CN106010523B - A kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point and its preparation method and application - Google Patents
A kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point and its preparation method and application Download PDFInfo
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- CN106010523B CN106010523B CN201610344777.9A CN201610344777A CN106010523B CN 106010523 B CN106010523 B CN 106010523B CN 201610344777 A CN201610344777 A CN 201610344777A CN 106010523 B CN106010523 B CN 106010523B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 40
- 239000011574 phosphorus Substances 0.000 title claims abstract description 40
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 18
- 229940033123 tannic acid Drugs 0.000 claims abstract description 18
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 18
- 229920002258 tannic acid Polymers 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000000975 dye Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000502 dialysis Methods 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000005718 Stomach Neoplasms Diseases 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- -1 carbonyl Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 206010017758 gastric cancer Diseases 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 201000011549 stomach cancer Diseases 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention relates to a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point preparation method and applications.The technical solution adopted is that：Take tannic acid and polyethyleneimine (PEI), add in deionized water and phosphoric acid, it is then transferred into hydrothermal reaction kettle, in in 140~240 DEG C of temperature ranges, 2~6h of insulation reaction, at room temperature natural cooling obtain light brown nanometer carbon dots crude product solution, it is refined by centrifuging, dialysing, freeze-drying, obtains carbon dots solid powder after purification.The carbon dots of the present invention can be used for cell imaging and the light degradation processing procedure containing organic dyestuff.Fluorescent carbon point fluorescence quantum yield prepared by the present invention is up to 25.4%.After preserving 6 months in the dark, brilliant blue fluorescence is still sent out under the ultra violet lamp of 365nm, illustrates carbon dots having good stability at room temperature.
Description
Technical field
The present invention relates to carbon nanomaterial technical fields, and in particular to one kind is in phosphoric acid medium, with tannic acid and poly- second
The synthesis of alkene imido is a kind of with the phosphorus doping fluorescent carbon point of blue-fluorescence and its application.
Background technology
Carbon dots (Carbon Dots) are a kind of spherical fluorescence carbon nano-particles of dispersion of size less than 10nm, are had
There is excellent photoluminescence performance.Compared with traditional organic fluorescent dye, fluorescent carbon point has higher photostability and resists
Photobleaching.In addition, fluorescent carbon point molecular weight and grain size are smaller, good biocompatibility, toxicity is low, exciting light spectrum width and company
It is continuous, it can realize that unitary excites polynary transmitting, be a kind of extraordinary fluorescent marker and imaging agents, and be successfully applied
In cell and living imaging.Fluorescent carbon point in itself have some special natures, make its photoelectric device, organic solar batteries,
Photocatalysis etc. is with a wide range of applications.Although carbon dots preparation method and related application research have had a large amount of reports,
But also relatively low there are fluorescence quantum yield, the problems such as preparation process is complicated, therefore find simple, quickly preparing has good hair
The method of the fluorescent carbon point of optical property is very necessary.
Invention content
The purpose of the present invention is to provide a kind of simple, effective phosphorus doping fluorescent carbons having compared with high-fluorescence quantum yield
Point and preparation method thereof.
Purpose to realize the present invention, the technical solution adopted by the present invention are as follows：A kind of high-fluorescence quantum yield phosphorus doping
Fluorescent carbon point, preparation method are as follows：Tannic acid and polyethylene imine are taken, sequentially adds deionized water and phosphoric acid, after stirring and dissolving,
It is transferred in reaction kettle, 2~6h of hydro-thermal reaction is cooled to room temperature, obtains crude product, through dialysis, freeze-drying, the phosphorus purified
Doping fluorescent carbon dots.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, in mass ratio, tannic acid:Polyethylene
Imido=1:1~5.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, every gram of tannic acid add in 15~80ml
Water.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, every gram of tannic acid add in 1.5~5ml
Phosphoric acid.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, hydrothermal temperature are 140~240
℃。
It is a further object of the present invention to provide application of the phosphorus doping fluorescent carbon point in bio-imaging and catalytic degradation dyestuff.
Application of the above-mentioned high-fluorescence quantum yield phosphorus doping fluorescent carbon point in degradating organic dye.Method is as follows：In
The tungsten trioxide photocatalyst of above-mentioned phosphorus doping fluorescent carbon point modification is added in solution containing organic dyestuff, in dark surrounds
After lower stirring and adsorbing 1h, with 500W high Hg lamp irradiations；The tungsten trioxide photocatalyst of described phosphorus doping fluorescent carbon point modification is：
By above-mentioned phosphorus doping fluorescent carbon point and WO3Mixing, under the conditions of 140~240 DEG C, 3~4h of heating reaction.
The beneficial effects of the invention are as follows：
1. preparation method of the present invention is simple, is easily industrialized production.Using tannic acid that is inexpensive, being easy to get, polyethylene
Imines and phosphoric acid, with hydro-thermal reaction technology one-step synthesis fluorescent carbon point.
2. nano fluorescent carbon dots biocompatibility prepared by the present invention is preferable, internal fluorescence imaging can be realized.
3. nano fluorescent carbon dots fluorescence quantum yield prepared by the present invention is up to 25.4%.
4. nano fluorescent carbon dots maximum excitation and launch wavelength prepared by the present invention are respectively 345nm and 469nm.In the dark
After preserving 6 months, brilliant blue fluorescence is still sent out under the ultra violet lamp of 365nm.Illustrate the stabilization of carbon dots at room temperature
Property is good.Fluorescent carbon point prepared by the present invention is water-soluble good and stablizes, and places 1 year and undergoes no deterioration under room temperature.
Description of the drawings
Fig. 1 is the transmission electron microscope photo of fluorescent carbon point.
Fig. 2 is the X-ray diffractogram of fluorescent carbon point.
Fig. 3 is the infrared spectrogram of fluorescent carbon point.
Fig. 4 is the zeta potential diagrams of fluorescent carbon point solution.
Fig. 5 is the UV-visible absorption spectrum of fluorescent carbon point solution.
Fig. 6 is the excitation and emission spectra figure of fluorescent carbon point solution.
Fig. 7 is the fluorescence emission spectrogram of compound of the lower fluorescent carbon point solution of different wavelengths of light excitation.
Fig. 8 is influence (λ ex=345nm) of the pH value to carbon dots solution fluorescence.
Fig. 9 is influence (λ ex=345nm) of the NaCl concentration to carbon dots solution fluorescence.
Figure 10 is influence (λ ex=345nm) of the illumination to carbon dots solution fluorescence.
Figure 11 is intake situation of the fluorescence microscope cell to carbon dots.
Figure 12 is that methylene blue light degradation changes over time curve under illumination and dark condition.
Specific embodiment
Embodiment 1
The tannic acid of 0.2g and the PEI of 0.2g are weighed, adds in the deionized water of 10ml, adds the phosphoric acid of 0.5ml, fully
Stirring and dissolving is transferred in the reaction kettle of 50ml, is put into air dry oven, in 140 DEG C heat 2h, cooled to room temperature,
Dark-brown carbon dots solution is obtained, then by dialysis and freeze-drying, finally obtains phosphorus doping fluorescent carbon point (CDs) solid powder
End.Fluorescence quantum yield is 25.4%.
The transmission electron microscope photo of phosphorus doping fluorescent carbon point is as shown in Figure 1.As seen from the figure, the grain size of carbon dots is in 9nm or so.
The X-ray diffraction spectrum of phosphorus doping fluorescent carbon point is as shown in Figure 2.X-ray diffraction analysis show carbon dots powder 2 θ=
23 ° nearby there is an apparent and wider diffraction maximum, and showing carbon dots is existed in a manner of amorphous state.
The infrared spectrum of phosphorus doping fluorescent carbon point is as shown in Figure 3.Infrared spectrogram shows that there is-OH and the flexible of-NH shakes
Dynamic absorption peak (3411cm-1), the stretching vibration absworption peak (1623cm of carbonyl-1), the stretching vibration that the doping of P-O keys generates absorbs
Peak is in 1088cm-1Near, C-N stretching vibration absworption peaks are in 1350cm-1Place.
The zeta current potentials of phosphorus doping fluorescent carbon point solution are as shown in figure 4, in solution in pH=6.0, the zeta of carbon dots
The inclined negative value of potential value shows carbon dots surface slightly negative electricity.
The uv-visible absorption spectra of phosphorus doping fluorescent carbon point solution is as shown in Figure 5.As seen from the figure, carbon dots solution
There is an apparent characteristic absorption peak at 350nm, range extends to visual field by ultra-violet (UV) band.
The fluorescence excitation and emission spectrum of phosphorus doping fluorescent carbon point solution are as shown in Figure 6.As seen from the figure, fluorescent carbon point is most
Big excitation wavelength and maximum emission wavelength are respectively 345nm and 469nm.
Under different wavelengths of light excitation, the fluorescence emission spectrum of fluorescent carbon point solution is as shown in Figure 7.By figure it can be found that
As excitation wavelength increases (from 330nm to 370nm), the gradual blue shift of fluorescence emission peak of fluorescent carbon point, it is indicated that prepared carbon
Point has excitation wavelength dependence.
The results are shown in Figure 8 for influence of the pH value to carbon dots solution fluorescence.As seen from the figure, fluorescence is most strong during pH=5, and when molten
When liquid pH value increases or decreases, carbon dots fluorescence intensity all decreases, and shows that solution acidity has one to the luminescence generated by light of carbon dots
Fixed influence.
Influence of the NaCl concentration to fluorescent carbon point solution fluorescence：Difference is separately added into 50 times of carbon dots solution is diluted
NaCl is measured, carbon dots fluorescent emission intensity is measured, has investigated influence of the NaCl concentration to carbon dots fluorescence intensity, as a result seen Fig. 9.By scheming
As it can be seen that in the range of 0~2.0mol/L, the fluorescence intensity of carbon dots solution has almost no change.Therefore, prepared fluorescent carbon point
With preferable saline-alkaline tolerance.
Influence of the illumination to carbon dots solution fluorescence：The carbon dots solution for determining 50 times of dilution respectively connects under 500W high mercury lamps
Fluorescence intensity after continuous irradiation 0.5,1,1.5,2,3,4,5h.As seen from Figure 10, the fluorescence intensity of carbon dots does not occur bright
Aobvious variation shows that carbon dots stability is good, anti-light bleaching.
Embodiment 2
The tannic acid of 0.2g and the PEI of 1.0g are weighed, adds in the deionized water of 15ml, adds the phosphoric acid of 1.0ml, fully
Stirring and dissolving is transferred in the reaction kettle of 50ml, is put into air dry oven, is heated 4 hours in 180 DEG C, is naturally cooled to room
Temperature obtains dark-brown carbon dots solution, then obtains phosphorus doping fluorescent carbon point solution by dialysis.
Embodiment 3
The tannic acid of 0.5g and the PEI of 1.2g are weighed, adds in the deionized water of 20ml, the phosphoric acid of 1.5ml is added in, fully stirs
Dissolving is mixed, is transferred in the reaction kettle of 50ml, is put into air dry oven, is heated 4 hours in 200 DEG C, cooled to room temperature,
Dark-brown carbon dots solution is obtained, then obtains phosphorus doping fluorescent carbon point solution eventually by dialysis.
Embodiment 4
The tannic acid of 1.0g and the PEI of 1.2g are weighed, adds in the deionized water of 20ml, adds the phosphoric acid of 1.5ml, fully
It after stirring, is transferred in the reaction kettle of 50ml, is put into air dry oven, heated 6 hours in 180 DEG C, cooled to room temperature,
Dark-brown carbon dots solution is obtained, then obtains phosphorus doping fluorescent carbon point solution by dialysis.
Embodiment 5
The tannic acid of 1.0g and the PEI of 1.2g are weighed, adds in the deionized water of 15ml, adds the phosphoric acid of 1.5ml, fully
It after stirring, is transferred in the reaction kettle of 50ml, is put into air dry oven, heated 6 hours in 180 DEG C, cooled to room temperature,
Dark-brown carbon dots solution is obtained, then obtains phosphorus doping fluorescent carbon point solution by dialysis.
Application of the 6 phosphorus doping fluorescent carbon point of embodiment in bio-imaging agent
A concentration of 100 μ g/L phosphorus doping fluorescent carbon point solution is co-cultured with stomach cancer cell BGC-823 at 37 DEG C, respectively
6 and for 24 hours when, with fluorescence microscope cell to the intake situation of carbon dots, as a result as shown in figure 11.As seen from the figure, with
Time increases, and cell is better to carbon dots intake effect, shows good cell imaging effect.
Application of the 7 phosphorus doping fluorescent carbon point of embodiment in degradating organic dye
Method：Tungsten trioxide photocatalyst (the CDs-WO of phosphorus doping fluorescent carbon point modification3)：Weigh 0.2g tannic acid and
The PEI of 0.4g adds in 15ml deionized waters and stirs evenly in beaker, adds in the phosphoric acid of 0.5ml, the hydro-thermal for being transferred to 50ml is anti-
It answers in kettle, adds in the WO of 0.5g3, in air dry oven at a temperature of 230 DEG C, react 3h.It is centrifuged after cooling room temperature, dry
Tungsten trioxide photocatalyst (the CDs-WO modified to carbon dots3)。
50ml methylene blue solutions (mass concentration 10mg/L) are taken in beaker, add in 50mg CDs-WO3, in dark
Stirring and adsorbing 1h under environment reaches adsorption and desorption balance, then with 500W high voltage mercury lamp radiations, takes at regular intervals
Sample is measured the absorbance of methylene blue solution at wavelength 664nm by UV, visible light-spectrophotometer, passes through below equation
Formula calculates the percent of decolourization of methylene blue：
In formula：A0The starting absorbance of solution for methylene blue, A are the absorbance value of different t moment methylene blues.
Comparative example 1：Phosphorus doping fluorescent carbon point (CDs)：The tannic acid of 0.2g and the PEI of 0.4g are weighed in beaker, and is added
Enter 15ml deionized waters to stir evenly, add in the phosphoric acid of 0.5ml, be transferred in the hydrothermal reaction kettle of 50ml, in air dry oven
At 140 DEG C, 2h is reacted.It is centrifuged after cooling room temperature, is dried to obtain phosphorus doping fluorescent carbon point.
50ml methylene blue solutions (mass concentration 10mg/L) are taken in beaker, add in 50mg phosphorus doping fluorescent carbon points,
The stirring and adsorbing 1h under dark surrounds reaches adsorption and desorption balance, then with 500W high voltage mercury lamp radiations, every one section
Time sampling measures the absorbance of methylene blue solution by UV, visible light-spectrophotometer at wavelength 664nm.
Comparative example 2：50ml methylene blue solutions (mass concentration 10mg/L) are taken in beaker, add in 50mg nanometers of WO3,
The stirring and adsorbing 1h under dark surrounds reaches adsorption and desorption balance, then with 500W high Hg lamp irradiations, when one section
Between sample, the absorbance of methylene blue solution is measured at wavelength 664nm by UV, visible light-spectrophotometer.
As a result as shown in figure 12.Research shows that WO is used alone3When, the photodegradation rate of methylene blue is 52.3%, and
The fluorescent carbon point that the present invention obtains is added in system, photodegradation rate reaches 80.7%.WO can be promoted by illustrating the carbon dots of the present invention3
Photodegradation to methylene blue.
Claims (5)
1. application of the high-fluorescence quantum yield phosphorus doping fluorescent carbon point in degradating organic dye, it is characterised in that：Method is as follows：
The tungsten trioxide photocatalyst of phosphorus doping fluorescent carbon point modification is added in the solution containing organic dyestuff, is stirred under dark surrounds
After mixing 1 h of absorption, with 500 W high voltage mercury lamp radiations；The tungsten trioxide photocatalyst of the phosphorus doping fluorescent carbon point modification
It is：By phosphorus doping fluorescent carbon point and WO3Mixing, under the conditions of 140~240 DEG C, 3 ~ 4h of heating reaction；The phosphorus doping fluorescence
The preparation method of carbon dots is：Tannic acid and polyethylene imine are taken, sequentially adds deionized water and phosphoric acid, after stirring and dissolving, transfer
Into reaction kettle, 2~6 h of hydro-thermal reaction is cooled to room temperature, obtains crude product, and through dialysis, freeze-drying obtains phosphorus doping fluorescence
Carbon dots.
2. application according to claim 1, it is characterised in that：In mass ratio, tannic acid:Polyethylene imine=1:1~
5。
3. application according to claim 1, it is characterised in that：Every gram of tannic acid adds in 15~80ml water.
4. application according to claim 1, it is characterised in that：Every gram of tannic acid adds in 1.5~5ml phosphoric acid.
5. application according to claim 1, it is characterised in that：Hydrothermal temperature is 140~240 DEG C.
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