CN106566534A - Red-light carbon dot of high yield and high quantum yield, and preparation method thereof - Google Patents
Red-light carbon dot of high yield and high quantum yield, and preparation method thereof Download PDFInfo
- Publication number
- CN106566534A CN106566534A CN201610965433.XA CN201610965433A CN106566534A CN 106566534 A CN106566534 A CN 106566534A CN 201610965433 A CN201610965433 A CN 201610965433A CN 106566534 A CN106566534 A CN 106566534A
- Authority
- CN
- China
- Prior art keywords
- carbon
- yield
- preparation
- hongguang
- quantum
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 125000000524 functional group Chemical group 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 40
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- -1 amino, carboxyl Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000011852 carbon nanoparticle Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002096 quantum dot Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 14
- 235000015165 citric acid Nutrition 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 230000000875 corresponding effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 206010008342 Cervix carcinoma Diseases 0.000 description 1
- 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 1
- 208000006105 Uterine Cervical Neoplasms Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 201000010881 cervical cancer Diseases 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000004940 nucleus Anatomy 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000000439 tumor marker Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a red-light carbon dot of high yield and high quantum yield, and a preparation method thereof. The preparation method is used for the large-scale synthesis of carbon dots, wherein the carbon dots are emitted within the red-light area (with the peak value thereof between 610-661 nm) and the quantum yield is 76% which is highest at present. The particle sizes of carbon nano particles are within 2-8 nm, and the carbon nano particles are mainly composed of a graphitized carbon core and an amorphous functional group shell. Meanwhile, the carbon nano particles are good in luminous efficiency, solubility and stability in common solvents. As a novel type of red fluorescent materials, the red-light carbon dot has the advantages of low production cost, large-scale preparation, extremely high luminous efficiency, good stability and other excellent properties. The red-light carbon dot is a most promising material for replacing conventional semiconductor quantum dots and serves as a low-toxicity nano new material in the fields of optoelectronic devices, fluorescent sensing and biological technology.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of HONGGUANG carbon point with high yield and quantum yield
And preparation method thereof.
Background technology
21 century is the epoch for being filled with opportunities and challenges, and the fields such as information, the energy, environment and national defence are sent out
Exhibition is put forward higher requirement, so as to Materials it is also proposed with the requirement all entered with day.Wherein, the miniaturization of device, intelligence
Energyization requires that the size of material is less and less, therefore nano material is rapidly become in new material research field to the future economy
With the object of study of social development important, be also in contemporary basic research the most enliven, closest to practical application
Field.Different from bulk material, nano material has the property of many uniquenesses, is even more as the photoluminescent property of one of them and is subject to
Strong research interest.In recent years, the semiconductor-quantum-point such as CdSe, ZnS and CdSe related core-shell structure nanometer particle because
Its unique optical property and extensive biomedical applications prospect have attracted everybody widely to pay close attention to.Semiconductor-quantum-point is being given birth to
Fluorescence imaging on thing repeatedly confirmed under lab, and clinically carries out the application of tumor marker and cutting all
There is successful precedent.However, this kind of quantum dot is all with heavy metal as indispensable element, particularly Cd, even if extremely low dense
Use under degree, also can bring huge harm to natural environment and human health, so as to limit this kind of semiconductor-quantum-point
Application potential, development and application particularly clinically.So, find a kind of brand-new, with preferable optical property, low toxicity
The nano material of property is necessary to replace heavy metal semiconductor-quantum-point playing a role just become.From carbon quantum dot in 2004
First by since chancing on, it has just promptly attracted the strong interest of vast scientists.This is that a class is brand-new, size
Carbon nanomaterial below 10 nanometers, and possess the advantageous property that semiconductor-quantum-point does not possess, mainly have：High
Blue-green fluorescent quantum yield, strong stability of photoluminescence, biologically inert and good bio-compatibility etc..Meanwhile, carbon quantum
Substantial amounts of functional group is contained on point surface, and for grafting other functions molecule possibility is provided, and has further expanded its application,
So as to be considered to be the optimal replacer of other semiconductor-quantum-points.It is important to note that the main component of carbon quantum dot
For carbon, thus with low-down toxicity, even if the toxicity still very little under the concentration of mg/ml rank.Additionally, this kind of carbon
Nano material also has outstanding opto-electronic conversion performance.These properties for projecting cause carbon quantum dot in biomarker, biological knowledge
Not, the aspect such as bio-imaging have more be widely applied prospect.By the great efforts of scientists in recent years, with regard to carbon amounts
Son point carbon source and synthetic method have been achieved for unprecedented development, the former mainly include glucose, ethanol, milk,
The organic substances such as coal；The method that the latter is related to mainly has hydro-thermal method, Microwave Digestion, laser ablation, calcination method and acid
Solution etc..Although thousands of carbon sources up to a hundred and preparation method are reported, the carbon nano-particles prepared by the overwhelming majority are most
It is good excite and launch wavelength all be located at blue-green region, and the absorption in long wavelength region, particularly red light region and send out
Penetrate weaker, this prepares bottleneck and not only brings serious photic damage to the cell in biomedical applications and biological tissue,
And with the critical defect such as tissue penetration and signal resolution be low, carbon quantum dot is seriously hindered in biomedicine
With the application development in the field such as photoelectric device.At present, although although the carbon quantum dot for having a few report has red fluorescence,
But its quantum yield is often below 10%, and launch wavelength is typically not greater than 620nm, more seriously, means of purification
The technology such as the very low column chromatography of separation efficiency and dialysis can be related to.Therefore, find a kind of easy, can amplifying, efficient
, intense red fluorescent carbon quantum dot can be prepared method it is just very crucial.Synthetic method proposed by the present invention can be effective
Solve an above-mentioned difficult problem.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention to provide one kind and there is high yield and quantum
HONGGUANG carbon point of yield and preparation method thereof, this nanoparticle by the graphitized area in core and surface amorphous domain two
Part constitutes, and their core diameter length is that between 2-8 nanometers, outer casing thickness is between 1-3 nanometers, to be shown generally as many
The torispherical structure of layer graphene composition.
Technical scheme：For achieving the above object, the technical solution used in the present invention is：
A kind of HONGGUANG carbon point with high yield and quantum yield, by the shell of internal core and its outside constitute it is spherical
Body, the core is graphited carbon, and the shell is amorphous functional group, and the kernel is with shell by covalently bonded；
Wherein, a diameter of 2～8nm of the core, the thickness of the shell is 1～3nm.
Further, described carbon core is Multi-layer graphite structure, and average aromatic region area is 4nm.
Further, the amorphous functional group in the shell be hydrophilic functional group, including hydroxyl, amino, carboxyl and
Carbonyl.
Further, the carbon point has absorption and launches, the redness under the light source activation of 460-600nm in visible region
Fluorescent carbon point, Fluorescent peal is between 610-661nm.
The above-mentioned preparation method with high yield and the HONGGUANG carbon point of quantum yield, comprises the following specific steps that：
(1) solvent-thermal method prepares red fluorescence carbon quantum dot mixture
Methanamide 5-15ml is put into centrifuge tube, adds citric acid 0.2-0.6g and ethylenediamine 100-1300 μ L, concussion to dissolve,
Mixed liquor is transferred in the autoclave containing 80mL dimethyl sulfoxides, is shaken up and sealing preserve；
Baking oven is preheated to 160-220 DEG C, the autoclave is put in baking oven and reacts 4-24h, and reaction is finished, and is turned off
Baking oven, naturally cools to room temperature；
(2) settlement separate red fluorescence carbon quantum dot
The mixed liquor obtained in step (1) is tentatively filtered, acetone 40-80mL is subsequently adding and is shaken, formed outstanding
Turbid liquid；The black solid powder of red fluorescence carbon quantum dot is obtained again by centrifugal treating；Jing after acetone 5-10mL washings, will
It is scattered in dissolution solvent, sealing preserve.
Further, in step (2), the condition of the centrifugal treating be with rotating speed 5000-10000 rev/min carry out 5-
10 minutes.
Further, in step (2), the dissolution solvent is deionized water or dimethyl sulfoxide.
Further, in step (1), the optimum feed stock ratio of the citric acid and ethylenediamine is 0.4g：700μL.
Further, it is 45-76% according to the quantum yield obtained by the method, carbon quantum dot mass yield after purification
For 29-84%.
Beneficial effect：A kind of HONGGUANG carbon point with high yield and quantum yield that the present invention is provided and preparation method thereof,
It is that one kind can synthesize in a large number in red light region (peak value is between 610-661nm) inner transmitting and quantum yield is current highest
The preparation method of 76% carbon quantum dot (abbreviation carbon point).This kind of carbon nano-particles size is between 2-8nm, mainly by graphite
The carbon core of change and unbodied functional group's shell are constituted, and have good luminous efficiency, dissolubility in common solvent
And stability.As the new red light flourescent material of a class, with low production cost, can large-scale prepare, luminous efficiency pole
The excellent property such as height, good stability, is most to be hopeful to replace traditional semiconductor-quantum-point at present in photoelectric device, glimmering
The hypotoxicity nanometer new material played a role in light sensing and biotechnology.
Description of the drawings
(a) is the transmission electron microscope photo of embodiment 1 in Fig. 1, and illustration is high-resolution-ration transmission electric-lens photo.Can from figure
To the interior nuclear diameter average out to 3-4 nanometers of carbon quantum dot, the spacing of lattice that carbon quantum dot is seen from illustration is 0.21 nanometer, correspondence
In 100 lattice planes of graphite, the graphitization core texture of carbon quantum dot is further characterized by.B () is that the atomic force in embodiment 1 shows
Micro- photo, it is highly the graphite flake of 3-4 layers to show carbon quantum dot.
Fig. 2 is the solid state powder figure (quality of starting carbon source is 1.0g) of the HONGGUANG carbon point of embodiment 1.Can from figure
Arrive, carbon quantum dot after purification is mainly black, is more importantly, by mass measurement, the mass yield of carbon point can reach
To 80%, with the potentiality for expanding preparation.
Fig. 3 is the uv absorption and fluorescence spectrum of the HONGGUANG carbon point in embodiment 1.As we can see from the figure carbon quantum dot exists
There is very strong absorption visible region, and obtained the maximum absorption is at 565nm；Simultaneously it can also be seen that the fluorescence peak of sample is
The transmitting for exciting is not relied on, peak position is mainly at 654nm.
Fig. 4 is photo of the HONGGUANG carbon point under natural light in embodiment 1.As we can see from the figure carbon quantum dot is in visible ray
Bright red fluorescence can be sent down, the fact that further demonstrate that the high quantum yield of sample.
Specific embodiment
The present invention is specially one kind and can synthesize in a large number and launch and measure red light region (peak value be 610-661nm between) is inner
Sub- yield is carbon quantum dot (abbreviation carbon point) of current highest 76% and preparation method thereof.This kind of carbon nano-particles size is in
Between 2-8nm, mainly it is made up of graphited carbon core and unbodied functional group's shell, and is had very in common solvent
Luminous efficiency well, dissolubility and stability.
The present invention is a kind of " graphite-amorphous carbon " hud typed red light Nano particle, and core is graphited carbon, diameter
Can be distributed in 2～8 nanometer ranges, shell is amorphous functional group, thickness can be adjusted in 1～3 nanometer range, kernel
With shell by covalently bonded.Wherein, carbon core is the Multi-layer graphite structure of highly crystalline, and aromatic region area is compared to it
He reports that carbon quantum dot is bigger than normal.Additionally, the impalpable structure in shell contains the parents such as substantial amounts of hydroxyl, amino, carboxyl and carbonyl
Aqueouss functional group.
The solvent used during the preparation of the HONGGUANG carbon quantum dot of the present invention is dimethyl sulfoxide, rather than other are logical
The water for often using and ethanol equal solvent.Dimethylsulfoxide solvent can prepare HONGGUANG carbon point, and water and ethanol can not, and select
Selecting it contributes to precipitate and separate sample.Preparation method specifically includes following concrete steps：
(1) solvent-thermal method prepares red fluorescence carbon quantum dot mixture：
First measure 5-15 milliliter Methanamides to be put in 50 milliliters of centrifuge tube, then weigh a certain amount of citric acid respectively
(0.2-0.6 gram) and a certain amount of ethylenediamine (100-1300 μ L) are added in centrifuge tube, and concussion will mix up to being completely dissolved
Liquid is transferred in the autoclave containing 80mL dimethyl sulfoxides, sealing preserve；First high temperature oven is preheated to after uniform temperature
(160-220 degree Celsius), then reactor is put in baking oven reacts several hours (4-24 hours), reaction is finished, and turns off baking oven,
Naturally cool to room temperature.
(2) settlement separate red fluorescence carbon quantum dot：
The mixed liquor obtained in step (1) is tentatively filtered, to remove not reacted impurity；Add 40-
The acetone of 80mL simultaneously shakes, and forms suspension；Subsequently, again by centrifugal treating (5000-10000 rev/min, 5-10 minutes)
Obtain the black solid powder of red fluorescence carbon quantum dot；After the experience 5-10mL washing with acetones of 2-4 time, distribute it to from
In the dissolution solvent such as sub- water and dimethyl sulfoxide, sealing preserve.
According to above-mentioned preparation and separation method, a kind of redness under the light source activation of 460-600nm is we obtain
Fluorescent carbon point, between 610-661nm, quantum yield is up to 45-76% to their Fluorescent peal.Calculated by quality versus
(with citric acid as substrate), carbon quantum dot mass yield after purification is up to 81%.This kind of carbon quantum dot has similar structure
Composition, average-size is about 4nm, is mainly shown as on pattern spherical.Meanwhile, with extremely strong optical stability, in biology
The field such as medical science and photoelectric device has a wide range of applications.
Specific experiment effect, by being further described to the present invention with reference to embodiment and accompanying drawing.
Embodiment 1
(1) mixed solution containing red fluorescence carbon point is prepared
First 0.4g citric acids are put in the conical flask of 100mL, the formamide solvent of 10mL is added, are formed by vibrating
Transparent solution；Subsequently, the ethylenediamine of 0.7mL is added, further vibration, makes sample dispersion uniform.Then, by transparent mixing
Liquid is transferred in the stainless steel cauldron containing 80mL dimethyl sulfoxides (150 milliliters), sealing preserve.First high temperature oven is preheated to
(heating rate after 190 degrees Celsius：5 DEG C/min), then stainless steel cauldron is put into into 6 hours of reaction in baking oven, react
Finish, turn off baking oven, open oven door, naturally cool to room temperature.
(2) purification contains the mixed solution of red fluorescence carbon point
The mixed liquor obtained after first reaction in step (1) is terminated carries out filtration treatment, with remove unreacted impurity and
The bulky grain of formation.In subsequently filtrate be transferred to the conical flask of 100mL, volume is about 25mL, is slow added into 40mL's
Acetone, now solution system can little by little become cloudy, static 1 hour, it can be seen that substantial amounts of black precipitate is arranged at conical flask bottom,
Black precipitate is obtained again by centrifugal treating (5000 revs/min, 10 minutes).Finally, the carbon quantum dot powder that will be obtained
Wash 3 times with the acetone soln of 2mL every time, it is possible to obtain more clean carbon quantum dot sample.Sample both can be as solid
Powder storage, it is also possible in being distributed to water and dimethyl sulfoxide polar solvent, so that the later stage uses.The red fluorescence carbon for obtaining eventually
The launch wavelength of point is 654 nanometers, and quantum yield and mass yield are respectively：76% and 81%.
As shown in Figure 1,2,3, 4, (a) is the transmission electron microscope photo of embodiment 1 in Fig. 1, and illustration is high-resolution-ration transmission electric-lens
Photo.As we can see from the figure the interior nuclear diameter average out to 3-4 nanometers of carbon quantum dot, see between the lattice of carbon quantum dot from illustration
Away from for 0.21 nanometer, corresponding to 100 lattice planes of graphite, the graphitization core texture of carbon quantum dot is further characterized by.B () is real
The atomic force micrograph in example 1 is applied, it is highly the graphite flake of 3-4 layers to show carbon quantum dot.
Fig. 2 is the solid state powder figure (quality of starting carbon source is 1.2g) of the HONGGUANG carbon point of embodiment 1.Can from figure
Arrive, carbon quantum dot after purification is mainly black, is more importantly, by mass measurement, the mass yield energy of carbon quantum dot
80% is enough reached, with the potentiality for expanding preparation.
Fig. 3 is the uv absorption and fluorescence spectrum of the HONGGUANG carbon point in embodiment 1.As we can see from the figure carbon quantum dot exists
There is very strong absorption visible region, and obtained the maximum absorption is at 565nm；Simultaneously it can also be seen that the fluorescence peak of sample is
The transmitting for exciting is not relied on, peak position is mainly at 654nm.
Fig. 4 is photo of the HONGGUANG carbon point under natural light in embodiment 1.As we can see from the figure carbon quantum dot is in visible ray
Bright red fluorescence can be sent down, the fact that further demonstrate that the high quantum yield of sample.
Embodiment 2
Preparation method is identical with embodiment 1, but reaction temperature is changed to 220 DEG C, and other conditions are constant, and what is finally given is red
The launch wavelength of color fluorescent carbon point is 661 nanometers.Launch wavelength compared to 190 DEG C, red shift 7 nanometers, this is attributed to higher
Reaction temperature caused by higher degree of graphitization.Meanwhile, the quantum yield after integrating sphere measurement but drops to 45%, this
Outward, mass yield is that the yield of sample is also improved, and reaches 84%.From the results of view, liter high reaction temperature can produce slight
Transmitting red shift and the increase of mass yield, and reduce quantum yield.
Embodiment 3
Preparation method is identical with embodiment 1, but when reaction temperature is reduced to into 160 DEG C, other conditions are constant, final
The launch wavelength of the red fluorescence carbon point for arriving is 631 nanometers, and the specific quantum yield calculated by integrating sphere is 59%, by claiming
The mass yield for restoring sample is 43%.From the results of view, reduce reaction temperature and generate the blue shift to launch wavelength and amount
The decline result of sub- yield and sample yield.Therefore, in the preparation process of this nano material, controlling reaction temperature is very
Crucial, it has severely impacted the Formation history and constituent of carbon quantum dot.
Embodiment 4
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
0.1mL.It is 610 nanometers that launch wavelength is obtained under the conditions of this, and corresponding quantum yield and sample quality yield are：18% He
29%.As can be seen here when ethylenediamine volume is inadequate, the above three index of carbon quantum dot has unfavorable trend, illustrates raw material
Ratio be also the key for preparing high performance carbon quantum dot.Therefore property shadow of the material rate to such nano material is carefully studied
Sound is also necessary.
Embodiment 5
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
0.3mL.It is 627 nanometers now to obtain launch wavelength, and corresponding quantum yield and sample quality yield are：48%53%.Thus
It can be seen that, when the ratio shared by raw material ethylenediamine rises, the photoluminescent property and mass yield of prepared carbon nanomaterial have
The trend of raising.It is presumed that being because that more ethylenediamines take part in the formation of carbon quantum dot.
Embodiment 6
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
0.5mL.It is 639 nanometers now to obtain launch wavelength, and corresponding quantum yield and sample quality yield are：54% and 65%.By
This is visible, and when the ratio shared by raw material ethylenediamine continues to rise, the photoluminescent property and quality of prepared carbon nanomaterial are produced
Rate has the trend for continuing to improve.
Embodiment 7
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
0.7mL.It is 654 nanometers now to obtain launch wavelength, and corresponding quantum yield and sample quality yield are：76% and 81%.By
This is visible, and when the ratio shared by raw material ethylenediamine is this situation, the photoluminescent property and quality of prepared carbon nanomaterial are produced
Rate has all reached fabulous level.
Embodiment 8
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
0.9mL.It is 656 nanometers now to obtain launch wavelength, and corresponding quantum yield and sample quality yield are：63% and 65%.By
This is visible, when the ratio shared by raw material ethylenediamine exceedes optimum, the quantum yield and quality of prepared carbon nanomaterial
The slight decline of yield, and launch wavelength is not substantially moved.
Embodiment 9
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
1.1mL.It is 658 nanometers now to obtain launch wavelength, and corresponding quantum yield and sample quality yield are：59% and 57%.By
This is visible, when the ratio shared by raw material ethylenediamine continues to exceed optimum, the launch wavelength of prepared carbon nanomaterial and
Quantum yield substantially remains unchanged, and mass yield continues to decline, and may be attributed to when washing excessive ethylenediamine
Also have lost a part of sample.
Embodiment 10
Preparation method is identical with embodiment 1, but the ratio of feed change ratio, i.e. citric acid and ethylenediamine is 0.4g:
1.3mL.It is 658 nanometers now to obtain launch wavelength, and corresponding quantum yield and sample quality yield are：47% and 53%.By
This is visible, when the ratio shared by raw material ethylenediamine continues to exceed optimum, the launch wavelength of prepared carbon nanomaterial and
Quantum yield substantially remains unchanged, and mass yield continues to decline, and may be attributed to when washing excessive ethylenediamine
Also have lost a part of sample.
Above-described embodiment can be summarized as a form：
The embodiment data statistic of table 1
The present invention employs solvent-thermal method (reactor), its synthesis side during intense red fluorescent carbon point is prepared
Method is simple, environmental protection, and the raw material for using is cheap, and reaction temperature is between 160-220 DEG C, additionally, purification is used
Organic sedimentation not only rapidly and efficiently but also yield is high, therefore this kind of preparation method has very big industrial production prospect.
Meanwhile, the carbon source used during reaction not only wide material sources, and be entirely Green Chemistry.During purification
Only need to carry out at normal temperatures, it is only necessary to which using relatively inexpensive organic reagent (acetone), and the amount for using is also smaller, while
These reagents can be reused further after simple distillation, so as to the very big cost reduced in production process.
Red fluorescence carbon point prepared by the present invention is main without what difference on composition compared with other carbon reported points
If carbon nucleuses area substantially becomes big.These carbon points contain substantial amounts of hydrophilic functional group, it is possible to water, ethanol,
There is good dissolubility in Methanamide, N,N-dimethylformamide polar solvent.Meanwhile, in wider pH value (2-12) model
Under the conditions of enclosing interior, higher ionic strength, the irradiation of the high intensity ultraviolet of long period and long-time storage etc., carbon point is red
The intensity of fluorescence and peak position essentially without changing, these test results all prove its biomedicine, photoelectric device,
Above there is prospect widely with the application in the field such as visible light catalytic.
The a length of 566nm of red fluorescence carbon point optimum excitation wave prepared by the present invention, optimal launch wavelength is in 654nm.It is most
Biological damage that is good to excite and launch all in visible region, being brought when efficiently avoid using traditional ultraviolet light.
In addition, carbon point has higher quantum yield, there is higher quantum yield in Methanamide, its value can reach 76%,
It is to report highest at present.In water phase, quantum yield can also be up to 43%.These carbon quantum dots show not rely on sharp
The transmitting sent out, the position of fluorescence peak is not substantially moved.Follow-up study proves that the red fluorescence of carbon point mainly comes from graphite
The cooperative effect of the surface state of the carbon core of change and surface functional group composition.
Red fluorescence carbon point prepared by the present invention has low-down toxicity, dense to the semilethal of human cervical cancer cell
Spend for 3-4 mg/mls, than most of report semiconductor-quantum-point (CdSe and CdTe) corresponding toxicities will it is low go out 3 numbers
It is more than magnitude.Therefore, the carbon point that prepared by this kind of method in the case where biomedicine needs concentration, completely do not interfere with cell growth and
Form, or even sometimes become the nutritious carbon sourc of cell.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of HONGGUANG carbon point with high yield and quantum yield, it is characterised in that：By internal core and its shell of outside
The spheroid of composition, the core is graphited carbon, and the shell is amorphous functional group, and the kernel is with shell by altogether
Valence link connects；Wherein, a diameter of 2～8nm of the core, the thickness of the shell is 1～3nm.
2. the HONGGUANG carbon point with high yield and quantum yield according to claim 1, it is characterised in that：Described carbon core
The heart is Multi-layer graphite structure, and average aromatic region area is 4nm.
3. the HONGGUANG carbon point with high yield and quantum yield according to claim 1, it is characterised in that：In the shell
Amorphous functional group be hydrophilic functional group, including hydroxyl, amino, carboxyl and carbonyl.
4. the HONGGUANG carbon point with high yield and quantum yield according to claim 1, it is characterised in that：The carbon point is can
See that there is absorption in light region and launches, the red fluorescence carbon point under the light source activation of 460-600nm, Fluorescent peal is in 610-
Between 661nm.
5., according to the arbitrary described preparation method with high yield and the HONGGUANG carbon point of quantum yield of Claims 1-4, it is special
Levy and be：Comprise the following specific steps that：
(1) solvent-thermal method prepares red fluorescence carbon quantum dot mixture
Methanamide 5-15ml is put into centrifuge tube, adds citric acid 0.2-0.6g and ethylenediamine 100-1300 μ L, and concussion dissolving will be mixed
Close liquid to be transferred in the autoclave containing 80mL dimethyl sulfoxides, shake up and sealing preserve；
Baking oven is preheated to 160-220 DEG C, the autoclave is put in baking oven and reacts 4-24h, and reaction is finished, and turns off baking
Case, naturally cools to room temperature；
(2) settlement separate red fluorescence carbon quantum dot
The mixed liquor obtained in step (1) is tentatively filtered, acetone 40-80mL is subsequently adding and is shaken, formed suspension；
The black solid powder of red fluorescence carbon quantum dot is obtained again by centrifugal treating；Jing after acetone 5-10mL washings, by its point
Dissipate in dissolution solvent, sealing preserve.
6. the preparation method with high-quality yield and the HONGGUANG carbon point of quantum yield according to claim 5, its feature
It is：In step (2), the condition of the centrifugal treating be with rotating speed 5000-10000 rev/min carry out 5-10 minutes.
7. the preparation method with high yield and the HONGGUANG carbon point of quantum yield according to claim 5, it is characterised in that：
In step (2), the dissolution solvent is deionized water or dimethyl sulfoxide.
8. the preparation method with high yield and the HONGGUANG carbon point of quantum yield according to claim 5, it is characterised in that：
In step (1), the optimum feed stock ratio of the citric acid and ethylenediamine is 0.4g：700μL.
9. the preparation method with high yield and the HONGGUANG carbon point of quantum yield according to claim 5, it is characterised in that：
It is 45-76% according to the quantum yield obtained by the method, carbon quantum dot mass yield after purification is 29-84%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610965433.XA CN106566534B (en) | 2016-11-04 | 2016-11-04 | A kind of feux rouges carbon dots and preparation method thereof with high yield and quantum yield |
| PCT/CN2017/000665 WO2018082204A1 (en) | 2016-11-04 | 2017-11-03 | Red-emitting carbon dot having high yield and quantum yield and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610965433.XA CN106566534B (en) | 2016-11-04 | 2016-11-04 | A kind of feux rouges carbon dots and preparation method thereof with high yield and quantum yield |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106566534A true CN106566534A (en) | 2017-04-19 |
| CN106566534B CN106566534B (en) | 2019-05-17 |
Family
ID=58535910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610965433.XA Expired - Fee Related CN106566534B (en) | 2016-11-04 | 2016-11-04 | A kind of feux rouges carbon dots and preparation method thereof with high yield and quantum yield |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106566534B (en) |
| WO (1) | WO2018082204A1 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106974659A (en) * | 2017-05-20 | 2017-07-25 | 复旦大学 | A kind of latent fingerprint detection method based on red fluorescence carbon point material |
| CN107746460A (en) * | 2017-10-31 | 2018-03-02 | 江南大学 | A kind of method of efficiently purification poly-dopamine nano-particle |
| CN107903893A (en) * | 2017-11-13 | 2018-04-13 | 中国科学院长春光学精密机械与物理研究所 | A kind of modified carbon nano tube point, its preparation method and its application near infrared absorption and near-infrared luminous characteristic |
| WO2018082204A1 (en) * | 2016-11-04 | 2018-05-11 | 中国矿业大学 | Red-emitting carbon dot having high yield and quantum yield and preparation method therefor |
| CN108046236A (en) * | 2017-05-24 | 2018-05-18 | 北京师范大学 | A kind of preparation method and application of high quantum production rate red carbon quantum dot |
| CN108070373A (en) * | 2017-12-27 | 2018-05-25 | 西南林业大学 | One kind has superelevation quantum yield and water-soluble good nitrogen-doped carbon quantum dot and preparation method and application |
| CN108659835A (en) * | 2018-07-16 | 2018-10-16 | 河北工业大学 | A kind of low temperature preparation method of red emission carbon quantum dot |
| CN108753282A (en) * | 2018-07-26 | 2018-11-06 | 大连理工大学 | A kind of method of red fluorescence carbon dots under synthesizing visible light source excitation |
| CN109207147A (en) * | 2017-07-05 | 2019-01-15 | 复旦大学 | It is a kind of with fluorescence, optoacoustic, the carbon nano dot of photo-thermal effect and its synthetic method |
| CN109628087A (en) * | 2019-01-04 | 2019-04-16 | 山西大学 | A kind of red fluorescence carbon dots and its preparation method and application |
| CN109652071A (en) * | 2018-10-26 | 2019-04-19 | 华南师范大学 | A kind of red emission carbon quantum dot and its domestic microwave preparation method |
| CN110272735A (en) * | 2019-06-03 | 2019-09-24 | 五邑大学 | A kind of white light LEDs red carbon fluorescent material and its methods for making and using same |
| CN110980690A (en) * | 2019-12-24 | 2020-04-10 | 云南大学 | Method for preparing narrow-band red fluorescent carbon quantum dots by using titanyl phthalocyanine |
| CN111088032A (en) * | 2019-12-13 | 2020-05-01 | 临沂大学 | Preparation method of fluorescent polymer for simultaneously detecting trivalent chromium ions and hexavalent chromium ions |
| CN111116990A (en) * | 2019-11-14 | 2020-05-08 | 华南农业大学 | Ultraviolet-blue light absorbent, preparation method thereof and prepared ultraviolet-blue light absorbent material |
| CN112126431A (en) * | 2020-09-29 | 2020-12-25 | 南京理工大学 | Preparation method and application of carbon quantum dot modified black phosphorus quantum dot nano particle material |
| CN115874490A (en) * | 2022-12-30 | 2023-03-31 | 福建泰兴特纸有限公司 | Multilayer anti-counterfeiting medium frame paper and preparation method thereof |
| WO2023142891A1 (en) * | 2022-01-28 | 2023-08-03 | 华东师范大学 | Preparation method and application of carbon quantum dots having high fluorescence quantum yield |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110208547B (en) * | 2019-06-27 | 2022-07-08 | 北京柏海达科技有限公司 | Pepsinogen immunochromatography detection kit based on carbon quantum dots and preparation method thereof |
| CN110589801B (en) * | 2019-10-10 | 2022-07-29 | 太原理工大学 | Solid-state fluorescent carbon quantum dot with variable light-emitting color and preparation method thereof |
| CN111088043A (en) * | 2019-12-18 | 2020-05-01 | 辽宁大学 | Visible light excited and long-wavelength emitted fluorescent carbon dot and preparation method and application thereof |
| CN111205862A (en) * | 2020-01-08 | 2020-05-29 | 辽宁大学 | Application of carbon quantum dot with multiple fluorescence emission centers as optical sensor in visual detection of trace water in organic solvent |
| CN111257967A (en) * | 2020-01-13 | 2020-06-09 | 苏州星烁纳米科技有限公司 | Oil field tracer and oil field tracing method |
| CN111410960B (en) * | 2020-04-29 | 2022-06-14 | 辽宁大学 | Single red light emitting composite nano fluorescent powder and preparation method thereof |
| CN111504971B (en) * | 2020-05-11 | 2021-11-05 | 吉林大学 | 2, 4-dichlorphenoxyacetic acid on-site quantitative detection platform based on integration of target response type 3D printing model and smart phone |
| CN111978597B (en) * | 2020-07-06 | 2022-05-24 | 东北林业大学 | Long afterglow material and preparation method and application thereof |
| CN113652224B (en) * | 2021-01-31 | 2024-02-23 | 重庆大学 | Anti-quenching carbon quantum dot solid compound, blue light prevention film and preparation method thereof |
| CN113201333A (en) * | 2021-04-29 | 2021-08-03 | 宁波萃英化学技术有限公司 | Full-color room temperature phosphorescent carbon dot under ultraviolet excitation and composition thereof |
| CN113403068B (en) * | 2021-06-16 | 2023-08-08 | 澳门大学 | Fused carbon dot, preparation method and application thereof |
| CN114609107A (en) * | 2022-03-14 | 2022-06-10 | 吉林大学 | Fluorescent probe based on red light carbon quantum dots and application of fluorescent probe in detection of ethanol concentration in ethanol-water system |
| CN114774119B (en) * | 2022-03-28 | 2023-08-18 | 太原理工大学 | Phosphorescent carbon quantum dot matrix composite material and preparation method thereof |
| CN114921245B (en) * | 2022-04-28 | 2024-04-02 | 澳门大学 | Near-infrared carbon dot and preparation method and application thereof |
| CN115057428B (en) * | 2022-06-02 | 2024-02-06 | 中国科学院合肥物质科学研究院 | Hydrophobic near-infrared emission carbon quantum dot and preparation method and application thereof |
| CN115044365A (en) * | 2022-06-22 | 2022-09-13 | 吉林大学 | Energy-level-controllable carbon dot fluorescent nano material and synthesis method thereof |
| CN115491197B (en) * | 2022-07-05 | 2023-10-27 | 广州新水平量子科技研究有限公司 | Solid fluorescent carbon quantum dot material and preparation method thereof |
| CN115125000B (en) * | 2022-07-06 | 2023-11-03 | 重庆国科医创科技发展有限公司 | Preparation method of red light emission carbon quantum dot and application of carbon quantum dot |
| CN115400723B (en) * | 2022-07-26 | 2024-05-28 | 天津万象恒远科技有限公司 | Carbon quantum dot bonded silica gel chromatographic stationary phase and preparation method and application thereof |
| CN115287065B (en) * | 2022-08-09 | 2023-07-18 | 山西大学 | Preparation method and application of nitrogen-phosphorus co-doped carbon dots |
| CN115504455B (en) * | 2022-09-14 | 2023-06-16 | 郑州大学 | Preparation method of full-spectrum laser emission carbon dot material |
| CN116285968B (en) * | 2022-12-06 | 2024-03-15 | 延安大学 | Cerium-nitrogen co-doped biomass carbon quantum dot and preparation method and application thereof |
| CN116179197B (en) * | 2023-02-27 | 2024-04-05 | 河北大学 | Preparation of Eu by one-step hydrothermal method 3+ Method for doping fluorescent carbon dots |
| CN116285973B (en) * | 2023-02-27 | 2024-02-20 | 大连海事大学 | Purple light carbon dot and preparation method and application thereof |
| CN116285974B (en) * | 2023-03-17 | 2024-07-19 | 中国科学院上海微系统与信息技术研究所 | Preparation method of carbon-based quantum dot with high quantum yield and light stability |
| CN116904191B (en) * | 2023-06-02 | 2024-06-18 | 齐齐哈尔大学 | Multicolor fluorescent carbon quantum dot, preparation method thereof and light-emitting diode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395771A (en) * | 2013-08-01 | 2013-11-20 | 吉林大学 | Carbon dots with high fluorescent quantum yield, and application thereof in fluorescent color development |
| CN105236383A (en) * | 2015-09-14 | 2016-01-13 | 复旦大学 | Wavelength adjustable carbon quantum dots, preparation method and applications thereof |
| CN106520116A (en) * | 2016-10-11 | 2017-03-22 | 杭州电子科技大学 | Red luminescent carbon quantum dot, preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617405A (en) * | 2014-11-04 | 2016-06-01 | 东北师范大学 | Simple and green preparation method for monodisperse core-shell-structured C-dots@SiO2 fluorescence imaging nanoprobe |
| CN104789217B (en) * | 2015-04-28 | 2017-01-18 | 安徽大学 | Amphipathy carbon quantum dot and preparation method thereof |
| CN106566534B (en) * | 2016-11-04 | 2019-05-17 | 中国矿业大学 | A kind of feux rouges carbon dots and preparation method thereof with high yield and quantum yield |
-
2016
- 2016-11-04 CN CN201610965433.XA patent/CN106566534B/en not_active Expired - Fee Related
-
2017
- 2017-11-03 WO PCT/CN2017/000665 patent/WO2018082204A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395771A (en) * | 2013-08-01 | 2013-11-20 | 吉林大学 | Carbon dots with high fluorescent quantum yield, and application thereof in fluorescent color development |
| CN105236383A (en) * | 2015-09-14 | 2016-01-13 | 复旦大学 | Wavelength adjustable carbon quantum dots, preparation method and applications thereof |
| CN106520116A (en) * | 2016-10-11 | 2017-03-22 | 杭州电子科技大学 | Red luminescent carbon quantum dot, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| DAQIN CHEN等: "Intense multi-state visible absorption and full-color luminescence of nitrogen-doped carbon quantum dots for blue-light-excitable solid-state-lighting", 《J. MATER. CHEM. C》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018082204A1 (en) * | 2016-11-04 | 2018-05-11 | 中国矿业大学 | Red-emitting carbon dot having high yield and quantum yield and preparation method therefor |
| CN106974659A (en) * | 2017-05-20 | 2017-07-25 | 复旦大学 | A kind of latent fingerprint detection method based on red fluorescence carbon point material |
| CN108046236A (en) * | 2017-05-24 | 2018-05-18 | 北京师范大学 | A kind of preparation method and application of high quantum production rate red carbon quantum dot |
| CN109207147B (en) * | 2017-07-05 | 2021-06-29 | 复旦大学 | Carbon nanodot with fluorescence, photoacoustic and photothermal effects and synthesis method thereof |
| CN109207147A (en) * | 2017-07-05 | 2019-01-15 | 复旦大学 | It is a kind of with fluorescence, optoacoustic, the carbon nano dot of photo-thermal effect and its synthetic method |
| CN107746460A (en) * | 2017-10-31 | 2018-03-02 | 江南大学 | A kind of method of efficiently purification poly-dopamine nano-particle |
| CN107903893A (en) * | 2017-11-13 | 2018-04-13 | 中国科学院长春光学精密机械与物理研究所 | A kind of modified carbon nano tube point, its preparation method and its application near infrared absorption and near-infrared luminous characteristic |
| CN107903893B (en) * | 2017-11-13 | 2021-01-05 | 中国科学院长春光学精密机械与物理研究所 | Modified carbon nanodot with near-infrared absorption and near-infrared luminescence characteristics, and preparation method and application thereof |
| CN108070373A (en) * | 2017-12-27 | 2018-05-25 | 西南林业大学 | One kind has superelevation quantum yield and water-soluble good nitrogen-doped carbon quantum dot and preparation method and application |
| CN108659835A (en) * | 2018-07-16 | 2018-10-16 | 河北工业大学 | A kind of low temperature preparation method of red emission carbon quantum dot |
| CN108753282A (en) * | 2018-07-26 | 2018-11-06 | 大连理工大学 | A kind of method of red fluorescence carbon dots under synthesizing visible light source excitation |
| CN109652071A (en) * | 2018-10-26 | 2019-04-19 | 华南师范大学 | A kind of red emission carbon quantum dot and its domestic microwave preparation method |
| CN109652071B (en) * | 2018-10-26 | 2022-04-01 | 华南师范大学 | Red light emitting carbon quantum dot and household microwave preparation method thereof |
| CN109628087B (en) * | 2019-01-04 | 2021-07-02 | 山西大学 | Red fluorescent carbon dot and preparation method and application thereof |
| CN109628087A (en) * | 2019-01-04 | 2019-04-16 | 山西大学 | A kind of red fluorescence carbon dots and its preparation method and application |
| CN110272735A (en) * | 2019-06-03 | 2019-09-24 | 五邑大学 | A kind of white light LEDs red carbon fluorescent material and its methods for making and using same |
| CN111116990A (en) * | 2019-11-14 | 2020-05-08 | 华南农业大学 | Ultraviolet-blue light absorbent, preparation method thereof and prepared ultraviolet-blue light absorbent material |
| CN111116990B (en) * | 2019-11-14 | 2021-07-09 | 华南农业大学 | Ultraviolet-blue light absorbent, preparation method thereof and prepared ultraviolet-blue light absorbent material |
| CN111088032A (en) * | 2019-12-13 | 2020-05-01 | 临沂大学 | Preparation method of fluorescent polymer for simultaneously detecting trivalent chromium ions and hexavalent chromium ions |
| CN111088032B (en) * | 2019-12-13 | 2023-07-21 | 临沂大学 | Preparation method of fluorescent polymer for simultaneously detecting trivalent chromium ions and hexavalent chromium ions |
| CN110980690A (en) * | 2019-12-24 | 2020-04-10 | 云南大学 | Method for preparing narrow-band red fluorescent carbon quantum dots by using titanyl phthalocyanine |
| CN110980690B (en) * | 2019-12-24 | 2023-03-28 | 云南大学 | Method for preparing narrow-band red fluorescent carbon quantum dots by using titanyl phthalocyanine |
| CN112126431A (en) * | 2020-09-29 | 2020-12-25 | 南京理工大学 | Preparation method and application of carbon quantum dot modified black phosphorus quantum dot nano particle material |
| WO2023142891A1 (en) * | 2022-01-28 | 2023-08-03 | 华东师范大学 | Preparation method and application of carbon quantum dots having high fluorescence quantum yield |
| CN115874490A (en) * | 2022-12-30 | 2023-03-31 | 福建泰兴特纸有限公司 | Multilayer anti-counterfeiting medium frame paper and preparation method thereof |
| CN115874490B (en) * | 2022-12-30 | 2023-12-01 | 福建泰兴特纸有限公司 | Multilayer anti-counterfeiting medium frame paper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106566534B (en) | 2019-05-17 |
| WO2018082204A1 (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106566534A (en) | Red-light carbon dot of high yield and high quantum yield, and preparation method thereof | |
| Liu et al. | Carbon dots: synthesis, formation mechanism, fluorescence origin and sensing applications | |
| Das et al. | Green approach to photoluminescent carbon dots for imaging of gram-negative bacteria Escherichia coli | |
| CN105236383B (en) | Carbon quantum dot of Wavelength tunable and its preparation method and application | |
| CN106141200B (en) | A kind of Preparation method and use of carbon dots/gold compound nano-particle | |
| CN103320125A (en) | Multicolor fluorescence fluorescent graphene quantum dot material preparation method | |
| KR101663748B1 (en) | Method of manufacturing nitrogen-doped carbon dots | |
| CN103160279A (en) | Functional carbon dots, and preparation and application thereof | |
| CN107603611A (en) | One kind has Catalyzed Synthesis By Peroxidase active fluoro carbon quantum dot and preparation method thereof | |
| CN113770372B (en) | Preparation method of gold nanoparticle aggregate material | |
| CN110776910A (en) | Double-function magnetic fluorescent nano composite Fe 3O 4Preparation method of @ CDs microspheres | |
| Tian et al. | Carbon dot-silica composite nanoparticle: an excitation-independent fluorescence material with tunable fluorescence | |
| KR102387805B1 (en) | Multi-component mesocrystalline nanoparticles and manufacturing method thereof | |
| CN106001608A (en) | Method for preparing silver nanoparticles with water-soluble starch | |
| CN108163836A (en) | A kind of purifying technique of metal ion mixing carbon quantum dot | |
| CN111218272B (en) | Preparation method of fluorescent sulfur quantum dots based on sulfur-amine solution | |
| Ghasemlou et al. | Fluorescent Nanocarbons: From Synthesis and Structure to Cancer Imaging and Therapy | |
| CN106010500A (en) | Magnetic nano-luminescent material with core-shell structure and preparation method of magnetic nano-luminescent material | |
| CN108084996A (en) | The method that extraction prepares fluorescent carbon quantum dot from beer | |
| CN109704312B (en) | Preparation method of water-soluble blue-green fluorescent graphene quantum dots | |
| Wang et al. | Synthesis and spectroscopic properties of silver-fluorescein co-doped phosphotungstate hollow spheres | |
| CN107603608B (en) | Method for preparing fluorescent carbon dots by taking gynostemma pentaphylla as carbon source | |
| CN111218285B (en) | Preparation method of fluorescent selenium nanoparticles based on selenium-amine mixed solution | |
| Kirubanithy et al. | Fluorescent carbon quantum dots synthesized from coconut shell for the detection of Fe3+ ion | |
| Wojtczak et al. | Diatomaceous Biosilica Doped with Heteroepitaxially Growing Ag/AgCl/CeO2 Composite Nanoparticles: Synthesis, Characterisation and Antibacterial Application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190517 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |