CN102921438B - Preparation for silver phosphate nano ball-graphene composite material and photocatalysis application - Google Patents
Preparation for silver phosphate nano ball-graphene composite material and photocatalysis application Download PDFInfo
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- CN102921438B CN102921438B CN201210437447.6A CN201210437447A CN102921438B CN 102921438 B CN102921438 B CN 102921438B CN 201210437447 A CN201210437447 A CN 201210437447A CN 102921438 B CN102921438 B CN 102921438B
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Abstract
The invention discloses a preparation for a silver phosphate nano ball-graphene composite material and photocatalysis application. The silver phosphate nano ball-graphene composite material is formed by in-situ growth silver phosphate nano balls decorated on the surface of graphene. In the composite material, the ratio of silver phosphate nano balls and the graphene is 100-25 milligram graphene oxide and the surface growth silver phosphate nano balls are 0.33 millimoles. The preparation method comprises steps of dissolving bovine serum albumin to distilled water, gradually dropping a silver nitrate solution, dropping a graphene oxide solution after a white colloid solution is formed, stirring for 2 hours, dropping a disodium hydrogen phosphate solution, stirring for four hours, conducting centrifugation, washing by using the distilled water, drying and obtaining the silver phosphate nano ball-graphene composite material. The composite material can serve as a visible-light-induced photocatalyst, and a photocatalysis experiment proves that the composite material has good visible-light catalytic activity. The preparation is simple and large-scale production can be achieved.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of visible light photocatalytic degradation organic pollutant, be specially preparation and the photocatalytic applications of silver orthophosphate nanosphere-graphene composite material.
Technical background
Current environmental protection and energy crisis become the mankind must in the face of the matter of utmost importance with solution.Semiconductor visible light catalytic degradation technology due to can make full use of solar energy, simple without the need to expensive instrument, preparation, become the advantages such as wood is cheap, non-secondary pollution becoming the effective means of water pollution government gradually.This technology can make full use of photochemical reaction and accelerate organic matter degradation with protection of the environment, contributes to alleviating day by day serious energy crisis simultaneously.
Catalysis material is introduced sewage treatment area by the people [1] such as Carey in 1976, and nano titanium oxide is because of its low price, nontoxic, has stable optical property, and the oxidation susceptibility of excellence becomes the hot research object of photocatalysis field.But because of the restriction of titanium dioxide broad stopband, make it can only at degradation of organic substances under ultraviolet lighting, quantization efficiency be lower in addition, is generally less than 10%.Therefore the visible light catalyst of development of new becomes the focus of this area research.
The bismuth series catalysts such as current pucherite, quantum dot composite catalyst, nano cuprous oxide, Ag@AgC etc. becomes the photochemical catalyst of a new generation.Although these catalyst also have visible light activity, catalytic efficiency need significantly to improve.
Its photoinduced electron of the structures shape of silver orthophosphate own is easy to be separated with hole, there is stronger visible light catalytic performance, be the visible light catalytic material of a new generation, if continue to improve the photoinduced electron of silver orthophosphate and the rate of departure in hole, can further improve its photocatalysis effect.
It is extremely low that Graphene has resistivity, and the speed of electron transfer is exceedingly fast, specific area is high and the advantage such as chemically stable becomes a kind of superior photoelectric material, in solar cell and field of photocatalytic material, is a kind of excellent electron acceptor.Preparing in the process of Graphene by graphite oxidation, the functional group , that surface distributed is enriched is as – COOH, and-OH, C=O etc., provide condition for it forms functional composite further.
If nano silver be modified on graphenic surface, significantly can improve the characteristic of silver orthophosphate absorbing dye, and improve the photoinduced electron-hole separative efficiency of silver orthophosphate, the visible light catalytic efficiency of silver orthophosphate can be significantly improved.
Summary of the invention
The object of the invention aims to provide preparation and the photocatalytic applications of a kind of silver orthophosphate nanosphere-graphene composite material.This silver orthophosphate nanosphere-graphene composite material has stable and that visible light activity is high feature, its preparation method mild condition, easy large-scale production.
In order to achieve the above object, present invention employs following technical scheme:
A kind of silver orthophosphate nanosphere-graphene composite material, this material is formed by being modified at growth in situ silver orthophosphate nanosphere on graphenic surface.In described composite, silver orthophosphate nanosphere and Graphene ratio are: 100 ~ 25 milligrams of graphenic surface grow silver orthophosphate nanosphere 0.33 mM.
The preparation method of silver orthophosphate nanosphere-graphene composite material of the present invention: take bovine serum albumin as additive, is first prepared into white colloidal solution with liquor argenti nitratis ophthalmicus reaction; Again this colloidal solution is mixed with graphene solution, then instill after disodium phosphate soln reacts 4 hours and obtain composite.
The preparation method of silver orthophosphate nanosphere-graphene composite material of the present invention is solwution method, gets bovine serum albumin and is dissolved in distilled water, instill liquor argenti nitratis ophthalmicus gradually, after white colloidal solution to be formed, then instill graphene oxide solution under room temperature; Stir after 2 hours, instillation disodium phosphate soln, stirred after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material.
In preparation method of the present invention, bovine serum albumin concentration of aqueous solution is 0.4mg/mL; Liquor argenti nitratis ophthalmicus concentration is 0.1 M, and disodium phosphate soln concentration is 0.1 M, and the mol ratio of silver nitrate and sodium hydrogen phosphate is 3:1.
In preparation method of the present invention, the concentration of its graphene oxide solution is 0.5 mg/mL, and sodium hydrogen phosphate and graphene oxide ratio are: 100 ~ 25 milligrams of graphene oxides, 0.33 mM of sodium hydrogen phosphate.
In preparation method of the present invention, the synthesis temperature that its silver orthophosphate nanosphere and Graphene form composite is 25 DEG C, reaction time 4 h.
Silver orthophosphate nanosphere-graphene composite material of the present invention is used as visible light catalyst degradable organic pollutant.
The method of silver orthophosphate nanosphere of the present invention-graphene composite material catalytic degradation organic dyestuff: 0.025 gram of silver orthophosphate nanosphere-graphene composite material is distributed to the rhodamine B solution that 50 mL concentration are 52 ppm, at dark state magnetic agitation 30 min, then 150 W xenon lamp simulated solar irradiations are used, take out 3 mL suspension at set intervals, after centrifugation, get clear liquid ultraviolet-visual spectrometer absorbance spectrum.
Silver orthophosphate nanosphere-graphene composite material prepared by the present invention, form by being modified at growth in situ silver orthophosphate nanosphere on graphenic surface, silver orthophosphate nanosphere is evenly distributed on the surface of Graphene; Described composite can absorb the visible ray that equal wavelength is less than 520nm.Under excited by visible light, there is good photocatalysis effect to rhodamine B, can be degradable by rhodamine B in 60min.
Feature of the present invention uses bovine serum albumin and liquor argenti nitratis ophthalmicus to form colloidal solution, thus ensure and graphene solution Homogeneous phase mixing, graphene oxide is reduced into Graphene by bovine serum albumin simultaneously, add sodium hydrogen phosphate growth in situ silver orthophosphate nanosphere on graphenic surface again, thus form composite.Its advantage is that preparation method is simple, and nano silver is evenly distributed at graphenic surface; Composite can be adsorbed with organic dye in a large number, increases the contact area of catalyst and organic dyestuff, can avoid the reunion between nano silver, and improve the stability of silver orthophosphate nanosphere.The distinctive structure of this composite has excellent photocatalysis performance and stability, has important using value in environmental protection, field of nanocomposite materials.
The present invention's chemical reagent used is purchased from Chinese traditional Chinese medicines group, and bovine serum albumin is purchased from Wu great Tian source, Wuhan bio tech ltd.
Accompanying drawing explanation
Fig. 1 is take bovine serum albumin as pattern controlling agent, the flying-spot microscope picture of the pure phosphoric acid silver nanoparticle ball of preparation;
Fig. 2 is the flying-spot microscope picture of silver orthophosphate nanosphere-graphene composite material;
Fig. 3 is the X-ray diffraction picture of material:
Wherein, a is take bovine serum albumin as pattern controlling agent, the X-ray diffractogram of the pure phosphoric acid silver nanoparticle ball of preparation, and b is the X-ray diffractogram of silver orthophosphate nanosphere-graphene composite material;
Fig. 4 is the uv-visible absorption spectra figure of silver orthophosphate nanosphere-graphene composite material;
Fig. 5 be silver orthophosphate nanosphere-graphene composite material under radiation of visible light condition, the time dependent abosrption spectrogram of rhodamine B;
Fig. 6 is silver orthophosphate nanosphere, the light degradation curve of silver orthophosphate nanosphere-graphene composite material catalysis rhodamine B under excited by visible light.
Detailed description of the invention
Illustrate content of the present invention further below in conjunction with instantiation, but these enforcements do not limit the scope of the invention.
Embodiment 1
Getting 0.04g bovine serum albumin under room temperature is dissolved in 100mL distilled water, instills 0.1M liquor argenti nitratis ophthalmicus 10mL gradually, after white colloidal solution to be formed, then instills graphene oxide solution 100mL(0.5mg/mL); Magnetic agitation is after 2 hours, and instillation 0.1M disodium phosphate soln 3.3mL, magnetic agitation is after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material.
Fig. 2 is shown in by the flying-spot microscope picture of product phosphoric acid silver nanoparticle ball-graphene composite material, and X-ray diffractogram is shown in b in Fig. 3, and the uv-visible absorption spectra of silver orthophosphate nanosphere-graphene composite material is shown in Fig. 4.
Will
0.025gram silver orthophosphate nanosphere-graphene composite material is distributed to the rhodamine B solution that 50 mL concentration are 52 ppm, at dark state magnetic agitation 30 min, then 150 W xenon lamp simulated solar irradiations are used, take out 3 mL suspension at set intervals, after centrifugation, get clear liquid ultraviolet-visual spectrometer absorbance spectrum.The results are shown in Figure 5, Fig. 6.
The preparation of pure phosphoric acid silver nanoparticle ball: get 0.04g bovine serum albumin under room temperature and be dissolved in 100mL distilled water, instill 0.1M liquor argenti nitratis ophthalmicus 10mL gradually, after white colloidal solution to be formed, instillation 0.1M disodium phosphate soln 3.3mL, magnetic agitation is after 4 hours, centrifugal, distilled water washs, drying obtains pure phosphoric acid silver nanoparticle ball, and the flying-spot microscope picture of prepared pure phosphoric acid silver nanoparticle ball is as Fig. 1; X-ray diffraction picture is as a in Fig. 3, and silver orthophosphate nanosphere light degradation curve of catalysis rhodamine B under excited by visible light is shown in Fig. 6.
Embodiment 2
Getting 0.04g bovine serum albumin under room temperature is dissolved in 100mL distilled water, instills 0.1M liquor argenti nitratis ophthalmicus 10mL gradually, after white colloidal solution to be formed, then instills graphene oxide solution 150mL(0.5mg/mL); Magnetic agitation is after 2 hours, and instillation 0.1M disodium phosphate soln 3.3mL, magnetic agitation is after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material.
Fig. 2 is shown in by the flying-spot microscope picture of product, and X-ray diffractogram is shown in b in Fig. 3, and uv-visible absorption spectra is shown in Fig. 4.Rhodamine B degradation solution experiments, with embodiment 1, the results are shown in Figure 5, Fig. 6.
Embodiment 3
Getting 0.04g bovine serum albumin under room temperature is dissolved in 100mL distilled water, instills 0.1M liquor argenti nitratis ophthalmicus 10mL gradually, after white colloidal solution to be formed, then instills graphene oxide solution 200mL(0.5mg/mL); Magnetic agitation is after 2 hours, and instillation 0.1M disodium phosphate soln 3.3mL, magnetic agitation is after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material.
Fig. 2 is shown in by the flying-spot microscope picture of product, and X-ray diffractogram is shown in b in Fig. 3, and uv-visible absorption spectra is shown in Fig. 4.Rhodamine B degradation solution experiments, with embodiment 1, the results are shown in Figure 5, Fig. 6.
Embodiment 4
Getting 0.02g bovine serum albumin under room temperature is dissolved in 100mL distilled water, instills 0.1M liquor argenti nitratis ophthalmicus 10mL gradually, after white colloidal solution to be formed, then instills graphene oxide solution 200mL(0.5mg/mL); Magnetic agitation is after 2 hours, and instillation 0.1M disodium phosphate soln 3.3mL, magnetic agitation is after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material.
Fig. 2 is shown in by the flying-spot microscope picture of product, and X-ray diffractogram is shown in b in Fig. 3, and uv-visible absorption spectra is shown in Fig. 4.Rhodamine B degradation solution experiments, with embodiment 1, the results are shown in Figure 5, Fig. 6.
Embodiment 5
Getting 0.04g bovine serum albumin under room temperature is dissolved in 100mL distilled water, instills 0.1M liquor argenti nitratis ophthalmicus 10mL gradually, after white colloidal solution to be formed, then instills graphene oxide solution 50mL(0.5mg/mL); Magnetic agitation is after 2 hours, and instillation 0.1M disodium phosphate soln 3.3mL, magnetic agitation is after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material.
Fig. 2 is shown in by the flying-spot microscope picture of product, and X-ray diffractogram is shown in b in Fig. 3, and uv-visible absorption spectra is shown in Fig. 4.Rhodamine B degradation solution experiments is with embodiment 1.The results are shown in Figure 5, Fig. 6.
Claims (4)
1. silver orthophosphate nanosphere-graphene composite material, it is characterized in that, described composite is formed by being modified at growth in situ silver orthophosphate nanosphere on graphenic surface, its preparation method is solwution method: get bovine serum albumin under room temperature and be dissolved in distilled water, form the bovine serum albumin aqueous solution, instill liquor argenti nitratis ophthalmicus gradually, after white colloidal solution to be formed, then instill graphene oxide solution; Magnetic agitation, after 2 hours, instills disodium phosphate soln, and magnetic agitation is after 4 hours, and centrifugal, distilled water washs, drying obtains silver orthophosphate nanosphere-graphene composite material; Wherein, described bovine serum albumin concentration of aqueous solution is 0.4mg/mL, described liquor argenti nitratis ophthalmicus concentration is 0.1 M, disodium phosphate soln concentration is 0.1 M, the mol ratio of silver nitrate and sodium hydrogen phosphate is 3:1, the concentration of graphene oxide solution is 0.5 mg/mL, and sodium hydrogen phosphate and graphene oxide ratio are: 100 ~ 25 milligrams of graphene oxides, sodium hydrogen phosphate 0.33 mM.
2. silver orthophosphate nanosphere-graphene composite material as claimed in claim 1, it is characterized in that, in described composite, silver orthophosphate nanosphere and Graphene ratio are: 100 ~ 25 milligrams of graphenic surface grow silver orthophosphate nanosphere 0.33 mM.
3. the application of silver orthophosphate nanosphere-graphene composite material as claimed in claim 1, is characterized in that, as visible light catalyst degradable organic pollutant.
4. the method for silver orthophosphate nanosphere-graphene composite material catalytic degradation organic dyestuff as claimed in claim 1, it is characterized in that, 0.025 gram of silver orthophosphate nanosphere-graphene composite material is distributed to the rhodamine B solution that 50 mL concentration are 52 ppm, at dark state magnetic agitation 30 min, then 150 W xenon lamp simulated solar irradiations are used, take out 3 mL suspension at set intervals, after centrifugation, get clear liquid ultraviolet-visual spectrometer absorbance spectrum.
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