CN103480398B - Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof - Google Patents
Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of photocatalysis, particularly to a micronano-structured and graphene based composite visible light catalytic material and a preparing method thereof. The method includes the following steps: dissolving oxidized graphene in water, and performing ultrasonic treatment to obtain an oxidized graphene dispersion liquid; ultrasonically dispersing silver nitrate and zinc oxide in deionized water to obtain a mixed solution, stirring and dropwise adding the solution into the oxidized graphene dispersion liquid, so as to obtain a mixed precursor; slowly and dropwise adding a prepared phosphate solution in the mixed precursor of the oxidized graphene, the silver nitrate and the zinc oxide, and continuously stirring, transferring a greyish-green product obtained through reaction into a hydrothermal reaction kettle, performing hydrothermal reaction at a certain temperature, cooling to the room temperature and centrifuging, then washing the product by the deionized water and absolute ethyl alcohol, and obtaining a composite after vacuum drying. According to the invention, the preparing technology is simple, the required raw materials are abundant, the performance of the product is superior, and motivated by visible light, the catalytic material has stronger degradation activity to organic dyestuff rhodamine B.
Description
Technical field
the present invention relates to photocatalysis technology field, refer in particular to graphene-based composite visible light catalytic material of a kind of micro-nano structure and preparation method thereof, specifically refer to that a kind of hydro-thermal method prepares the method with micro-nano structure Graphene/silver phosphate/zinc oxide composite visible light catalytic material fast, belong to composite, photocatalysis technology and field for the treatment of of water pollution.
Background technology
Zinc oxide is a kind of semi-conducting material of photoelectric properties uniqueness, having the advantages such as activity is high, pollution-free, reserves are many, cheap makes it be subject to extensive concern in photocatalysis field, but due to zinc oxide band gap comparatively large (3.7 eV), the light of whole visible spectrum about 4% can only be utilized to be excited to produce electron-hole pair; And its band structure easily makes the carrier of generation to generation compound, its photocatalysis efficiency is caused to reduce further, in the visible light-responded scope of expansion zinc oxide, extend in many trials of carrier lifetime, the semi-conducting material being compounded to form heterojunction structure with narrow bandgap semiconductor material and zinc oxide is a kind of effective method.
Silver orthophosphate is a kind of narrow bandgap semiconductor material (2.4 eV), has strong visible light-responded characteristic and efficient pollutant catalytic degradation performance; Simultaneously, silver orthophosphate can well mate with zinc oxide band structure, therefore, Zinc oxide nanoparticle is compounded in conductor photocatalysis material silver orthophosphate particulate being formed there is heterojunction structure, the visible light-responded scope of zinc oxide can not only be widened, and when visible ray excitation produces electron-hole pair, the electronics in zinc oxide conduction band can transfer to rapidly the conduction band (conduction band: ZnO>Ag of silver orthophosphate
3pO
4), the valence band (valence band: Ag of zinc oxide is transferred to rapidly in the hole in silver orthophosphate
3pO
4> ZnO), avoid the quick compound of photo-generated carrier, the silver ion generation reduction reaction that also prevent in electronics and silver orthophosphate makes silver orthophosphate decompose, and improves the catalytic efficiency of photochemical catalyst and the cyclical stability of reinforcing material.
Graphene is a kind of new material of the individual layer laminated structure be made up of carbon atom, monolayer carbon original thickness not only makes it not only be applicable to the growth of function nano material, and there is good electronic conductivity, be acknowledged as the ideal carrier material of catalyst, experiment is using graphene oxide as precursor material, silver orthophosphate coring and increment is controlled in the process of reaction, final zinc oxide/silver orthophosphate/Graphene the composite photocatalyst material generated is made to have homogeneous pattern and less size, the high transmission rate of Graphene, high specific area makes obtained composite photocatalyst material have well dispersed and adsorptivity in the solution, its high electrical conductance accelerates the separation of Pair production further, extend the life-span of active component, enhance the catalytic activity of composite photocatalyst material, investigate through data, with commercialization zinc oxide, graphene oxide, silver nitrate and phosphate for raw material, hydro-thermal method Fast back-projection algorithm is used to have the Graphene/zinc oxide/silver orthophosphate composite visible light catalytic material of micro-nano structure and have no report for photocatalysis degradation organic contaminant and resource of purifying waste water.
Summary of the invention
The object of the present invention is to provide that a kind of flow process is simple, environmental friendliness, the method preparing the Graphene/zinc oxide/silver orthophosphate composite visible light catalytic material of the micro-nano structure of controllable appearance with low cost, the composite photocatalyst material of preparation has strong visible light-responded characteristic and remarkable photocatalytic pollutant degradation performance.
Realizing the technical solution adopted in the present invention is: take graphene oxide as precursor material, is compounded on the graphene sheet layer of nanoscale by hydro-thermal method by the bar-shaped zinc oxide of micrometer structure and silver orthophosphate uniform particles, and its concrete preparation method's step is as follows:
(1) graphene oxide is dissolved in deionized water for ultrasonic dispersion, obtains the graphene oxide dispersion that concentration is 0.02-0.2 wt%;
(2) be dissolved in deionized water by silver nitrate and zinc oxide, obtain the mixing precursor solution A of silver nitrate and zinc oxide after ultrasonic process, in mixing precursor solution A, the concentration of silver nitrate is 0.09 mol/L, and oxidation zinc concentration is 0.2-0.8 wt%; Mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic agitation condition, the volume ratio of mixing precursor solution A and graphene oxide dispersion is 1:1, mixed solution at room temperature continues to stir 6-12h, obtains mixing precursor solution B;
(3) phosphate is dissolved in deionized water, obtains the phosphate solution that concentration is 0.15 mol/L;
(4) phosphate solution prepared by step (3) is dropwise slowly added in mixing precursor solution B prepared by step (2) under the condition of magnetic agitation, phosphate solution is 1:5 with the volume ratio mixing precursor solution B, until occur in reaction system that celadon is muddy, mixed solution is transferred in polytetrafluoroethylliner liner after continuing stirring 30-60min, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20-30 h is reacted under 160-200 ° of C condition, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Phosphate described in step 3 is sodium hydrogen phosphate, sodium dihydrogen phosphate or sodium phosphate.
Described mixed solution in step 2 at room temperature continues to stir 6-12h and refers to continue to stir 6-12h with the speed of 100 revs/min.
In step 4, mixed solution is transferred to polytetrafluoroethylliner liner middle finger and is stirred 30min-60min with the speed of 200 revs/min continuation after continuing to stir 30min-60min.
The present invention has the following advantages compared with prior art:
A) zinc oxide and silver orthophosphate have the band structure matched, and they are compounded to form the separation that heterojunction semiconductor material can promote to encourage the electron-hole pair produced, and can also improve the cyclical stability of material.
B) catalysis material obtained by has wider visible light-responded scope and the efficiency of light energy utilization.
C) using graphene oxide as presoma, the active attachment point of surface of graphene oxide can the effectively particle diameter of controlled oxidization zinc and silver orthophosphate particle and the distribution in graphene base body.
D) specific area that Graphene is large and high electric conductivity make composite photocatalyst material have the low plyability of good dispersiveness, adsorptivity and electron-hole pair, make material under visible ray effect, have efficient catalytic oxidation ability.
E) technique prepared is simple, with low cost, energy-conserving and environment-protective and the superior performance of material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the graphene-based composite visible light catalytic material of micro-nano structure;
Fig. 2 is the X ray diffracting spectrum of the graphene-based composite visible light catalytic material of micro-nano structure;
Fig. 3 is the UV-Vis diffuse reflection spectroscopy figure of the graphene-based composite visible light catalytic material of micro-nano structure;
Fig. 4 is the photocatalytic degradation curve map to rhodamine B under the graphene-based composite visible light catalytic material visible ray of micro-nano structure.
Detailed description of the invention
Illustrate content of the present invention further below in conjunction with specific embodiment, but these embodiments do not limit the scope of the invention.
Embodiment 1
10 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 200 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 6 hours, obtain mixing precursor solution B, take 0.426 g Na
2hPO
4be dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under stirring condition, the disodium phosphate soln prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 30 h are reacted under 160 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 2
20 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 300 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 8 hours, obtain mixing precursor solution B, take 0.426 g Na
2hPO
4be dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under stirring condition, the disodium phosphate soln prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 24 h are reacted under 180 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 3
50 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 400 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 10 hours, obtain mixing precursor solution B, take 0.426 g Na
2hPO
4be dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under stirring condition, the disodium phosphate soln prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20 h are reacted under 200 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 4
100 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 800 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 12 hours, obtain mixing precursor solution B, take 0.426 g Na
2hPO
4be dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under stirring condition, the disodium phosphate soln prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20 h are reacted under 200 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 5
10 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 200 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 6 hours, obtain mixing precursor solution B, take 0.36 g NaH
2pO
4be dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under stirring condition, the sodium dihydrogen phosphate prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 30 h are reacted under 160 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 6
20 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 300 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 8 hours, obtain mixing precursor solution B, take 0.36 g NaH
2pO
4be dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under stirring condition, the sodium dihydrogen phosphate prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 24 h are reacted under 180 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 7
50 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 400 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 10 hours, obtain mixing precursor solution B, take 0.36 g NaH
2pO
4be dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under stirring condition, the sodium dihydrogen phosphate prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20 h are reacted under 200 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 8
100 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion, take 1.529 g silver nitrates and 800 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 12 hours, obtain mixing precursor solution B, take 0.36 g NaH
2pO
4be dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under stirring condition, the sodium dihydrogen phosphate prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20 h are reacted under 200 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
Embodiment 9
10 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion.Take 1.529 g silver nitrates and 200 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 6 hours, obtain mixing precursor solution B; Take 0.49 g Na
3pO
4be dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under stirring condition, the sodium radio-phosphate,P-32 solution prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 30 h are reacted under 160 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, washs final vacuum drying respectively after the product centrifugation obtained with deionized water and absolute ethyl alcohol.
Embodiment 10
20 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion.Take 1.529 g silver nitrates and 300 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 8 hours, obtain mixing precursor solution B; Take 0.49 g Na
3pO
4be dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under stirring condition, the sodium radio-phosphate,P-32 solution prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 24 h are reacted under 180 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, washs final vacuum drying respectively after the product centrifugation obtained with deionized water and absolute ethyl alcohol.
Embodiment 11
50 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion.Take 1.529 g silver nitrates and 400 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 10 hours, obtain mixing precursor solution B; Take 0.49 g Na
3pO
4be dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under stirring condition, the sodium radio-phosphate,P-32 solution prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20 h are reacted under 200 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, washs final vacuum drying respectively after the product centrifugation obtained with deionized water and absolute ethyl alcohol.
Embodiment 12
100 mg graphene oxides are scattered in 50 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion.Take 1.529 g silver nitrates and 800 mg ZnO were dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic stirring, continues stirring with the speed of 100 revs/min under room temperature and within 10 hours, obtain mixing precursor solution B; Take 0.49 g Na
3pO
4be dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under stirring condition, the sodium radio-phosphate,P-32 solution prepared is added drop-wise in mixing precursor solution B, until occur in reaction system that celadon is muddy, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner with the speed of 200 revs/min continuation stirring after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20 h are reacted under 200 ° of C conditions, reaction terminates rear reactor and naturally cools to room temperature, washs final vacuum drying respectively after the product centrifugation obtained with deionized water and absolute ethyl alcohol.
Fig. 1 is the scanning electron microscope (SEM) photograph of the prepared graphene-based composite visible light catalytic material of micro-nano structure, as can be seen from figure we, tiny Ag
3pO
4particle aggregation, around oxidation zinc bar, also can see laminar graphene sheet layer in figure; Fig. 2 is the X-ray diffractogram of the prepared graphene-based composite visible light catalytic material of micro-nano structure, diffraction maximums all in diffraction pattern all well corresponds to silver orthophosphate and the zinc oxide of response, less owing to adding graphene oxide amount in reactant, so the Graphene content obtained after reduction is also lower, in addition Graphene diffraction peak intensity relative to the silver orthophosphate of crystallization and zinc oxide diffraction maximum very weak, so fail to observe the diffraction maximum deriving from Graphene in X ray diffracting spectrum; Fig. 3 is the UV-Vis diffuse reflection spectroscopy figure of the prepared graphene-based composite visible light catalytic material of micro-nano structure, as can be seen from figure we, this composite all has good absorption at whole ultraviolet-visible district (200-800 nm), and absorbance is more than 0.8.
By graphene-based for the micro-nano structure of 50 mg composite visible light catalytic material ultrasonic disperse in the rhodamine B solution of 100 milliliter of 25 mg/L after ultrasonic 10 minutes, the dispersion liquid mixed is transferred in the quartzy bottle in xenon lamp catalytic reactor, stir under dark condition after within 30 minutes, making it reach adsorption equilibrium and open xenon source, extracting the postradiation mixed dispersion liquid of 4 mL every 10 minutes with syringe transfers in the centrifuge tube of mark, radiation of visible light closed xenon source after 1 hour, by the sample centrifugation in all centrifuge tubes, centrifugal rear obtained supernatant liquor transfers in quartz colorimetric utensil the absorbance measured on ultraviolet-visible spectrophotometer under the different photocatalysis time further, thus under obtaining each time period the graphene-based composite visible light catalytic material of micro-nano structure under visible light illumination to the photocatalytic degradation curve map of rhodamine B.
The micro-nano structure graphene-based composite visible light catalytic material of Fig. 4 prepared by embodiment 1 under visible light conditions (200-800 nm) to the photocatalytic degradation curve map of rhodamine B, as can be seen from Figure 4, this composite radiation of visible light after 30 minutes to the degradation rate of rhodamine B close to 80%, radiation of visible light after 40 minutes degradation rate reach 100%, photocatalytic degradation curve map shows that the Graphene/silver phosphate/zinc oxide composite photocatalyst material of micro-nano structure has efficient photocatalytic degradation effect to organic dyestuff rhodamine B under visible light illumination.
Claims (4)
1. a preparation method for the graphene-based composite visible light catalytic material of micro-nano structure, described composite visible light catalytic material is formed by zinc oxide, silver orthophosphate and Graphene three kinds of Material claddings; This composite visible light catalytic material all has good absorption in the ultraviolet-visible district of 200-800 nm, and absorbance is more than 0.8; Described composite visible light catalytic material has efficient photocatalytic degradation effect to organic dyestuff rhodamine B under the UV, visible light optical excitation of 200-800 nm: to rhodamine B solution 30 minutes degradation rates of 25 mg/L more than 80%, within 40 minutes, degradation rate reaches 100%, it is characterized in that comprising the steps:
(1) graphene oxide is dissolved in deionized water for ultrasonic dispersion, obtains the graphene oxide dispersion that concentration is 0.02-0.2 wt%;
(2) be dissolved in deionized water by silver nitrate and zinc oxide, obtain the mixing precursor solution A of silver nitrate and zinc oxide after ultrasonic process, in mixing precursor solution A, the concentration of silver nitrate is 0.09 mol/L, and oxidation zinc concentration is 0.2-0.8 wt%; Mixing precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion under magnetic agitation condition, the volume ratio of mixing precursor solution A and graphene oxide dispersion is 1:1, mixed solution at room temperature continues to stir 6-12h, obtains mixing precursor solution B;
(3) phosphate is dissolved in deionized water, obtains the phosphate solution that concentration is 0.15 mol/L;
(4) phosphate solution prepared by step (3) is dropwise slowly added in mixing precursor solution B prepared by step (2) under the condition of magnetic agitation, phosphate solution is 1:5 with the volume ratio mixing precursor solution B, until occur in reaction system that celadon is muddy, mixed solution is transferred in polytetrafluoroethylliner liner after continuing stirring 30-60min, and inner bag is sealed in stainless steel hydrothermal reaction kettle, 20-30 h is reacted under 160-200 ° of C condition, reaction terminates rear reactor and naturally cools to room temperature, final vacuum drying is washed respectively with deionized water and absolute ethyl alcohol after the product centrifugation obtained.
2. the preparation method of the graphene-based composite visible light catalytic material of a kind of micro-nano structure as claimed in claim 1, the described mixed solution that it is characterized in that in step (2) at room temperature continues to stir 6-12h and refers to continue to stir 6-12h with the speed of 100 revs/min.
3. the preparation method of the graphene-based composite visible light catalytic material of a kind of micro-nano structure as claimed in claim 1, is characterized in that the phosphate described in step (3) is sodium hydrogen phosphate, sodium dihydrogen phosphate or sodium phosphate.
4. the preparation method of the graphene-based composite visible light catalytic material of a kind of micro-nano structure as claimed in claim 1, is characterized in that in step (4), mixed solution transfers to polytetrafluoroethylliner liner middle finger with the speed of 200 revs/min continuation stirring 30min-60min after continuing to stir 30min-60min.
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| CN106279645A (en) * | 2016-08-29 | 2017-01-04 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of photochromic poly-lactic acid material |
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