CN106010523A - Phosphorus-doped fluorescent carbon point with high fluorescent quantum yield as well as preparation method and application thereof - Google Patents
Phosphorus-doped fluorescent carbon point with high fluorescent quantum yield as well as preparation method and application thereof Download PDFInfo
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- CN106010523A CN106010523A CN201610344777.9A CN201610344777A CN106010523A CN 106010523 A CN106010523 A CN 106010523A CN 201610344777 A CN201610344777 A CN 201610344777A CN 106010523 A CN106010523 A CN 106010523A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 107
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000003384 imaging method Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims description 43
- 239000011574 phosphorus Substances 0.000 claims description 43
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000001782 photodegradation Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 229910021392 nanocarbon Inorganic materials 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 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 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000005284 excitation Effects 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000012216 imaging agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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 description 1
- 208000005718 Stomach Neoplasms Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000003501 co-culture Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 230000005611 electricity Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 206010017758 gastric cancer Diseases 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 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
- 238000000746 purification Methods 0.000 description 1
- 201000011549 stomach cancer Diseases 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/39—
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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"
Abstract
The invention relates to a phosphorus-doped fluorescent carbon point with a high fluorescent quantum yield as well as a preparation method and application thereof. According to the technical scheme, purified carbon point solid powder is obtained by taking tannic acid and polyethylenimine (PEI), adding de-ionized water and phosphoric acid, then transferring the mixture into a hydrothermal reaction kettle, keeping the heat and reacting for 2h to 6h in a temperature range of 140 DEG C to 240 DEG C, naturally cooling at a room temprature to obtain a light brown nano carbon point crude product solution, and centrifuging, dialyzing, refining, freezing and drying. The carbon point provided by the invention can be used for cell imaging and a photodegradation treatment process of contained organic dyestuffs. The fluorescent quantum yield of the prepared fluorescent carbon point can reach 25.4 percent. After being stored in a dark place for 6 months, the carbon point still can emit bright blue fluorescent light under the illumination of a 365nm ultraviolet lamp and the carbon point has good stability at a room temperature.
Description
Technical field
The present invention relates to carbon nanomaterial technical field, be specifically related to a kind of in phosphoric acid medium, with tannic acid and PEI
Synthesize a kind of phosphorus doping fluorescent carbon point with blue-fluorescence and application thereof.
Background technology
Carbon point (Carbon Dots) is the fluorescent carbon nano-particle that a kind of scattered class being smaller in size than 10nm is spherical, has excellent
Good photoluminescence performance.Compared with traditional organic fluorescent dye, fluorescent carbon point has higher light stability and anti-light bleaching
Property.Additionally, fluorescent carbon point molecular weight and particle diameter are less, good biocompatibility, toxicity is low, exciting light spectrum width and also continuously, can
To realize a polynary transmitting of elementary excitation, be a kind of extraordinary fluorescent labeling and imaging agents, and be successfully applied cell with
In living imaging.Fluorescent carbon point itself has some special natures so that it is in photoelectric device, organic solar batteries, photocatalysis
Etc. aspect be with a wide range of applications.Although carbon point preparation method and related application research have had a large amount of report, but there is also
The problems such as fluorescence quantum yield is relatively low, and preparation process is complicated, therefore find simple, and quickly preparation has good luminous performance
The method of fluorescent carbon point is the most necessary.
Summary of the invention
It is an object of the invention to provide a kind of phosphorus doping fluorescent carbon point simply, effectively with relatively high-fluorescence quantum yield and
Preparation method.
For realizing the purpose of the present invention, the technical solution used in the present invention is as follows: a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon
Point, preparation method is as follows: take tannic acid and PEI, is sequentially added into deionized water and phosphoric acid, after stirring and dissolving, transfer
In reactor, hydro-thermal reaction 2～6h, it is cooled to room temperature, obtains crude product, through dialysis, lyophilization, obtain the phosphorus of purification
Doping fluorescent carbon point.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, in mass ratio, tannic acid: polyethyleneimine
Ammonia=1:1～5.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, every gram of tannic acid adds 15～80ml water.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, every gram of tannic acid adds 1.5～5ml phosphoric acid.
Preferably, above-mentioned a kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point, hydrothermal temperature is 140～240 DEG C.
It is a further object of the present invention to provide the application in bio-imaging and catalytic degradation dyestuff of the phosphorus doping fluorescent carbon point.
The application in degradating organic dye of the above-mentioned high-fluorescence quantum yield phosphorus doping fluorescent carbon point.Method is as follows: in having
Adding the tungsten trioxide photocatalyst that above-mentioned phosphorus doping fluorescent carbon point is modified in the solution of organic dye, under dark surrounds, stirring is inhaled
After attached 1h, with 500W height Hg lamp irradiation；The tungsten trioxide photocatalyst that described phosphorus doping fluorescent carbon point is modified is: by upper
The phosphorus doping fluorescent carbon point stated and WO3Mixing, under the conditions of 140～240 DEG C, reacting by heating 3～4h.
The invention has the beneficial effects as follows:
Preparation method the most of the present invention is simple, be easily achieved industrialized production.Use tannic acid inexpensive, that be easy to get, polymine and
Phosphoric acid, with hydro-thermal reaction technology one-step synthesis fluorescent carbon point.
2. the nano fluorescent carbon point biocompatibility that prepared by the present invention is preferable, it is possible to achieve internal fluorescence imaging.
3. the nano fluorescent carbon point fluorescence quantum yield that prepared by the present invention is up to 25.4%.
4. the nano fluorescent carbon point maximum excitation that prepared by the present invention and transmitting wavelength are respectively 345nm and 469nm.In the dark preserve 6
After individual month, under the ultra violet lamp of 365nm, still send brilliant blue fluorescence.Carbon point stability at room temperature is described
Well.Fluorescent carbon point water solublity prepared by the present invention is good and stable, places and undergo no deterioration for 1 year under room temperature.
Accompanying drawing explanation
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 diagram of fluorescent carbon point solution.
Fig. 5 is the uv-visible absorption spectra figure 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 that different wavelengths of light excites lower fluorescent carbon point solution.
Fig. 8 is the pH value impact (λ ex=345nm) on carbon point solution fluorescence.
Fig. 9 is the NaCl concentration impact (λ ex=345nm) on carbon point solution fluorescence.
Figure 10 is the illumination impact (λ ex=345nm) on carbon point solution fluorescence.
Figure 11 is the fluorescence microscope cell picked-up situation to carbon point.
Figure 12 is that under illumination and dark condition, methylene blue light degradation changes over curve.
Detailed description of the invention
Embodiment 1
Weigh the tannic acid of 0.2g and the PEI of 0.2g, add the deionized water of 10ml, add the phosphoric acid of 0.5ml, fully
Stirring and dissolving, transfers to, in the reactor of 50ml, put in air dry oven, heats 2h in 140 DEG C, naturally cools to room
Temperature, obtains dark-brown carbon point solution, is then passed through dialysis and lyophilization, finally gives phosphorus doping fluorescent carbon point (CDs)
Pressed powder.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 particle diameter of carbon point is at about 9nm.
The X-ray diffraction spectrum of phosphorus doping fluorescent carbon point is as shown in Figure 2.X-ray diffraction analysis shows, carbon point powder exists
One obvious and wider diffraction maximum occurs near 2 θ=23 °, shows that carbon point is to exist in amorphous state mode.
The infrared spectrum of phosphorus doping fluorescent carbon point is as shown in Figure 3.Infrared spectrogram shows that the stretching vibration that there is-OH and-NH is inhaled
Receive peak (3411cm-1), the stretching vibration absworption peak (1623cm of carbonyl-1), the stretching vibration absworption peak that the doping of P-O key produces
At 1088cm-1Near, C-N stretching vibration absworption peak is at 1350cm-1Place.
The zeta current potential of phosphorus doping fluorescent carbon point solution as shown in Figure 4, in the solution when pH=6.0, the zeta current potential of carbon point
It is worth inclined negative value, shows carbon point 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 point solution exists
Having an obvious characteristic absorption peak at 350nm, scope is extended to visual field by ultra-violet (UV) band.
The fluorescence excitation of phosphorus doping fluorescent carbon point solution and emission spectrum are as shown in Figure 6.As seen from the figure, the maximum of fluorescent carbon point swashs
Send out wavelength and maximum emission wavelength is respectively 345nm and 469nm.
Under different wavelengths of light excites, the fluorescence emission spectrum of fluorescent carbon point solution is as shown in Figure 7.By figure it is found that along with
Excitation wavelength increases (from 330nm to 370nm), the fluorescence emission peak of fluorescent carbon point gradually blue shift, it is indicated that prepared carbon
Point has excitation wavelength dependency.
PH value affects result as shown in Figure 8 to carbon point solution fluorescence.As seen from the figure, during pH=5, fluorescence is the strongest, and works as solution
When pH value is increased or decreased, carbon point fluorescence intensity all decreases, and shows that the luminescence generated by light of carbon point is had necessarily by solution acidity
Impact.
The NaCl concentration impact on fluorescent carbon point solution fluorescence: be separately added into the most commensurability in the carbon point solution dilute 50 times
NaCl, measures carbon point fluorescent emission intensity, has investigated the NaCl concentration impact on carbon point fluorescence intensity, and result is shown in Fig. 9.By
Scheming visible, in the range of 0～2.0mol/L, the fluorescence intensity of carbon point solution has almost no change.Therefore, prepared fluorescence
Carbon point has preferable saline-alkaline tolerance.
The illumination impact on carbon point solution fluorescence: the carbon point solution determining dilution 50 times respectively is continuous under 500W height mercury lamp
Irradiate 0.5,1,1.5,2,3,4, fluorescence intensity after 5h.As seen from Figure 10, the fluorescence intensity of carbon point is not sent out
Raw significantly change, shows carbon point good stability, anti-light bleaching.
Embodiment 2
Weigh the tannic acid of 0.2g and the PEI of 1.0g, add the deionized water of 15ml, add the phosphoric acid of 1.0ml, fully stir
Mix dissolving, transfer to, in the reactor of 50ml, put in air dry oven, heat 4 hours in 180 DEG C, naturally cool to
Room temperature, obtains dark-brown carbon point solution, is then passed through dialysis and obtains phosphorus doping fluorescent carbon point solution.
Embodiment 3
Weigh the tannic acid of 0.5g and the PEI of 1.2g, add the deionized water of 20ml, add the phosphoric acid of 1.5ml, fully stir
Mix dissolving, transfer to, in the reactor of 50ml, put in air dry oven, heat 4 hours in 200 DEG C, naturally cool to
Room temperature, obtains dark-brown carbon point solution, is then passed through dialysis and obtains phosphorus doping fluorescent carbon point solution eventually.
Embodiment 4
Weigh the tannic acid of 1.0g and the PEI of 1.2g, add the deionized water of 20ml, add the phosphoric acid of 1.5ml, fully
After stirring, transfer to, in the reactor of 50ml, put in air dry oven, heat 6 hours in 180 DEG C, naturally cool to
Room temperature, obtains dark-brown carbon point solution, is then passed through dialysis and obtains phosphorus doping fluorescent carbon point solution.
Embodiment 5
Weigh the tannic acid of 1.0g and the PEI of 1.2g, add the deionized water of 15ml, add the phosphoric acid of 1.5ml, fully
After stirring, transfer to, in the reactor of 50ml, put in air dry oven, heat 6 hours in 180 DEG C, naturally cool to
Room temperature, obtains dark-brown carbon point solution, is then passed through dialysis and obtains phosphorus doping fluorescent carbon point solution.
The application in bio-imaging agent of the embodiment 6 phosphorus doping fluorescent carbon point
It is that 100 μ g/L phosphorus doping fluorescent carbon point solution co-culture with stomach cancer cell BGC-823 at 37 DEG C by concentration, exists respectively
When 6 and 24h, by the fluorescence microscope cell picked-up situation to carbon point, result is as shown in figure 11.As seen from the figure, with
Time of increases, and cell is the best to carbon point picked-up effect, demonstrates good cell imaging effect.
The application in degradating organic dye of the embodiment 7 phosphorus doping fluorescent carbon point
Method: the tungsten trioxide photocatalyst (CDs-WO that phosphorus doping fluorescent carbon point is modified3): weigh 0.2g tannic acid and
The PEI of 0.4g is in beaker, and adds 15ml deionized water and stir, and adds the phosphoric acid of 0.5ml, proceeds to the water of 50ml
In thermal response still, add the WO of 0.5g3, in air dry oven at a temperature of 230 DEG C, react 3h.Cooling room temperature after from
The heart, is dried to obtain the tungsten trioxide photocatalyst (CDs-WO that carbon point is modified3)。
Take 50ml methylene blue solution (mass concentration is 10mg/L) in beaker, add 50mg CDs-WO3, in dark
Stirring and adsorbing 1h under environment so that it is reach adsorption and desorption balance, then use 500W high voltage mercury lamp radiation, every one section time
Between sample, at wavelength 664nm, measured the absorbance of methylene blue solution by UV, visible light-spectrophotometer, by following
The percent of decolourization of equation calculating methylene blue:
In formula: A0For the initial absorbance of the solution of methylene blue, A is the absorbance of different t methylene blue.
Comparative example 1: phosphorus doping fluorescent carbon point (CDs): weigh the tannic acid of 0.2g and the PEI of 0.4g in beaker, and add
Enter 15ml deionized water to stir, add the phosphoric acid of 0.5ml, proceed in the hydrothermal reaction kettle of 50ml, at air dry oven
In at 140 DEG C, react 2h.It is centrifuged after cooling room temperature, is dried to obtain phosphorus doping fluorescent carbon point.
Take 50ml methylene blue solution (mass concentration is 10mg/L) in beaker, add 50mg phosphorus doping fluorescent carbon point,
Stirring and adsorbing 1h under dark surrounds so that it is reach adsorption and desorption balance, then use 500W high voltage mercury lamp radiation, every
A period of time samples, and is measured the absorbance of methylene blue solution at wavelength 664nm by UV, visible light-spectrophotometer.
Comparative example 2: take 50ml methylene blue solution (mass concentration is 10mg/L) in beaker, adds 50mg nanometer
WO3, stirring and adsorbing 1h under dark surrounds so that it is reach adsorption and desorption balance, then with 500W height Hg lamp irradiation,
Sample at set intervals, at wavelength 664nm, measured the extinction of methylene blue solution by UV, visible light-spectrophotometer
Degree.
Result is as shown in figure 12.Research shows, is used alone WO3Time, the photodegradation rate of methylene blue is 52.3%, and
Adding the fluorescent carbon point that the present invention obtains in system, photodegradation rate reaches 80.7%.Illustrate that the carbon point of the present invention can promote WO3
Photodegradation to methylene blue.
Claims (8)
1. a high-fluorescence quantum yield phosphorus doping fluorescent carbon point, it is characterised in that preparation method is as follows: take tannic acid and polyethyleneimine
Ammonia, is sequentially added into deionized water and phosphoric acid, after stirring and dissolving, transfers in reactor, hydro-thermal reaction 2～6h, cooling
To room temperature, obtain crude product, through dialysis, lyophilization, obtain high-fluorescence quantum yield phosphorus doping fluorescent carbon point.
A kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point the most according to claim 1, it is characterised in that: in mass ratio,
Tannic acid: PEI=1:1～5.
A kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point the most according to claim 1, it is characterised in that: every gram of tannic acid
Add 15～80ml water.
A kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point the most according to claim 1, it is characterised in that: every gram of tannic acid
Add 1.5～5ml phosphoric acid.
A kind of high-fluorescence quantum yield phosphorus doping fluorescent carbon point the most according to claim 1, it is characterised in that: hydro-thermal reaction temperature
Degree is 140～240 DEG C.
6. the application in bio-imaging of the high-fluorescence quantum yield phosphorus doping fluorescent carbon point described in claim 1.
7. the application in degradating organic dye of the high-fluorescence quantum yield phosphorus doping fluorescent carbon point described in claim 1.
Application the most according to claim 7, it is characterised in that: method is as follows: add power in the solution containing organic dyestuff
Profit requires the tungsten trioxide photocatalyst that the phosphorus doping fluorescent carbon point described in 1 is modified, stirring and adsorbing 1h under dark surrounds
Afterwards, 500W high voltage mercury lamp radiation is used；The tungsten trioxide photocatalyst that described phosphorus doping fluorescent carbon point is modified is: will
Phosphorus doping fluorescent carbon point described in claim 1 and WO3Mixing, under the conditions of 140～240 DEG C, reacting by heating
3～4h.
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