetylacetone, and potassium borohydride (KBH 4 ) 1g was mixed and placed in a high pressure reactor, and reacted at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 18의 (a)와 같으며, 500nm에서 흡수계수는 0.480이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 18의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1910, 0.1899)와 (0.2109, 0.3193) 이다. 도 18의 (d)는 합성한 용액이 담긴 시험관 사진이다. 합성한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 18의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 18의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 18 (a), the absorption coefficient is 0.480 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 18B and 18C, respectively, and the color coordinates of fluorescence are (0.1910, 0.1899) and (0.2109, 0.3193), respectively. 18 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the synthesized solution is shown in Figure 18 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 18 ( f).
[실시예 19]Example 19
도 19, 즉 도 19a 내지 도 19d는 본 발명의 방법으로 합성한 탄소양자점의 합성예 19의 특성을 정리한 결과로서, 표 1의 합성 예 19의 경우, 메탄올 500cc, 아세틸아세톤 36g, 질산 12g을 혼합하여 내부부피가 1200cc인 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 19, namely, FIGS. 19A to 19D show results of Synthesis Example 19 of the carbon quantum dots synthesized by the method of the present invention. In the case of Synthesis Example 19 of Table 1, 500 cc of methanol, 36 g of acetylacetone, and 12 g of nitric acid were used. The mixture was placed in a high pressure reactor having an internal volume of 1200 cc and maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/15 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 19의 (a)와 같으며, 500nm에서 흡수계수는 0.241이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 3.62이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 19의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1776, 0.1763)와 (0.1964, 0.2739) 이다. 도 19의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/15 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 19의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 19의 (f)이다.The UV-Vis absorption spectrum of the diluted solution of the synthetic solution at 1/15 ratio is shown in FIG. 19 (a), and the absorption coefficient at 0.2 nm is 0.241. According to the diluted ratio, the absorption coefficient of the synthetic solution is 3.62. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 19B and 19C, respectively, and the color coordinates of fluorescence are (0.1776, 0.1763) and (0.1964, 0.2739), respectively. 19 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 19 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
합성용액의 TEM 사진은 도 19의 (g)와 같다. 50nm의 스케일(scale)에서 측정한 TEM 사진에서는 응집되지 않고 분산된 양자점 입자들을 볼 수 있으며, 각 입자를 확대한 5개의 사진에서는 결정격자면이 선명하였다. TEM 사진에서 측정한 양자점 입자의 평균 크기는 4.15nm이며, 크기에 따른 분포는 도 19의 (h)와 같다. 합성한 용액의 FT-IR 스펙트럼은 도 19의 (i)와 같다. IR스펙트럼에서 O-H, C-H, C=O, C-O, C-O-C 결합에 의한 흡수 피크들을 확인할 수 있으며, 이는 탄소양자점의 표면에 -COOH, -OH, =O 등의 화학기가 붙어있음을 추정할 수 있다.TEM photograph of the synthetic solution is shown in (g) of FIG. TEM images measured on a 50 nm scale show quantum dot particles dispersed and not aggregated, and crystal lattice planes were clear in five photographs in which each particle was enlarged. The average size of the quantum dot particles measured in the TEM image is 4.15nm, the distribution according to the size is shown in Figure 19 (h). The FT-IR spectrum of the synthesized solution is shown in FIG. 19 (i). Absorption peaks by O-H, C-H, C = O, C-O, and C-O-C bonds in the IR spectrum can be confirmed, and it can be estimated that chemical groups such as -COOH, -OH, and = O are attached to the surface of the carbon quantum dot.
[실시예 20]Example 20
도 20은 본 발명의 방법으로 합성한 탄소양자점의 합성예 20의 특성을 정리한 결과로서, 표 1의 합성 예 20의 경우, 메탄올 37.5cc, 아세틸아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 20 shows the results of Synthesis Example 20 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 20 of Table 1, 37.5 cc of methanol, 3 g of acetylacetone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/15 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 20의 (a)와 같으며, 500nm에서 흡수계수는 0.129이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.94이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 20의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1768, 0.1754)와 (0.1939, 0.2716) 이다. 도 20의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/15 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 20의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 20의 (f)이다.The UV-Vis absorption spectrum of the solution diluted by the 1/15 ratio of the synthetic solution is shown in FIG. 20 (a), and the absorption coefficient at 500 nm is 0.129. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.94. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 20B and 20C, respectively, and the color coordinates of fluorescence are (0.1768, 0.1754) and (0.1939, 0.2716), respectively. (D) of FIG. 20 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 20 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
[실시예 21]Example 21
도 21은 본 발명의 방법으로 합성한 탄소양자점의 합성예 21의 특성을 정리한 결과로서, 표 1의 합성 예 21의 경우, 메탄올 20cc, 증류수 20cc, 아세틸아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 21 is a result of synthesizing the properties of Synthesis Example 21 of the carbon quantum dot synthesized by the method of the present invention. In the case of Synthesis Example 21 of Table 1, 20 cc of methanol, 20 cc of distilled water, 3 g of acetylacetone, and 1 g of nitric acid were mixed. And reacted while maintaining at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/5 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 21의 (a)와 같으며, 500nm에서 흡수계수는 0.136이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 0.679이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 21의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1708, 0.1534)와 (0.1962, 0.2784) 이다. 도 21의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/5 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 21의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 21의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/5 is shown in FIG. 21 (a), and the absorption coefficient at 500 nm is 0.136. According to the diluted ratio, the absorption coefficient of the synthetic solution is 0.679. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 21B and 21C, respectively, and the color coordinates of fluorescence are (0.1708, 0.1534) and (0.1962, 0.2784), respectively. 21 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 21 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at 1/5 ratio. Is Fig. 21 (f).
[실시예 22]Example 22
도 22는 본 발명의 방법으로 합성한 탄소양자점의 합성예 22의 특성을 정리한 결과로서, 표 1의 합성 예 22의 경우, 메탄올 37.5cc, 아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 22 shows the results of Synthesis Example 22 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 22 of Table 1, 37.5 cc of methanol, 3 g of acetone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/10 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 22의 (a)와 같으며, 500nm에서 흡수계수는 0.152이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.52이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 22의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1722, 0.1671)와 (0.1848, 0.2632) 이다. 도 22의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/10 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 22의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 22의 (f)이다. The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a 1/10 ratio is shown in FIG. 22 (a), and the absorption coefficient at 500 nm is 0.152. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 1.52. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 22B and 22C, respectively, and the color coordinates of fluorescence are (0.1722, 0.1671) and (0.1848, 0.2632), respectively. (D) of FIG. 22 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 22 (e) irradiated with an ultraviolet LED (380 nm) emitted from the bottom of a glass bottle containing a solution diluted at a ratio of 1/10 is (e), and photographed with blue LED (460 nm). Is (f) of FIG.
[실시예 23]Example 23
도 23은 본 발명의 방법으로 합성한 탄소양자점의 합성예 23의 특성을 정리한 결과로서, 표 1의 합성 예 23의 경우, 메탄올 37.5cc, 아세토페논 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 23 shows the properties of Synthesis Example 23 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 23 of Table 1, 37.5 cc of methanol, 3 g of acetophenone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/7 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 23의 (a)와 같으며, 500nm에서 흡수계수는 0.144이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.01이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 23의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1689, 0.1111)와 (0.2016, 0.2659) 이다. 도 23의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/7 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 23의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 23의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/7 is shown in FIG. 23 (a), and the absorption coefficient at 500 nm is 0.144. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.01. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 23B and 23C, respectively, and the color coordinates of fluorescence are (0.1689, 0.1111) and (0.2016, 0.2659), respectively. Figure 23 (d) is a test tube picture containing the synthesized solution. Photograph (e) of FIG. 23 (e) irradiated with an ultraviolet LED (380 nm) emitted from the bottom of a glass bottle containing a solution diluted at a ratio of 1/7 is (e), the photo taken with blue LED (460 nm) fluorescence Is (f) of FIG.
[실시예 24]Example 24
도 24는 본 발명의 방법으로 합성한 탄소양자점의 합성예 24의 특성을 정리한 결과로서, 표 1의 합성 예 24의 경우, 메탄올 37.5cc, 올레익산 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 24 shows the results of Synthesis Example 24 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 24 of Table 1, 37.5 cc of methanol, 3 g of oleic acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 24의 (a)와 같으며, 500nm에서 흡수계수는 0.254이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 24의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1836, 0.1137)와 (0.2038, 0.2861) 이다. 도 24의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/7 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 24의 (e)이며, 청색LED (460nm)로 조사하여 형광을 찍은 사진은 도 24의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 24 (a), the absorption coefficient is 0.254 at 500nm. Fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 24B and 24C, respectively, and the color coordinates of fluorescence are (0.1836, 0.1137) and (0.2038, 0.2861), respectively. 24 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 24 (e) irradiated with an ultraviolet LED (380 nm) emitted from the bottom of a glass bottle containing a solution diluted at a ratio of 1/7 is (e), and photographed with a blue LED (460 nm). Is (f) of FIG.
[실시예 25]Example 25
도 25, 즉 도 25a 내지 도 25e는 본 발명의 방법으로 합성한 탄소양자점의 합성예 25의 특성을 정리한 결과로서, 표 1의 합성 예 25의 경우, 에탄올 550cc, 아세틸아세톤 36g, 질산 5.4g을 혼합하여 내부부피가 1200cc인 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물에는 탄소양자점이 생성되었다. 검은색의 액체상태인 합성물을 포(pore) 크기가 0.1㎛인 멤브레인 필터로 여과하여 검은색 투과액(permeate)을 분리하였다. 투과액은 탄소양자점의 특성을 보였다. 25, 25A to 25E summarize the characteristics of Synthesis Example 25 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 25 of Table 1, 550cc of ethanol, 36g of acetylacetone, and 5.4g of nitric acid. The reaction mixture was mixed into a high-pressure reactor having an internal volume of 1200 cc and maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. Carbon quantum dots were produced in the composite. The black permeate was isolated by filtering the membrane composite with a pore size of 0.1 μm. Permeate showed the characteristic of carbon quantum dot.
투과용액을 1/20 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 25의 (a)와 같으며, 500nm에서 흡수계수는 0.263이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 5.25이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 25의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1772, 0.1111)와 (0.1955, 0.2759) 이다. 도 25의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/20 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 25의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 25의 (f)이다. 투과액의 FT-IR 스펙트럼은 도 25의 (g)와 같다. IR스펙트럼에서 O-H, C-H, C=O, C-O, C-O-C 결합에 의한 흡수 피크들을 확인할 수 있다. 투과액을 건조하여 측정한 X-선 회절패턴은 도 25의 (h)와 같다. The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a 1/20 ratio is shown in FIG. 25 (a), and the absorption coefficient at 0.2 nm is 0.263. According to the diluted ratio, the absorption coefficient of the synthetic solution is 5.25. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 25B and 25C, respectively, and the color coordinates of fluorescence are (0.1772, 0.1111) and (0.1955, 0.2759), respectively. 25 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/20 is (e) of FIG. 25, the photo was taken by fluorescence by the blue LED (460 nm). Is (f) of FIG. The FT-IR spectrum of the permeate is shown in FIG. 25 (g). Absorption peaks by O-H, C-H, C = O, C-O, and C-O-C bonds can be identified in the IR spectrum. The X-ray diffraction pattern measured by drying the permeate liquid is shown in FIG. 25 (h).
도 25의 (i), (j), (k)는 투과액의 TEM으로 측정한 사진과 결과들이다. TEM 사진 도 25의 (i-1)에서 구형 CQD의 크기를 확인할 수 있다. 도 25의 (i-2)는 도 25의 (i-1)의 부분을 확대하여 측정한 사진이며, 결정격자면이 뚜렷이 보이는 CQD이다. 도 25의 (i-2)의 한 입자의 결정격자를 푸리에변환한 회절패턴은 도 25의 (i-3)이다. 회절패턴이 찌그러진 6각형을 형성하였다. 도 25의 (j-1), (j-2)는 결정격자면이 뚜렷이 측정되는 탄소양자점들이며, 측정된 격자거리와 면지수를 표시하였다. 도 25의 (j-2)는 결정격자를 푸리에변환한 회절패턴이다. 도 25의 (k)는 TEM으로 측정한 탄소양자점 입자의 크기분포를 나타낸 것이며, 평균 크기는 약 4.40nm이다. (I), (j) and (k) of FIG. 25 are photographs and results measured by TEM of a permeate solution. TEM photograph It can be confirmed the size of the spherical CQD in Fig. 25 (i-1). FIG. 25 (i-2) is an enlarged photograph of part of FIG. 25 (i-1), and is a CQD in which the crystal lattice plane is clearly visible. The diffraction pattern obtained by Fourier transforming the crystal lattice of one particle in FIG. 25 (i-2) is shown in FIG. 25 (i-3). The diffraction pattern formed a crushed hexagon. 25 (j-1) and (j-2) are carbon quantum points in which crystal lattice planes are clearly measured, and the measured lattice distances and surface indices are indicated. 25 (j-2) shows a diffraction pattern obtained by Fourier transforming a crystal lattice. Figure 25 (k) shows the size distribution of carbon quantum dot particles measured by TEM, the average size is about 4.40nm.
[실시예 26]Example 26
도 26은 본 발명의 방법으로 합성한 탄소양자점의 합성예 26의 특성을 정리한 결과로서, 표 1의 합성 예 26의 경우, 에탄올 45cc, 아세틸아세톤 3g, 질산 0.45g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 26 shows the results of Synthesis Example 26 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 26 of Table 1, 45 cc of ethanol, 3 g of acetylacetone, and 0.45 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/15 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 26의 (a)와 같으며, 500nm에서 흡수계수는 0.148이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 2.23이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 26의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1747, 0.1694)와 (0.1887, 0.2590) 이다. 도 26의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/15 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 26의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 26의 (f)이다.The UV-Vis absorption spectrum of the solution diluted by the 1/15 ratio of the synthetic solution is shown in FIG. 26 (a), and the absorption coefficient at 500 nm is 0.148. According to the diluted ratio, the absorption coefficient of the synthetic solution is 2.23. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 26B and 26C, respectively, and the color coordinates of fluorescence are (0.1747, 0.1694) and (0.1887, 0.2590), respectively. (D) of FIG. 26 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 26 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
[실시예 27]Example 27
도 27은 본 발명의 방법으로 합성한 탄소양자점의 합성예 27의 특성을 정리한 결과로서, 표 1의 합성 예 27의 경우, 에탄올 45cc, 아세틸아세톤 3g, 질산 0.45g을 혼합하여 고압반응기에 넣고 230℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 27 shows the results of Synthesis Example 27 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 27 of Table 1, 45 cc of ethanol, 3 g of acetylacetone, and 0.45 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 230 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/5 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 27의 (a)와 같으며, 500nm에서 흡수계수는 0.233이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.16이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 27의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1711, 0.1608)와 (0.1857, 0.2573) 이다. 도 27의 는 합성한 용액이 담긴 시험관 사진이다. 1/5 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 27의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 27의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/5 is shown in FIG. 27A, and the absorption coefficient at 0.2 nm is 0.233. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.16. The fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 27B and 27C, respectively, and the color coordinates of fluorescence are (0.1711, 0.1608) and (0.1857, 0.2573), respectively. Figure 27 is a test tube picture containing the synthesized solution. Photograph (e) of FIG. 27 (e) irradiated with an ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing a solution diluted at a ratio of 1/5 is (e), and photographed with a blue LED (460 nm). Is Fig. 27F.
[실시예 28]Example 28
도 28은 본 발명의 방법으로 합성한 탄소양자점의 합성예 28의 특성을 정리한 결과로서, 표 2의 합성 예 28의 경우, 에탄올 45cc, 아세틸아세톤 3g, 질산 0.45g을 혼합하여 고압반응기에 넣고 280℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 28 shows the results of Synthesis Example 28 of the carbon quantum dots synthesized by the method of the present invention.In the Synthesis Example 28 of Table 2, 45 cc of ethanol, 3 g of acetylacetone, and 0.45 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 280 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/15 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 28의 (a)와 같으며, 500nm에서 흡수계수는 0.0875이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.31이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 28의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1809, 0.1794)와 (0.2035, 0.3331)이다. 도 28의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/15 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 28의(e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 28의 (f)이다.The UV-Vis absorption spectrum of the diluted solution of the synthetic solution at 1/15 ratio is shown in FIG. 28 (a), and the absorption coefficient at 500 nm is 0.0875. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.31. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 28B and 28C, respectively, and the color coordinates of fluorescence are (0.1809, 0.1794) and (0.2035, 0.3331), respectively. Figure 28 (d) is a test tube picture containing the synthesized solution. Photograph (e) of FIG. 28 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/15. Is (f) of FIG.
[실시예 29]Example 29
도 29는 본 발명의 방법으로 합성한 탄소양자점의 합성예 29의 특성을 정리한 결과로서, 표 2의 합성 예 29의 경우, 에탄올 37.5cc, 아세틸아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 29 is a summary of the characteristics of the synthesis example 29 of the carbon quantum dot synthesized by the method of the present invention, in the case of the synthesis example 29 of Table 2, ethanol 37.5cc, acetylacetone 3g, 1g nitric acid were mixed and placed in a high pressure reactor The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/36 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 29의 (a)와 같으며, 500nm에서 흡수계수는 0.173이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 6.24이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 29의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1808, 0.1770)와 (0.1978, 0.2777) 이다. 도 29의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/36 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 29의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 29의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/36 is shown in FIG. 29 (a), and the absorption coefficient at 500 nm is 0.173. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 6.24. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 29B and 29C, respectively, and the color coordinates of fluorescence are (0.1808, 0.1770) and (0.1978, 0.2777), respectively. (D) of FIG. 29 is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 29 is a photo of fluorescence emitted by ultraviolet LED (380 nm) emitted from the bottom of a glass bottle containing a solution diluted at 1/36 ratio. Is (f) of FIG.
[실시예 30]Example 30
도 30은 본 발명의 방법으로 합성한 탄소양자점의 합성예 30의 특성을 정리한 결과로서, 표 2의 합성 예 30의 경우, 에탄올 20cc, 아세틸아세톤 9g, 질산 3g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. 30 is a summary of the characteristics of Synthesis Example 30 of the carbon quantum dot synthesized by the method of the present invention, in the case of Synthesis Example 30 of Table 2, 20cc of ethanol, 9g of acetylacetone, 3g of nitric acid were mixed and placed in a high pressure reactor 250 The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/500 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 30의 (a)와 같으며, 500nm에서 흡수계수는 0.117이다. 희석한 비율에 따라 환산하면 투과액의 흡수계수는 58.6이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 30의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1973, 0.2186)와 (0.2219, 0.3130) 이다. 도 30의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/500 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 30의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 30의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a ratio of 1/500 is shown in FIG. 30 (a), and the absorption coefficient at 500 nm is 0.117. In terms of dilution ratio, the absorption coefficient of permeate is 58.6. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 30B and 30C, respectively, and the color coordinates of fluorescence are (0.1973, 0.2186) and (0.2219, 0.3130), respectively. (D) of FIG. 30 is a photograph of a test tube containing the synthesized solution. Photograph (e) of FIG. 30 (e) irradiated with ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/500 is (e), the photo taken with blue LED (460 nm) fluorescence Is (f) of FIG.
[실시예 31]Example 31
도 31은 본 발명의 방법으로 합성한 탄소양자점의 합성예 31의 특성을 정리한 결과로서, 표 1의 합성 예 31의 경우, 에탄올 20cc, 아세틸아세톤 15g, 질산 5g을 혼합하여 고압반응기에 넣고 250℃에서 20시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. 31 is a summary of the characteristics of Synthesis Example 31 of the carbon quantum dot synthesized by the method of the present invention, in the case of Synthesis Example 31 of Table 1, 20cc of ethanol, 15g of acetylacetone, 5g of nitric acid were mixed into a high pressure reactor 250 The reaction was maintained at 20 ° C. for 20 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/200 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 31의 (a)와 같으며, 500nm에서 흡수계수는 0.376이다. 희석한 비율에 따라 환산하면 투과액의 흡수계수는 75.1이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 31의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1870, 0.1943)와 (0.2086, 0.2942) 이다. 도 31의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/200 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 31의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 31의 (f)이다. The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a 1/200 ratio is shown in FIG. 31 (a), and the absorption coefficient at 0.3 nm is 0.376. In terms of the diluted ratio, the absorption coefficient of the permeate is 75.1. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 31B and 31C, respectively, and the color coordinates of fluorescence are (0.1870, 0.1943) and (0.2086, 0.2942), respectively. (D) of FIG. 31 is a photograph of a test tube containing a synthesized solution. Photograph (e) of FIG. 31 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/200. Is Fig. 31 (f).
[실시예 32]Example 32
도 32는 본 발명의 방법으로 합성한 탄소양자점의 합성예 32의 특성을 정리한 결과로서, 표 2의 합성 예 32의 경우, 에탄올 45cc, 구연산 3g, 질산 0.45g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 32 is a summary of the characteristics of the synthesis example 32 of the carbon quantum dots synthesized by the method of the present invention, in the case of the synthesis example 32 of Table 2, ethanol 45cc, 3g citric acid, 0.45g nitric acid was mixed and put into a high pressure reactor 250 The reaction was maintained at 35 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 32의 (a)와 같으며, 500nm에서 흡수계수는 0.345이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 32의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1809, 0.1811)와 (0.1949, 0.2645) 이다. 도 32의 (d)는 합성한 용액이 담긴 시험관 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 32의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 32의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 32 (a), the absorption coefficient is 0.345 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 32B and 32C, respectively, and the color coordinates of fluorescence are (0.1809, 0.1811) and (0.1949, 0.2645), respectively. (D) of FIG. 32 is a photograph of a test tube containing a synthesized solution. The photo of the fluorescence emitted by the ultraviolet LED (380nm) from the bottom of the glass bottle containing the solution is shown in Figure 32 (e), the photo taken with fluorescence by blue LED (460nm) is shown in Figure 32 (f). to be.
[실시예 33]Example 33
도 33은 본 발명의 방법으로 합성한 탄소양자점의 합성예 33의 특성을 정리한 결과로서, 표 2의 합성 예 33의 경우, 에탄올 40cc, 비타민C 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 33 shows the results of Synthesis Example 33 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 33 of Table 2, ethanol 40cc, vitamin C 3g, and nitric acid 1g were mixed and placed in a high pressure reactor. The reaction was maintained at 35 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/100 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 33의 (a)와 같으며, 500nm에서 흡수계수는 0.256이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 25.6이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 33의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1931, 0.2127)와 (0.2143, 0.3034) 이다. 도 33의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/100 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 33의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 33의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/100 is shown in FIG. 33 (a), and the absorption coefficient at 500 nm is 0.256. According to the diluted ratio, the absorption coefficient of the synthetic solution is 25.6. The fluorescence spectra measured by excitation with 365 nm and 400 nm light are shown in FIGS. 33B and 33C, respectively, and the color coordinates of fluorescence are (0.1931, 0.2127) and (0.2143, 0.3034), respectively. 33 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 33 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the 1/100 ratio. Is (f) of FIG.
[실시예 34]Example 34
도 34는 본 발명의 방법으로 합성한 탄소양자점의 합성예 34의 특성을 정리한 결과로서, 표 2의 합성 예 34의 경우, 에탄올 20cc, 비타민C 9g, 질산 3.24g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. FIG. 34 shows the results of Synthesis Example 34 of the carbon quantum dots synthesized by the method of the present invention. In Synthesis Example 34 of Table 2, 20 cc of ethanol, 9 g of vitamin C, and 3.24 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/100 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 34의 (a)와 같으며, 500nm에서 흡수계수는 0.363이다. 희석한 비율에 따라 환산하면 투과용액의 흡수계수는 36.3이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 34의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1795, 0.1834)와 (0.1997, 0.2888) 이다. 도 34의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/100 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 34의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 34의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at 1/100 ratio is shown in FIG. 34 (a), and the absorption coefficient at 0.3 nm is 0.363. According to the diluted ratio, the absorption coefficient of permeate solution is 36.3. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 34B and 34C, respectively, and the color coordinates of fluorescence are (0.1795, 0.1834) and (0.1997, 0.2888), respectively. 34 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 34 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the 1/100 ratio. Is Fig. 34 (f).
[실시예 35]Example 35
도 35는 본 발명의 방법으로 합성한 탄소양자점의 합성예 35의 특성을 정리한 결과로서, 표 2의 합성 예 35의 경우, 에탄올 37.5cc, 글루타민 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. FIG. 35 shows the results of Synthesis Example 35 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 35 of Table 2, 37.5 cc of ethanol, 3 g of glutamine, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/31 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 35의 (a)와 같으며, 500nm에서 흡수계수는 0.210이다. 희석한 비율에 따라 환산하면 투과용액의 흡수계수는 6.51이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 35의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1816, 0.1790)와 (0.1994, 0.2777) 이다. 도 35의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/31 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 35의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 35의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a ratio of 1/31 is shown in FIG. 35 (a), and the absorption coefficient at 0.2 nm is 0.210. According to the diluted ratio, the absorption coefficient of the permeate solution is 6.51. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 35B and 35C, respectively, and the color coordinates of fluorescence are (0.1816, 0.1790) and (0.1994, 0.2777), respectively. 35 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 35 shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/31. Is (f) of FIG.
[실시예 36]Example 36
도 36은 본 발명의 방법으로 합성한 탄소양자점의 합성예 36의 특성을 정리한 결과로서, 표 2의 합성 예 36의 경우, 에탄올 37.5cc, 글루코스 1g, 질산 3g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 36 shows the results of Synthesis Example 36 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 36 of Table 2, 37.5 cc of ethanol, 1 g of glucose, and 3 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/81비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 36의 (a)와 같으며, 500nm에서 흡수계수는 0.320이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 25.9이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 36의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1931, 0.2300)와 (0.2079, 0.3019) 이다. 도 36의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/81 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 36의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 36의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/81 is shown in FIG. 36 (a), and the absorption coefficient at 0.3 nm is 0.320. According to the diluted ratio, the absorption coefficient of the synthetic solution is 25.9. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 36B and 36C, respectively, and the color coordinates of fluorescence are (0.1931, 0.2300) and (0.2079, 0.3019), respectively. 36 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 36 (e) irradiated with ultraviolet LED (380 nm) to emit light from the bottom of the glass bottle containing a solution diluted at the ratio of 1/81 is (e), the photo was taken by irradiation with blue LED (460 nm). Is (f) of FIG.
[실시예 37]Example 37
도 37은 본 발명의 방법으로 합성한 탄소양자점의 합성예 37의 특성을 정리한 결과로서, 표 2의 합성 예 36의 경우, 에탄올 37.5cc, 흰 설탕 1g, 질산 3g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. 37 shows the properties of Synthesis Example 37 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 36 of Table 2, 37.5 cc of ethanol, 1 g of white sugar, and 3 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과용액을 1/81비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 37의 (a)와 같으며, 500nm에서 흡수계수는 0.339이다. 희석한 비율에 따라 환산하면 투과용액의 흡수계수는 27.5이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 37의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1958, 0.2317)와 (0.2206, 0.3368) 이다. 도 37의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/81 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 37의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 37의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a ratio of 1/81 is shown in FIG. 37 (a), and the absorption coefficient at 0.3 nm is 0.339. According to the diluted ratio, the absorption coefficient of the permeate solution is 27.5. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 37B and 37C, respectively, and the color coordinates of fluorescence are (0.1958, 0.2317) and (0.2206, 0.3368), respectively. 37 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 37 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/81. Is (f) of FIG.
[실시예 38]Example 38
도 38은 본 발명의 방법으로 합성한 탄소양자점의 합성예 38의 특성을 정리한 결과로서, 표 2의 합성 예 38의 경우, 에탄올 20cc, 흰 설탕 15g, 질산 5g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 38 shows the characteristics of Synthesis Example 38 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 38 of Table 2, 20 cc of ethanol, 15 g of white sugar, and 5 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/81 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 38의 (a)와 같으며, 500nm에서 흡수계수는 0.248이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 20.1이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 38의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1916, 0.2133)와 (0.2232, 0.3121) 이다. 도 38의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/81 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 38의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 38의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/81 is shown in FIG. 38 (a), and the absorption coefficient at 0.2 nm is 0.248. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 20.1. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 38 (b) and 38 (c), respectively, and the color coordinates of fluorescence are (0.1916, 0.2133) and (0.2232, 0.3121), respectively. 38 (d) is a test tube photograph containing the synthesized solution. The photo of fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/81 is (e) of FIG. 38, and the photo was taken by fluorescence by the blue LED (460 nm). Is (f) of FIG.
[실시예 39]Example 39
도 39는 본 발명의 방법으로 합성한 탄소양자점의 합성예 39의 특성을 정리한 결과로서, 표 2의 합성 예 39의 경우, 에탄올 37.5cc, 흰 설탕 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 39 shows the results of Synthesis Example 39 of the carbon quantum dots synthesized by the method of the present invention. The reaction was maintained at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/111 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 39의 (a)와 같으며, 500nm에서 흡수계수는 0.201이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 22.4이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 39의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.2146, 0.2467)와 (0.2505, 0.3324) 이다. 도 39의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/111 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 39의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 39의 (f)이다.The UV-Vis absorption spectrum of the diluted solution of the synthesis solution at 1/111 ratio is shown in FIG. 39 (a), and the absorption coefficient at 0.2 nm is 0.201. Converted according to the diluted ratio, the absorption coefficient of the synthetic solution is 22.4. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 39B and 39C, respectively, and the color coordinates of fluorescence are (0.2146, 0.2467) and (0.2505, 0.3324), respectively. 39 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 39 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/111. Is (f) of FIG.
[실시예 40]Example 40
도 40은 본 발명의 방법으로 합성한 탄소양자점의 합성예 40의 특성을 정리한 결과로서, 표 2의 합성 예 40의 경우, 에탄올 37.5cc, 주석산 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. 40 shows the characteristics of Synthesis Example 40 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 40 of Table 2, 37.5 cc of ethanol, 3 g of tartaric acid, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/11비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 40의 (a)와 같으며, 500nm에서 흡수계수는 0.391이다. 희석한 비율에 따라 환산하면 투과액의 흡수계수는 4.30이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 40의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1945, 0.2139)와 (0.2187, 0.2951) 이다. 도 40의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/11 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 40의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 40의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a 1/11 ratio is shown in FIG. 40 (a), and the absorption coefficient at 0.3 nm is 0.391. According to the diluted ratio, the absorption coefficient of the permeate is 4.30. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 40B and 40C, respectively, and the color coordinates of fluorescence are (0.1945, 0.2139) and (0.2187, 0.2951), respectively. 40 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 40 shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/11. Is (f) of FIG.
[실시예 41]Example 41
도 41은 본 발명의 방법으로 합성한 탄소양자점의 합성예 41의 특성을 정리한 결과로서, 표 2의 합성 예 41의 경우, 에탄올 45cc, 요소 3g, 질산 3g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 41 shows the characteristics of Synthesis Example 41 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 41 of Table 2, 45 cc of ethanol, 3 g of urea, and 3 g of nitric acid were mixed and placed in a high pressure reactor at 245 ° C. The reaction was maintained for 30 hours at. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/13비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 41의 (a)와 같으며, 500nm에서 흡수계수는 0.128이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.66이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 41의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1749, 0.1496)와 (0.0.2060, 0.2565) 이다. 도 41의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/13 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 41의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 41의 (f)이다.UV-Vis absorption spectrum of the solution diluted with the synthesis solution at 1/13 ratio is shown in Figure 41 (a), the absorption coefficient is 0.128 at 500nm. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.66. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 41B and 41C, respectively, and the color coordinates of fluorescence are (0.1749, 0.1496) and (0.0.2060, 0.2565), respectively. 41 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 41 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/13. Is Fig. 41 (f).
[실시예 42]Example 42
도 42는 본 발명의 방법으로 합성한 탄소양자점의 합성예 42의 특성을 정리한 결과로서, 표 2의 합성 예 42의 경우, 에탄올 37.5cc, 아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 42 shows the results of Synthesis Example 42 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 42 of Table 2, 37.5 cc of ethanol, 3 g of acetone, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/10 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 42의 (a)와 같으며, 500nm에서 흡수계수는 0.156이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.56이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 42의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1692, 0.1439)와 (0.0.1884, 0.2437) 이다. 도 42의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/10 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 42의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 42의 (f)이다. The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/10 is shown in FIG. 42 (a), and the absorption coefficient at 500 nm is 0.156. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.56. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 42B and 42C, respectively, and the color coordinates of fluorescence are (0.1692, 0.1439) and (0.0.1884, 0.2437), respectively. 42 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 42 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/10. Is (f) of FIG.
[실시예 43]Example 43
도 43은 본 발명의 방법으로 합성한 탄소양자점의 합성예 43의 특성을 정리한 결과로서, 표 2의 합성 예 43의 경우, 에탄올 37.5cc, 에틸렌글리콜 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. 43 shows the characteristics of Synthesis Example 43 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 43 of Table 2, 37.5 cc of ethanol, 3 g of ethylene glycol, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과용액을 1/15 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 43의 (a)와 같으며, 500nm에서 흡수계수는 0.252이다. 희석한 비율에 따라 환산하면 투과용액의 흡수계수는 3.78이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 43의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1951, 0.2402)와 (0.2221, 0.3180) 이다. 도 43의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/15 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 43의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 43의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a ratio of 1/15 is shown in FIG. 43 (a), and the absorption coefficient at 0.25 nm is 0.252. According to the diluted ratio, the absorption coefficient of the permeate solution is 3.78. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 43B and 43C, respectively, and the color coordinates of fluorescence are (0.1951, 0.2402) and (0.2221, 0.3180), respectively. 43 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of Figure 43 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing a solution diluted at a ratio of 1/15, and was taken by fluorescence by blue LED (460 nm). Is (f) of FIG.
[실시예 44]Example 44
도 44는 본 발명의 방법으로 합성한 탄소양자점의 합성예 44의 특성을 정리한 결과로서, 표 2의 합성 예 44의 경우, 에탄올 37.5cc, 전분 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. FIG. 44 shows the results of Synthesis Example 44 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 44 of Table 2, 37.5 cc of ethanol, 3 g of starch, and 1 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과용액을 1/56 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 44의 (a)와 같으며, 500nm에서 흡수계수는 0.699이다. 희석한 비율에 따라 환산하면 투과용액의 흡수계수는 39.1이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 44의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.2084, 0.2464)와 (0.2402, 0.3322) 이다. 도 44의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/56 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 44의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 44의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at 1/56 ratio is shown in FIG. 44 (a), and the absorption coefficient at 0.6 nm is 0.699. According to the diluted ratio, the absorption coefficient of permeate solution is 39.1. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 44B and 44C, respectively, and the color coordinates of fluorescence are (0.2084, 0.2464) and (0.2402, 0.3322), respectively. 44 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 44 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution diluted at the ratio of 1/56. Is (f) of FIG.
[실시예 45]Example 45
도 45는 본 발명의 방법으로 합성한 탄소양자점의 합성예 45의 특성을 정리한 결과로서, 표 2의 합성 예 45의 경우, 에탄올 45cc, 올레익산 3g, 질산 0.16g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 45 shows the results of Synthesis Example 45 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 45 of Table 2, 45 cc of ethanol, 3 g of oleic acid, and 0.16 g of nitric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 45의 (a)와 같으며, 500nm에서 흡수계수는 0.650이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 45의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1801, 0.1885)와 (0.1951, 2838) 이다. 도 45의 (d)는 합성한 용액이 담긴 시험관 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 45의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 45의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 45 (a), the absorption coefficient is 0.650 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 45B and 45C, respectively, and the color coordinates of fluorescence are (0.1801, 0.1885) and (0.1951, 2838), respectively. 45 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) from the bottom of the glass bottle containing the solution is shown in Figure 45 (e), and the photograph taken by fluorescence by the blue LED (460 nm) is shown in Figure 45 (f). to be.
[실시예 46]Example 46
도 46은 본 발명의 방법으로 합성한 탄소양자점의 합성예 46의 특성을 정리한 결과로서, 표 2의 합성 예 46의 경우, 2-프로판올 40cc, 아세틸아세톤 3g, 질산 3g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 46 shows the results of Synthesis Example 46 of the carbon quantum dots synthesized by the method of the present invention. The reaction was carried out while maintaining at 250 ℃ for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/20 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 46의 (a)와 같으며, 500nm에서 흡수계수는 0.214이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 4.27이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 46의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1778, 0.1724)와 (0.1956, 0.2712) 이다. 도 46의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/20 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 46의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 46의 (f)이다.The UV-Vis absorption spectrum of the solution diluted by the 1/20 ratio of the synthetic solution is shown in FIG. 46 (a), and the absorption coefficient at 0.2 nm is 0.214. Based on the diluted ratio, the absorption coefficient of the synthetic solution is 4.27. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 46B and 46C, respectively, and the color coordinates of fluorescence are (0.1778, 0.1724) and (0.1956, 0.2712), respectively. 46 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing a solution diluted at the 1/20 ratio is shown in (e) of FIG. 46, and the fluorescence was emitted by the blue LED (460 nm). Is (f) of FIG.
[실시예 47]Example 47
도 47은 본 발명의 방법으로 합성한 탄소양자점의 합성예 47의 특성을 정리한 결과로서, 표 2의 합성 예 47의 경우, n-프로판올 37.5cc, 아세틸아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 250℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 47 is a result of synthesizing the properties of Synthesis Example 47 of the carbon quantum dots synthesized by the method of the present invention. And reacted while maintaining at 250 ℃ for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/36 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 47의 (a)와 같으며, 500nm에서 흡수계수는 0.147이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 5.28이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 47의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1796, 0.1714)와 (0.2039, 0.2648) 이다. 도 47의 는 합성한 용액이 담긴 시험관 사진이다. 1/36 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 47의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 47의 (f)이다. The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a ratio of 1/36 is shown in FIG. 47 (a), and the absorption coefficient at 500 nm is 0.147. Converted according to the diluted ratio, the absorption coefficient of the synthetic solution is 5.28. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 47B and 47C, respectively, and the color coordinates of fluorescence are (0.1796, 0.1714) and (0.2039, 0.2648), respectively. 47 is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing a solution diluted at 1/36 ratio is shown in (e) of Figure 47, the photo was fluorescence by irradiation with a blue LED (460 nm). Is Fig. 47 (f).
[실시예 48]Example 48
도 48은 본 발명의 방법으로 합성한 탄소양자점의 합성예 48의 특성을 정리한 결과로서, 표 2의 합성 예 48의 경우, 클로로벤젠 37.5cc, 아세틸아세톤 3g, 질산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. FIG. 48 shows the results of Synthesis Example 48 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 48 of Table 2, 37.5 cc of chlorobenzene, 3 g of acetylacetone, and 1 g of nitric acid were mixed to the high pressure reactor. The reaction was carried out while maintaining at 245 ℃ for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과용액을 1/46 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 48의 (a)와 같으며, 500nm에서 흡수계수는 0.446이다. 희석한 비율에 따라 환산하면 투과용액의 흡수계수는 20.5이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 48의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1893, 0.2005)와 (0.2165, 0.2884) 이다. 도 48의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/46 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 48의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 48의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate solution at a 1/46 ratio is shown in FIG. 48 (a), and the absorption coefficient at 0.4 nm is 0.446. According to the diluted ratio, the absorption coefficient of the permeate solution is 20.5. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 48B and 48C, respectively, and the color coordinates of fluorescence are (0.1893, 0.2005) and (0.2165, 0.2884), respectively. 48 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 48 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the diluted solution at 1/46 ratio. Is (f) of FIG.
[실시예 49]Example 49
도 49는 본 발명의 방법으로 합성한 탄소양자점의 합성예 49의 특성을 정리한 결과로서, 표 2의 합성 예 49의 경우, 에탄올 37.5cc, 글루코스 3g, 황산 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. FIG. 49 shows the results of Synthesis Example 49 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 49 of Table 2, 37.5 cc of ethanol, 3 g of glucose, and 1 g of sulfuric acid were mixed and placed in a high pressure reactor. The reaction was maintained at 30 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/36비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 49의 (a)와 같으며, 500nm에서 흡수계수는 0.039이다. 희석한 비율에 따라 환산하면 투과액의 흡수계수는 1.42이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 49의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1795, 0.1848)와 (0.2148, 0.2917) 이다. 도 49의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/36 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 49의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 49의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a ratio of 1/36 is shown in FIG. 49 (a), and the absorption coefficient at 500 nm is 0.039. According to the diluted ratio, the absorption coefficient of the permeate is 1.42. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 49B and 49C, respectively, and the color coordinates of fluorescence are (0.1795, 0.1848) and (0.2148, 0.2917), respectively. 49 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing a solution diluted at 1/36 ratio is shown in (e) of FIG. 49, and the fluorescence was emitted by the blue LED (460 nm). Is FIG. 49 (f).
[실시예 50]Example 50
도 50은 본 발명의 방법으로 합성한 탄소양자점의 합성예 50의 특성을 정리한 결과로서, 표 2의 합성 예 50의 경우, 에탄올 40cc, 흰 설탕 1g, 칼륨보로하이드라이드(KBH4) 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 합성물을 포(pore) 크기가 0.2㎛인 멤브레인 필터로 여과하여 검은색 투과액을 분리하였다. FIG. 50 shows the properties of Synthesis Example 50 of the carbon quantum dots synthesized by the method of the present invention. In the Synthesis Example 50 of Table 2, ethanol 40 cc, white sugar 1 g, potassium borohydride (KBH 4 ) 1 g The mixture was put into a high pressure reactor and reacted while maintaining at 245 ℃ for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled. The composite was filtered through a membrane filter with a pore size of 0.2 μm to separate black permeate.
투과액을 1/36비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 50의 (a)와 같으며, 500nm에서 흡수계수는 0.294이다. 희석한 비율에 따라 환산하면 투과액의 흡수계수는 10.6이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 50의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.2051, 0.2260)와 (0.2416, 0.3150) 이다. 도 50의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/36 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 50의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 50의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the permeate at a 1/36 ratio is shown in FIG. 50 (a), and the absorption coefficient at 0.2 nm is 0.294. According to the diluted ratio, the absorption coefficient of the permeate is 10.6. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 50B and 50C, respectively, and the color coordinates of fluorescence are (0.2051, 0.2260) and (0.2416, 0.3150), respectively. 50 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 50 shows the fluorescence emitted by the ultraviolet LED (380 nm) and emitted from the bottom of the glass bottle containing the solution diluted at 1/36 ratio. Is (f) of FIG.
[실시예 51]Example 51
도 51은 본 발명의 방법으로 합성한 탄소양자점의 합성예 51의 특성을 정리한 결과로서, 표 2의 합성 예 51의 경우, 에탄올 40cc, 아세틸아세톤 3g, 칼륨보로하이드라이드(KBH4) 1g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. Fig. 51 shows the results of Synthesis Example 51 of the carbon quantum dots synthesized by the method of the present invention. In the case of Synthesis Example 51 of Table 2, ethanol 40cc, acetylacetone 3g, potassium borohydride (KBH 4 ) 1g The mixture was put into a high pressure reactor and reacted while maintaining at 245 ℃ for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/13비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 51의 (a)와 같으며, 500nm에서 흡수계수는 0.303이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 3.94이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 51의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.2286, 0.2540)와 (0.2667, 0.3235) 이다. 도 51의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/13 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 51의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 51의 (f)이다.The UV-Vis absorption spectrum of the diluted solution of the synthesis solution at 1/13 ratio is shown in FIG. 51 (a), and the absorption coefficient at 0.3 nm is 0.303. According to the diluted ratio, the absorption coefficient of the synthetic solution is 3.94. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 51B and 51C, respectively, and the color coordinates of fluorescence are (0.2286, 0.2540) and (0.2667, 0.3235), respectively. 51 (d) is a test tube photograph containing the synthesized solution. Photograph (e) of FIG. 51 (e) irradiated with ultraviolet LED (380 nm) to emit light from the bottom of the glass bottle containing a solution diluted at the ratio of 1/13 is (e), the photo taken with blue LED (460 nm) fluorescence Is (f) of FIG.
[실시예 52]Example 52
도 52는 본 발명의 방법으로 합성한 탄소양자점의 합성예 52의 특성을 정리한 결과로서, 표 2의 합성 예 52의 경우, 에탄올 37.5cc, 벤젠 3g, 칼륨보로하이드라이드(KBH4) 0.69g을 혼합하여 고압반응기에 넣고 245℃에서 30시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. 52 is a result of synthesizing the properties of Synthesis Example 52 of the carbon quantum dot synthesized by the method of the present invention; in the Synthesis Example 52 of Table 2, 37.5 cc of ethanol, 3 g of benzene, and potassium borohydride (KBH 4 ) 0.69 The mixture was mixed and placed in a high pressure reactor to react at 245 ° C. for 30 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액을 1/11 비율로 희석한 용액의 UV-Vis 흡수스펙트럼은 도 52의 (a)와 같으며, 500nm에서 흡수계수는 0.142이다. 희석한 비율에 따라 환산하면 합성용액의 흡수계수는 1.56이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 52의 (c)와 같으며 형광의 색좌표는 각각 (0.1853, 0.1906)와 (0.2199, 0.2992) 이다. 도 52의 (d)는 합성한 용액이 담긴 시험관 사진이다. 1/11 비율로 희석한 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 52의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 52의 (f)이다.The UV-Vis absorption spectrum of the solution obtained by diluting the synthetic solution at a 1/11 ratio is shown in FIG. 52 (a), and the absorption coefficient at 500 nm is 0.142. According to the diluted ratio, the absorption coefficient of the synthetic solution is 1.56. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIG. 52 (c), respectively, and the color coordinates of fluorescence are (0.1853, 0.1906) and (0.2199, 0.2992), respectively. (D) of FIG. 52 is a test tube photograph containing the synthesized solution. Photograph (e) of Figure 52 (e) shows the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution diluted at the ratio of 1/11 is a photo taken by the blue LED (460 nm). Is (f) of FIG.
[실시예 53]Example 53
도 53은 본 발명의 방법으로 합성한 탄소양자점의 합성예 53의 특성을 정리한 결과로서, 표 2의 합성 예 53의 경우, 에탄올 45cc, 아세틸아세톤 3g, Fe2O3 나노입자 0.3g을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 53 shows the results of Synthesis Example 53 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 53 of Table 2, 45 cc of ethanol, 3 g of acetylacetone, and 0.3 g of Fe 2 O 3 nanoparticles were mixed. The reaction mixture was placed in a high pressure reactor and maintained at 250 ° C. for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 53의 (a)와 같으며, 500nm에서 흡수계수는 0.047이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 53의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1781, 0.1751)와 (0.2045, 0.2750) 이다. 도 53의 (d)는 합성한 용액이 담긴 시험관 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 53의 (e)이며, 청색LED(460nm)로 조사하여 형광을 찍은 사진은 도 53의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 53 (a), the absorption coefficient is 0.047 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 53B and 53C, respectively, and the color coordinates of fluorescence are (0.1781, 0.1751) and (0.2045, 0.2750), respectively. Figure 53 (d) is a test tube picture containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution is shown in Figure 53 (e), the fluorescence emitted by the blue LED (460 nm) is shown in Figure 53 (f). to be.
[실시예 54]Example 54
도 54는 본 발명의 방법으로 합성한 탄소양자점의 합성예 54의 특성을 정리한 결과로서, 표 2의 합성 예 54의 경우, 에탄올 42.5cc, 아세틸아세톤 3g, 초산0.5cc을 혼합하여 고압반응기에 넣고 250℃에서 35시간 동안 유지하면서 반응하였다. 반응 중 용액을 균일하게 유지하기 위하여 처음 9시간 동안 200rpm으로 자기 교반하였다. 반응이 끝난 고압반응기는 자연 냉각하였다. FIG. 54 shows the results of Synthesis Example 54 of the carbon quantum dots synthesized by the method of the present invention. In the synthesis example 54 of Table 2, 42.5 cc of ethanol, 3 g of acetylacetone, and 0.5 cc of acetic acid were mixed. The reaction was carried out while maintaining at 250 ℃ for 35 hours. The mixture was magnetically stirred at 200 rpm for the first 9 hours to keep the solution uniform during the reaction. After the reaction, the high pressure reactor was naturally cooled.
합성용액의 UV-Vis 흡수스펙트럼은 도 54의 (a)와 같으며, 500nm에서 흡수계수는 0.0173이다. 365nm와 400nm의 광으로 여기하여 측정한 형광스펙트럼은 각각 도 54의 (b), (c)와 같으며 형광의 색좌표는 각각 (0.1745, 0.1637)와 (0.1988, 0.2505)이다. 도 54의 (d)는 합성한 용액이 담긴 시험관 사진이다. 용액이 든 유리병의 아래쪽에서 자외선 LED(380nm)로 조사하여 방출하는 형광을 찍은 사진은 도 54의 (e)이며, 청색 LED(460nm)로 조사하여 형광을 찍은 사진은 도 54의 (f)이다.UV-Vis absorption spectrum of the synthetic solution is shown in Figure 54 (a), the absorption coefficient is 0.0173 at 500nm. Fluorescence spectra measured by excitation with light at 365 nm and 400 nm are shown in FIGS. 54B and 54C, respectively, and the color coordinates of fluorescence are (0.1745, 0.1637) and (0.1988, 0.2505), respectively. 54 (d) is a test tube photograph containing the synthesized solution. The photograph of the fluorescence emitted by the ultraviolet LED (380 nm) emitted from the bottom of the glass bottle containing the solution is shown in Figure 54 (e), the fluorescence emitted by the blue LED (460 nm) is shown in Figure 54 (f). to be.
지금까지 본 발명에 따른 구체적인 실시예에 관하여 설명하였으나, 본 발명의 범위에서 벗어나지 않는 한도 내에서는 여러 가지 변형이 가능함은 물론이다. 그러므로, 본 발명의 범위는 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 특허 청구의 범위뿐 아니라 이 특허 청구의 범위와 균등한 것들에 의해 정해져야 한다.While specific embodiments of the present invention have been described so far, various modifications are possible without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below, but also by the equivalents of the claims.
이상과 같이 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 이는 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다. 따라서, 본 발명 사상은 아래에 기재된 특허청구범위에 의해서만 파악되어야 하고, 이의 균등 또는 등가적 변형 모두는 본 발명 사상의 범주에 속한다고 할 것이다.As described above, the present invention has been described by way of limited embodiments and drawings, but the present invention is not limited to the above-described embodiments, which can be variously modified and modified by those skilled in the art to which the present invention pertains. Modifications are possible. Accordingly, the spirit of the present invention should be understood only by the claims set forth below, and all equivalent or equivalent modifications thereof will belong to the scope of the present invention.

Claims (6)

  1. 유기화합물과, Organic compounds,
    메탄올, 에탄올, 2-프로판올, n- 프로판올, 과산화수소, 클로로벤젠 중 어느 하나 이상인 용매와,Solvents of any one or more of methanol, ethanol, 2-propanol, n-propanol, hydrogen peroxide and chlorobenzene,
    촉진제를 혼합하여 용액을 만드는 단계; 및 Mixing the promoter to make a solution; And
    상기 용액을 220℃ 이상의 온도에서 고압반응기를 사용하여 가열하는 단계를 포함하는 탄소양자점 제조방법.Carbon quantum dot manufacturing method comprising the step of heating the solution using a high pressure reactor at a temperature of 220 ℃ or more.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 촉진제가 산화제, 환원제, 촉매 중 어느 하나 이상인 것을 특징으로 하는 탄소양자점 제조방법.The accelerator is a carbon quantum dot production method, characterized in that any one or more of an oxidizing agent, a reducing agent, a catalyst.
  3. 제 2 항에 있어서,The method of claim 2,
    상기 산화제가 질산, 황산, 과산화수소 중 어느 하나 이상인 것을 특징으로 하는 탄소양자점 제조방법.Carbon quantum dot production method characterized in that the oxidizing agent is any one or more of nitric acid, sulfuric acid, hydrogen peroxide.
  4. 제 2 항에 있어서, The method of claim 2,
    상기 환원제가 칼륨보로하이드라이드인 것을 특징으로 하는 탄소양자점 제조방법.Carbon quantum dot production method characterized in that the reducing agent is potassium borohydride.
  5. 제 2 항에 있어서, The method of claim 2,
    상기 촉매가 Fe2O3 나노입자인 것을 특징으로 하는 탄소양자점 제조방법.Carbon catalyst quantum dot production method characterized in that the catalyst is Fe 2 O 3 nanoparticles.
  6. 제 1 항에 있어서,The method of claim 1,
    상기 유기화합물이 설탕, 전분, 비타민 C, 글루코스, 주석산, 구연산, 올레익산, 글루타민, 글루타민산, 요소, 벤젠, 아세틸아세톤, 아세토페논, 초산 중 어느 하나 이상인 것을 특징으로 하는 탄소양자점 제조방법.Method of producing a carbon quantum dot, characterized in that the organic compound is any one or more of sugar, starch, vitamin C, glucose, tartaric acid, citric acid, oleic acid, glutamine, glutamic acid, urea, benzene, acetylacetone, acetophenone, acetic acid.
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