CN113583668A - Preparation method of environment-friendly graphene quantum dots - Google Patents
Preparation method of environment-friendly graphene quantum dots Download PDFInfo
- Publication number
- CN113583668A CN113583668A CN202110879052.0A CN202110879052A CN113583668A CN 113583668 A CN113583668 A CN 113583668A CN 202110879052 A CN202110879052 A CN 202110879052A CN 113583668 A CN113583668 A CN 113583668A
- Authority
- CN
- China
- Prior art keywords
- graphene quantum
- mesoporous silica
- quantum dots
- graphene
- quantum dot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 58
- 239000002096 quantum dot Substances 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 18
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000174 gluconic acid Substances 0.000 claims description 9
- 235000012208 gluconic acid Nutrition 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 9
- 229960004889 salicylic acid Drugs 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 7
- 230000005284 excitation Effects 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 238000012984 biological imaging Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000006552 photochemical reaction Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000000502 dialysis Methods 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BXOXVTWMJCUYLW-UHFFFAOYSA-N 1,3,6-trinitropyrene Chemical compound C1=C2C([N+](=O)[O-])=CC=C(C=C3)C2=C2C3=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 BXOXVTWMJCUYLW-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides an environment-friendly preparation method of graphene quantum dots. According to the method, mesoporous silica is used as a template to limit growth and agglomeration of graphene quantum dots in ultraviolet radiation synthesis, a large number of aromatic free radicals are generated through first ultraviolet excitation, the aromatic free radicals generate fragmented two-dimensional graphene through coupling recombination, then hydrogen peroxide is excited through second ultraviolet excitation to generate high-activity free radicals, photochemical reaction is carried out, the fragmented two-dimensional graphene is converted into the graphene quantum dots, and the graphene quantum dots with controllable particle sizes are obtained. The preparation method of the environment-friendly graphene quantum dot has the advantages of simple steps, cheap and easily-obtained raw materials, environmental friendliness, uniform size of the prepared graphene quantum dot, good light and heat stability, high fluorescence intensity, strong photobleaching resistance, low toxicity and controllable emission wavelength, and is expected to replace inorganic quantum dots to be applied to the fields of biological analysis, biological imaging and the like.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of an environment-friendly graphene quantum dot.
Background
The graphene quantum dot is a quasi-zero-dimensional nano material, and because the movement of electrons in the graphene quantum dot in all directions is limited, the quantum confinement effect of the graphene quantum dot is very obvious, and the unique physicochemical property of the graphene quantum dot brings revolutionary changes to the application of the graphene quantum in the fields of electronics, photoelectricity and electromagnetism. Compared with the traditional fluorescent material, the graphene quantum dot has the outstanding advantages of extremely high biocompatibility, fluorescence stability, controllable emission wavelength, wide excitation wavelength range, low biotoxicity, good solubility and the like, so that the graphene quantum dot becomes a good biological imaging probe, and therefore, the graphene quantum dot can be widely applied to the aspects of biosensing, biological imaging, biological drug delivery and the like.
At present, graphene quantum dots mainly have two synthesis paths of 'top-down' and 'bottom-up', a top-down method is to cut and peel off single graphite microcrystals by a physical or chemical means to obtain the graphene quantum dots, but a strong oxidant and acid are inevitably used in the process of the graphene quantum dots to cause great pollution to the environment, a bottom-up method is to synthesize the graphene quantum dots by pyrolyzing or carbonizing organic micromolecules under specific conditions, but the crystallinity of the graphene quantum dots generated by a traditional solvothermal bottom-up method is poor, and the problem that the solvothermal process belongs to a disordered polymerization process is particularly necessary to develop an environment-friendly and efficient method for synthesizing the graphene quantum dots.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an environment-friendly preparation method of graphene quantum dots, and solves the problem that a universal environment-friendly method for preparing high-crystallinity graphene quantum dots is not available.
(II) technical scheme
Based on the above, the invention provides an environment-friendly preparation method of graphene quantum dots, which comprises the following steps:
(1) adding mesoporous silica and a precursor into an ethanol solution, stirring, and performing centrifugal separation to obtain mesoporous silica with the precursor adsorbed in a pore channel;
(2) adding the mesoporous silica with the precursor adsorbed in the pore channel prepared in the step (1) into absolute ethyl alcohol, and carrying out ultraviolet radiation under the condition of magnetic stirring to obtain the mesoporous silica with fragmented graphene in the pore channel;
(3) adding the mesoporous silica containing fragmented graphene in the pore canal prepared in the step (2) and hydrogen peroxide into absolute ethyl alcohol, then carrying out ultraviolet radiation, and finally carrying out centrifugal separation to obtain the mesoporous silica containing graphene quantum dots in the pore canal;
(4) and (4) etching the mesoporous silica containing the graphene quantum dots in the pore channels prepared in the step (3) by hydrofluoric acid to obtain the graphene quantum dots.
Preferably, the pores of the mesoporous silica in the step (1) are 2-10 nm;
preferably, the precursor in step (1) is a natural extract capable of generating aromatic free radicals under ultraviolet irradiation, including but not limited to salicylic acid, gluconic acid;
preferably, the mass ratio of the mesoporous silicon dioxide, the precursor and the ethanol solution in the step (1) is 10:3-5: 30-45;
preferably, the stirring condition in the step (1) is stirring at room temperature for 2-4 h;
preferably, the mass ratio of the mesoporous silica with the precursor adsorbed in the step (2) to the deionized water is 10: 40-60;
preferably, the ultraviolet radiation in the step (2) is performed under the ultraviolet light of 180-;
preferably, the ratio of the mesoporous silica containing fragmented graphene in the pore channel in the step (3), hydrogen peroxide and absolute ethyl alcohol is 10:50-150: 100-;
preferably, the ultraviolet radiation in the step (3) is irradiated for 1-1.5h under the ultraviolet light of 180-500nm and 200-500W;
preferably, the mass ratio of the mesoporous silica containing the graphene quantum dots in the pore channel in the step (4) to the hydrofluoric acid is 10: 50-80;
preferably, the concentration of the hydrofluoric acid solution in the step (4) is 3% -10%, and the etching time is 1-2 days.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
(1) according to the preparation method of the environment-friendly graphene quantum dot, the mesoporous silica is used as the template, the increase size of the graphene quantum dot in the synthesis of the precursor in the mesoporous silica under the irradiation of ultraviolet light is limited, the agglomeration problem is improved, and the graphene quantum dot with controllable particle size can be obtained.
(2) According to the preparation method of the environment-friendly graphene quantum dot, a large amount of free radical high-light-energy photons are generated by exciting the wavelength between solvent molecules through first ultraviolet, salicylic acid or gluconic acid rapidly captures free radicals and generates a large amount of secondary aromatic free radicals, the secondary aromatic free radicals generate anthracene nuclei bonded to the edge of graphene through coupling recombination, the reaction is continued to obtain fragmented two-dimensional graphene, then hydrogen peroxide is excited through second ultraviolet excitation to generate high-activity free radicals, photochemical reaction is carried out, and the fragmented two-dimensional graphene is converted into the graphene quantum dot.
(3) The preparation method of the environment-friendly graphene quantum dot is simple, the raw materials are cheap and easy to obtain, the environment is protected, the prepared graphene quantum dot is uniform in size, and the environment-friendly graphene quantum dot not only has good thermal stability and light stability, but also has the characteristics of high fluorescence intensity, strong photobleaching resistance, low toxicity and controllable emission wavelength, and is expected to replace inorganic quantum dots to be applied to the fields of biological analysis, biological imaging and the like.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples:
an environment-friendly preparation method of graphene quantum dots comprises the following steps:
example 1
(1) Firstly, 10g of mesoporous silica with a pore passage of 5nm and 4g of salicylic acid are added into 35g of ethanol solution, stirred for 3.5 hours at room temperature, and centrifugally separated to obtain the mesoporous silica with salicylic acid adsorbed in the pore passage;
(2) adding 10g of mesoporous silica with salicylic acid adsorbed in the pore channel prepared in the step (1) into 50ml of absolute ethyl alcohol, and irradiating for 1h under the ultraviolet light of 300W at 350nm under the condition of magnetic stirring to obtain the mesoporous silica with fragmented graphene in the pore channel;
(3) adding 8g of mesoporous silica containing fragmented graphene in the pore channel prepared in the step (2) and 100g of hydrogen peroxide into 120g of absolute ethyl alcohol, irradiating for 1.5h under ultraviolet light of 300W at 350nm, and finally performing centrifugal separation to obtain mesoporous silica containing graphene quantum dots in the pore channel;
(4) and (3) etching 5g of mesoporous silica containing the graphene quantum dots in the pore channels prepared in the step (3) for 1 day by 30g of hydrofluoric acid with the concentration of 8% to obtain the graphene quantum dots.
Example 2
An environment-friendly preparation method of graphene quantum dots comprises the following steps:
(1) adding 8g of mesoporous silica with a pore passage of 8nm and 4g of salicylic acid into 35g of ethanol solution, stirring for 4 hours at room temperature, and performing centrifugal separation to obtain the mesoporous silica with salicylic acid adsorbed in the pore passage;
(2) adding 6g of mesoporous silica with salicylic acid adsorbed in the pore channel prepared in the step (1) into 35ml of absolute ethyl alcohol, and irradiating for 1h under the ultraviolet light of 400W at 300nm under the condition of magnetic stirring to obtain the mesoporous silica with fragmented graphene in the pore channel;
(3) adding 5g of mesoporous silica containing fragmented graphene in the pore channel prepared in the step (2) and 50g of hydrogen peroxide into 75g of absolute ethyl alcohol, irradiating for 1.5h under ultraviolet light of 300W at 350nm, and finally performing centrifugal separation to obtain mesoporous silica containing graphene quantum dots in the pore channel;
(4) and (3) etching 3.5g of mesoporous silica containing the graphene quantum dots in the pore channels prepared in the step (3) for 2 days by 35g of hydrofluoric acid with the concentration of 5% to obtain the graphene quantum dots.
Example 3
An environment-friendly preparation method of graphene quantum dots comprises the following steps:
(1) adding 10g of mesoporous silica with a pore passage of 10nm and 4g of gluconic acid into 35g of ethanol solution, stirring at room temperature for 3.5h, and performing centrifugal separation to obtain the mesoporous silica with the gluconic acid adsorbed in the pore passage;
(2) adding 10g of mesoporous silica with gluconic acid adsorbed in the pore channel prepared in the step (1) into 50ml of absolute ethyl alcohol, and irradiating for 1h under the ultraviolet light of 300W at 350nm under the condition of magnetic stirring to obtain the mesoporous silica with fragmented graphene in the pore channel;
(3) adding 8g of mesoporous silica containing fragmented graphene in the pore channel prepared in the step (2) and 100g of hydrogen peroxide into 120g of absolute ethyl alcohol, irradiating for 1.5h under ultraviolet light of 300W at 350nm, and finally performing centrifugal separation to obtain mesoporous silica containing graphene quantum dots in the pore channel;
(4) and (3) etching 5g of mesoporous silica containing the graphene quantum dots in the pore channels prepared in the step (3) for 1.5 days by 30g of hydrofluoric acid with the concentration of 8% to obtain the graphene quantum dots.
Example 4
An environment-friendly preparation method of graphene quantum dots comprises the following steps:
(1) adding 7.5g of mesoporous silica with a pore passage of 4nm and 3.5g of gluconic acid into 40g of ethanol solution, stirring for 3 hours at room temperature, and performing centrifugal separation to obtain the mesoporous silica with the gluconic acid adsorbed in the pore passage;
(2) adding 5g of mesoporous silica with gluconic acid adsorbed in the pore channel prepared in the step (1) into 30ml of absolute ethyl alcohol, and irradiating for 0.5h under ultraviolet light of 350W at 250nm under the condition of magnetic stirring to obtain mesoporous silica with fragmented graphene in the pore channel;
(3) adding 4g of mesoporous silica containing fragmented graphene in the pore channel prepared in the step (2) and 40g of hydrogen peroxide into 50g of absolute ethyl alcohol, irradiating for 1h under the ultraviolet light of 280nm and 450W, and finally performing centrifugal separation to obtain mesoporous silica containing graphene quantum dots in the pore channel;
(4) and (3) etching 3g of mesoporous silica containing the graphene quantum dots in the pore channels prepared in the step (3) for 2 days by 20g of hydrofluoric acid with the concentration of 7.5% to obtain the graphene quantum dots.
Comparative example 1
A method for preparing graphene quantum dots under the assistance of microwaves comprises the following steps:
(1) 1,3, 6-trinitropyrene is used as a precursor, 0.5g of 1,3, 6-trinitropyrene is uniformly dispersed in 50mL of water under the ultrasonic condition to form a precursor solution, and then 5mL of NaOH solution with the molar concentration of 1M is used for adjusting the pH value of the precursor solution to be alkaline; continuing ultrasonic dispersion to uniformly mix the alkaline precursor solution; then transferring the alkaline precursor solution into a quartz microwave reaction tube with the volume of 100mL, and reacting in an Antopa microwave 400 instrument under the conditions that: under the condition of applying microwaves at the temperature of 180 ℃, taking an alkaline precursor solution as a reaction liquid system, and carrying out rapid reaction for 5min by directly heating the solution by microwaves to obtain a graphene quantum dot product mixed solution;
(2) and (2) after the mixed solution of the graphene quantum dot products prepared in the step (1) is cooled, carrying out purification treatment: taking the graphene quantum dot product mixed solution out of the reaction tube, filtering with a microporous filter membrane with the micropore size of 220nm, transferring the filtered filtrate into a dialysis bag for dialysis treatment, removing unreacted precursors and insoluble intermediate products, finally obtaining a purified graphene quantum dot solution containing the graphene quantum dots, and drying in vacuum to obtain the graphene quantum dots.
Comparative example 2
A preparation method of graphene quantum dots comprises the following steps:
(1) adding 1g of glucose into 40ml of deionized water to fully dissolve the glucose, adding 0.7ml of ammonia water, uniformly mixing to obtain a mixed solution A, putting 2ml of the mixed solution A into a 4ml of glass bottle covered and sealed, heating for 3min in microwave with the heating power of 640W to obtain a reaction solution, taking 10ml of the reaction solution, performing dialysis treatment by using a dialysis bag with the molecular weight cutoff of 1000, replacing the solution with deionized water for 24h, and replacing the solution twice to obtain a graphene quantum dot solution;
(2) adding 1ml of deionized water into 0.8g of sodium silicate, fully dissolving to obtain a sodium silicate aqueous solution, adding 2.5ml of graphene quantum dot solution into the sodium silicate aqueous solution, stirring with a glass rod for 10min to obtain a mixed solution B, placing the mixed solution B in a microwave oven for microwave heating, setting the heating power to be 640W, heating for 5min, taking out, and cooling to obtain the graphene quantum dot solid. And grinding the graphene quantum dot solid for 2h by using a grinding pot to obtain solid powder graphene quantum dots.
Detection of
1) The statistical results of the particle size distribution of each of the graphene quantum dots prepared in examples 1 to 4 and comparative examples 1 to 2 were obtained by observation with a transmission electron microscope, and are shown in table 1.
Table 1:
the embodiments 1 to 4 of the present invention are prepared in mesoporous silica having sizes of 5nm, 8nm, 10nm and 4nm, and as can be seen from table 1, the sizes of more than 70% of the graphene quantum dots in the embodiments 1 to 4 are in accordance with the sizes of the mesoporous silica, which indicates that the graphene quantum dots prepared by the present invention have uniform sizes and can obtain the graphene quantum dots with controllable particle sizes, whereas the sizes of the graphene quantum dots prepared by the comparative examples 1 to 2 are dispersed, and thus the sizes of the graphene quantum dots are difficult to control.
2) Each of the graphene quantum dots prepared in examples 1 to 4 and comparative examples 1 to 2 was prepared as a 1mg/ml aqueous graphene quantum dot solution, and both the examples and comparative examples were yellow solutions when observed under visible light, and had no fluorescence effect when observed in the dark, but had bright fluorescence effect under ultraviolet lamp irradiation, and the solutions appeared yellow-green, and then the examples and comparative examples were subjected to ultraviolet-visible absorption spectroscopy, and the results obtained are shown in table 2.
Table 2:
as can be seen from Table 2, the fluorescence intensities of the graphite quantum dots prepared in examples 1-4 and comparative examples 1-2 change with the change of the excitation wavelength, and are all increased when the excitation wavelength is increased, while the fluorescence intensities of the graphene quantum dots prepared in examples 1-4 under the ultraviolet excitation light with the wavelength of 320-380nm are all greater than those of comparative examples 1-2 at the maximum, which indicates that the graphene quantum dots prepared by the invention have the characteristic of high fluorescence intensity.
In conclusion, the preparation method of the environment-friendly graphene quantum dot provided by the invention has the advantages that mesoporous silica is used as the template, the growth and agglomeration of the graphene quantum dot in ultraviolet radiation synthesis are limited, the graphene quantum dot with controllable particle size is obtained, the preparation method is simple, the raw materials are cheap and easy to obtain, the environment is protected, the size of the prepared graphene quantum dot is uniform, the prepared graphene quantum dot not only has good thermal stability and light stability, but also has high fluorescence intensity, and the preparation method is expected to replace inorganic quantum dots to be applied to the fields of biological analysis, biological imaging and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. An environment-friendly graphene quantum dot preparation method is characterized by comprising the following steps:
(1) adding mesoporous silica and a precursor into an ethanol solution, stirring, and performing centrifugal separation to obtain mesoporous silica with the precursor adsorbed in a pore channel;
(2) adding the mesoporous silica with the precursor adsorbed in the pore channel prepared in the step (1) into absolute ethyl alcohol, and carrying out ultraviolet radiation under the condition of magnetic stirring to obtain the mesoporous silica with fragmented graphene in the pore channel;
(3) adding the mesoporous silica containing fragmented graphene in the pore canal prepared in the step (2) and hydrogen peroxide into absolute ethyl alcohol, then carrying out ultraviolet radiation, and finally carrying out centrifugal separation to obtain the mesoporous silica containing graphene quantum dots in the pore canal;
(4) and (4) etching the mesoporous silica containing the graphene quantum dots in the pore channels prepared in the step (3) by hydrofluoric acid to obtain the graphene quantum dots.
2. The method for preparing the environmentally-friendly graphene quantum dot according to claim 1, wherein the pore channel of the mesoporous silica is 2-10 nm.
3. The method for preparing environmentally friendly graphene quantum dots according to claim 1, wherein the precursor in the step (1) is a natural extract capable of generating aromatic radicals under ultraviolet irradiation, including but not limited to salicylic acid and gluconic acid.
4. The preparation method of the environmentally-friendly graphene quantum dot according to claim 1, wherein the mass ratio of the mesoporous silica to the precursor to the ethanol solution is 10:3-5: 30-45.
5. The method for preparing the environmentally friendly graphene quantum dot according to claim 1, wherein the stirring condition in the step (1) is stirring at room temperature for 2-4 h.
6. The method for preparing the environmentally-friendly graphene quantum dot according to claim 1, wherein the mass ratio of the mesoporous silica with the precursor adsorbed in the step (2) to the deionized water is 10: 40-60.
7. The method as claimed in claim 1, wherein the ultraviolet radiation in step (2) is performed under the conditions of 180-260nm and 200-500W for 0.5-1 h.
8. The method as claimed in claim 1, wherein the ratio of mesoporous silica, hydrogen peroxide and absolute ethyl alcohol in the pore channel containing fragmented graphene is 10:50-150: 100-200.
9. The method as claimed in claim 1, wherein the ultraviolet radiation in step (3) is performed under the conditions of 500nm at 180 nm and 500W at 200-.
10. The method for preparing the environmentally-friendly graphene quantum dot according to claim 1, wherein the mass ratio of mesoporous silica containing the graphene quantum dot in the pore channel in the step (4) to hydrofluoric acid is 10:50-80, the concentration of the hydrofluoric acid solution in the step (4) is 3% -10%, and the etching time is 1-2 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110879052.0A CN113583668A (en) | 2021-08-02 | 2021-08-02 | Preparation method of environment-friendly graphene quantum dots |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110879052.0A CN113583668A (en) | 2021-08-02 | 2021-08-02 | Preparation method of environment-friendly graphene quantum dots |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113583668A true CN113583668A (en) | 2021-11-02 |
Family
ID=78253627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110879052.0A Pending CN113583668A (en) | 2021-08-02 | 2021-08-02 | Preparation method of environment-friendly graphene quantum dots |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113583668A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724435A (en) * | 2022-12-15 | 2023-03-03 | 深圳先进电子材料国际创新研究院 | Silicon dioxide powder and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591163A (en) * | 2014-12-29 | 2015-05-06 | 上海交通大学 | Graphene preparation method based on soft-hard mold plates |
| CN107098336A (en) * | 2017-04-28 | 2017-08-29 | 成都川烯科技有限公司 | A kind of method that graphene quantum dot is prepared based on photochemical method |
| CN107236541A (en) * | 2017-07-14 | 2017-10-10 | 河北民族师范学院 | The preparation method of nitrogen-doped graphene quantum dot and the detection method of ascorbic acid |
| CN112354357A (en) * | 2020-06-04 | 2021-02-12 | 长沙理工大学 | Bimetal doped graphene nano material and application thereof |
-
2021
- 2021-08-02 CN CN202110879052.0A patent/CN113583668A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591163A (en) * | 2014-12-29 | 2015-05-06 | 上海交通大学 | Graphene preparation method based on soft-hard mold plates |
| CN107098336A (en) * | 2017-04-28 | 2017-08-29 | 成都川烯科技有限公司 | A kind of method that graphene quantum dot is prepared based on photochemical method |
| CN107236541A (en) * | 2017-07-14 | 2017-10-10 | 河北民族师范学院 | The preparation method of nitrogen-doped graphene quantum dot and the detection method of ascorbic acid |
| CN112354357A (en) * | 2020-06-04 | 2021-02-12 | 长沙理工大学 | Bimetal doped graphene nano material and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JINLI ZHU等: "Green, Rapid, and Universal Preparation Approach of Graphene Quantum Dots under Ultraviolet Irradiation", 《ACS APPL. MATER. INTERFACES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724435A (en) * | 2022-12-15 | 2023-03-03 | 深圳先进电子材料国际创新研究院 | Silicon dioxide powder and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102807209B (en) | Method for preparing graphene quantum dots | |
| De et al. | A green and facile approach for the synthesis of water soluble fluorescent carbon dots from banana juice | |
| EP3085665B1 (en) | Large-scale preparation method for graphene quantum dots | |
| CN107418567B (en) | Biomass-based carbon quantum dot and preparation method thereof | |
| CN106044743B (en) | A kind of preparation method and applications of the Water-soluble carbon quantum dot based on egg shell membrane | |
| CN108128767A (en) | A kind of method and its application that carbon quantum dot is quickly prepared in room temperature environment | |
| CN107522190B (en) | Synthesis method of carbon quantum dots | |
| Liu et al. | A review of carbon dots in synthesis strategy | |
| CN104530089B (en) | Fluorescent molecular TPCA and preparation method thereof | |
| CN106829922A (en) | A kind of method for synthesizing carbon quantum dot as carbon source with polyethyleneimine | |
| CN111072013A (en) | Green method for preparing graphene quantum dots by using phloroglucinol | |
| CN113583668A (en) | Preparation method of environment-friendly graphene quantum dots | |
| CN105664955A (en) | Preparation method of copper-zinc co-doped carbon dots | |
| CN103275701B (en) | Dendritic molecule-modified fluorescent quantum dots, and preparation method and application thereof | |
| CN109941989A (en) | A kind of method that hydro-thermal method prepares nitrogen-doped graphene quantum dot | |
| CN113403068A (en) | Fused carbon dot, preparation method and application thereof | |
| CN107722974B (en) | Preparation method of biomass tar derived carbon quantum dots | |
| CN108014850B (en) | Preparation method and application of tetracarboxyphenyl porphyrin supramolecular photocatalyst | |
| Jiu et al. | The synthesis and photoluminescence property of YPO4: Eu3+ hollow microspheres | |
| CN110550617B (en) | Preparation method of carbon quantum dots | |
| CN108358187A (en) | A kind of preparation method of the golden yellow fluorescent carbon point of hair | |
| CN115851271B (en) | Preparation method of nitrogen-doped fluorescent carbon dots | |
| CN115057428B (en) | Hydrophobic near-infrared emission carbon quantum dot and preparation method and application thereof | |
| CN109704312B (en) | Preparation method of water-soluble blue-green fluorescent graphene quantum dots | |
| Huang et al. | Chaos to order: an eco-friendly way to synthesize graphene quantum dots |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211102 |