CN103480398A - 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
- Publication number
- CN103480398A CN103480398A CN201310429025.9A CN201310429025A CN103480398A CN 103480398 A CN103480398 A CN 103480398A CN 201310429025 A CN201310429025 A CN 201310429025A CN 103480398 A CN103480398 A CN 103480398A
- Authority
- CN
- China
- Prior art keywords
- visible light
- graphene
- precursor solution
- solution
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
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 the photocatalysis technology field, refer in particular to graphene-based composite visible light catalysis material of a kind of micro-nano structure and preparation method thereof, particularly refer to a kind of with hydro-thermal method fast preparation there is the method for micro-nano structure Graphene/phosphoric acid silver/zinc oxide composite visible light catalysis material, belong to composite, photocatalysis technology and water pollution control field.
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 in photocatalysis field, be subject to extensive concern, but, due to zinc oxide band gap large (3.7 eV), can only utilize the light of whole visible spectrum 4% left and right to be excited to produce electron-hole pair; And its band structure easily makes the carrier of generation compound to occurring, cause its photocatalysis efficiency further to reduce, in many trials of the visible light-responded scope of expansion zinc oxide, prolongation carrier lifetime, the semi-conducting material that is 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 and zinc oxide band structure can well be mated, therefore, Zinc oxide nanoparticle is compounded on the silver orthophosphate particulate and forms the conductor photocatalysis material with heterojunction structure, not only can widen the visible light-responded scope of zinc oxide, and when visible ray excitation produces electron-hole pair, the electronics in the zinc oxide conduction band can transfer to rapidly silver orthophosphate conduction band (conduction band: ZnO>Ag
3pO
4), the valence band (valence band: Ag of zinc oxide is transferred to rapidly in the hole in silver orthophosphate
3pO
4znO), avoided the compound fast of photo-generated carrier, also prevented that the silver ion generation reduction reaction in electronics and silver orthophosphate from decompose silver orthophosphate, improved the catalytic efficiency of photochemical catalyst the cyclical stability of reinforcing material.
Graphene is a kind of new material of the individual layer laminated structure consisted of carbon atom, the 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 usingd graphene oxide as precursor material, control silver orthophosphate nucleation and growth in the process of reaction, make the final zinc oxide/silver orthophosphate generated/Graphene composite photocatalyst material there is the pattern of homogeneous and less size, the high transmission rate of Graphene, high specific area makes prepared composite photocatalyst material have good dispersiveness and adsorptivity in solution, its high electrical conductance is further accelerated the separation of Pair production, extend the life-span of active component, strengthened the catalytic activity of composite photocatalyst material, through data, investigate, take commercialization zinc oxide, graphene oxide, silver nitrate and phosphate as raw material, use hydro-thermal method synthetic Graphene/zinc oxide with micro-nano structure/silver orthophosphate composite visible light catalysis material have no report for photocatalysis degradation organic contaminant and the resource of purifying waste water fast.
Summary of the invention
The object of the present invention is to provide that a kind of flow process is simple, the method for environmental friendliness, the Graphene/zinc oxide for preparing the micro-nano structure of controllable appearance with low cost/silver orthophosphate composite visible light catalysis material, the composite photocatalyst material of preparation has strong visible light-responded characteristic and remarkable photocatalytic degradation pollutant performance.
Realize that the technical solution adopted in the present invention is: take graphene oxide as precursor material, by hydro-thermal method by the bar-shaped zinc oxide of micrometer structure and silver orthophosphate uniform particles be compounded on the graphene sheet layer of nanoscale, its concrete preparation method's step is as follows:
(1) graphene oxide is dissolved in to deionized water for ultrasonic and disperses, the graphene oxide dispersion liquid that to obtain concentration be 0.02-0.2 wt%;
(2) silver nitrate and zinc oxide are dissolved in deionized water, obtain the mixing precursor solution A of silver nitrate and zinc oxide after ultrasonic processing, the concentration of mixing silver nitrate in precursor solution A is 0.09 mol/L, and the oxidation zinc concentration is 0.2-0.8 wt%; To mix precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion liquid under the magnetic agitation condition, the volume ratio of mixing precursor solution A and graphene oxide dispersion liquid 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) in the mixing precursor solution B that the phosphate solution prepared by step (3) under the condition of magnetic agitation dropwise slowly adds step (2) to prepare, phosphate solution is 1:5 with the volume ratio of mixing precursor solution B, until occur the celadon muddiness in reaction system, mixed solution is transferred in polytetrafluoroethylliner liner after continuing to stir 30-60min, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20-30 h under 160-200 ° of C condition, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
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 that the speed with 100 rev/mins continues to stir 6-12h.
Transfer to the polytetrafluoroethylliner liner middle finger after mixed solution continuation stirring 30min-60min in step 4 and stir 30min-60min with the speed continuation of 200 rev/mins.
The present invention has the following advantages compared with prior art:
A) zinc oxide and silver orthophosphate have the band structure be complementary, and they are compounded to form the separation that the heterojunction semiconductor material can promote the electron-hole pair that excitation produces, and can also improve the cyclical stability of material.
B) prepared catalysis material has wider visible light-responded scope and the efficiency of light energy utilization.
C), using graphene oxide as presoma, the active attachment point on graphene oxide surface can effectively be controlled particle diameter and the distribution on the Graphene matrix of zinc oxide and silver orthophosphate particle.
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 have efficient catalytic oxidation ability under the visible ray effect.
E) technique prepared is simple, with low cost, the superior performance of energy-conserving and environment-protective and material.
The accompanying drawing explanation
The scanning electron microscope diagram that Fig. 1 is the graphene-based composite visible light catalysis material of micro-nano structure;
The X ray diffracting spectrum that Fig. 2 is the graphene-based composite visible light catalysis material of micro-nano structure;
The UV-Vis DRS spectrogram that Fig. 3 is the graphene-based composite visible light catalysis material of micro-nano structure;
Fig. 4 is to the photocatalytic degradation curve map of rhodamine B under the graphene-based composite visible light catalysis material of micro-nano structure visible ray.
The specific embodiment
Further illustrate content of the present invention below in conjunction with specific embodiment, but these embodiment do not limit the scope of the invention.
Embodiment 1
10 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 200 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 30 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 30 h under 160 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 2
20 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 300 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 40 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 24 h under 180 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 3
50 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 400 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 50 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20 h under 200 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 4
100 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 800 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 60 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20 h under 200 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 5
10 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 200 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 30 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 30 h under 160 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 6
20 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 300 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 40 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 24 h under 180 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 7
50 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 400 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 50 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20 h under 200 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 8
100 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid, take 1.529 g silver nitrates and 800 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 60 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20 h under 200 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
Embodiment 9
10 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid.Take 1.529 g silver nitrates and 200 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 30 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 30 h under 160 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, washs respectively the final vacuum drying.
Embodiment 10
20 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid.Take 1.529 g silver nitrates and 300 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 40 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 24 h under 180 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, washs respectively the final vacuum drying.
Embodiment 11
50 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid.Take 1.529 g silver nitrates and 400 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 50 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20 h under 200 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, washs respectively the final vacuum drying.
Embodiment 12
100 mg graphene oxides are scattered in to 50 ml deionized water for ultrasonic and within 5 hours, obtain the graphene oxide dispersion liquid.Take 1.529 g silver nitrates and 800 mg ZnO and be dissolved in 50 ml deionized water for ultrasonic after 30 minutes, obtain mixing precursor solution A, to mix precursor solution A and be added drop-wise under magnetic agitation in above-mentioned graphene oxide dispersion liquid, and under room temperature, with the speed continuation of 100 rev/mins, stir 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 to and mixes in precursor solution B, until occur the celadon muddiness in reaction system, dropwising rear mixed solution transfers in polytetrafluoroethylliner liner after 60 minutes with the speed continuation stirring of 200 rev/mins, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20 h under 200 ° of C conditions, after reaction finishes, reactor naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, washs respectively the final vacuum drying.
The scanning electron microscope (SEM) photograph that Fig. 1 is the prepared graphene-based composite visible light catalysis material of micro-nano structure, from figure, we can find out, tiny Ag
3pO
4particle aggregation, around the oxidation zinc bar, also can be seen laminar graphene sheet layer in figure; The X-ray diffractogram that Fig. 2 is the prepared graphene-based composite visible light catalysis material of micro-nano structure, diffraction maximums all in diffraction pattern are all well corresponding to the silver orthophosphate and the zinc oxide that respond, owing to adding in reactant, the graphene oxide amount is less, so the Graphene content obtained after reduction is also lower, the silver orthophosphate of the relative crystallization of diffraction peak intensity of Graphene and zinc oxide diffraction maximum are very weak in addition, so fail to observe the diffraction maximum that derives from Graphene in X ray diffracting spectrum; The UV-Vis DRS spectrogram that Fig. 3 is the prepared graphene-based composite visible light catalysis material of micro-nano structure, from figure, we can find out, this composite all has preferably and absorbs at whole ultraviolet-visible district (200-800 nm), and absorbance surpasses 0.8.
By after in the ultrasonic rhodamine B solution that is scattered in 100 milliliter of 25 mg/L of the graphene-based composite visible light catalysis material of the micro-nano structure of 50 mg ultrasonic 10 minutes, the dispersion liquid mixed is transferred in the quartzy bottle in the xenon lamp catalytic reactor, open xenon source after under dark condition, stirring makes it reach adsorption equilibrium in 30 minutes, extracted the postradiation mixed dispersion liquid of 4 mL transfers in the centrifuge tube of mark every 10 minutes with syringe, radiation of visible light was closed xenon source after 1 hour, by the sample centrifugation in all centrifuge tubes, centrifugal rear resulting supernatant liquor is further transferred in quartz colorimetric utensil and measure the absorbance under the different photocatalysis time on ultraviolet-visible spectrophotometer, thereby obtain the photocatalytic degradation curve map to rhodamine B under radiation of visible light of the graphene-based composite visible light catalysis material of micro-nano structure under each time period.
Fig. 4 is the graphene-based composite visible light catalysis material of the prepared micro-nano structure of embodiment 1 (200-800 nm) photocatalytic degradation curve map to rhodamine B under the visible ray condition, as can be seen from Figure 4, this composite radiation of visible light after 30 minutes the degradation rate to rhodamine B approach 80%, radiation of visible light after 40 minutes degradation rate reach 100%, the photocatalytic degradation curve map shows that the Graphene of micro-nano structure/phosphoric acid silver/zinc oxide composite photocatalyst material has efficient photocatalytic degradation effect to the organic dyestuff rhodamine B under radiation of visible light.
Claims (5)
1. the graphene-based composite visible light catalysis material of micro-nano structure, it is characterized in that: described composite visible light catalysis material is formed by zinc oxide, silver orthophosphate and three kinds of Material claddings of Graphene; This composite visible light catalysis material all has absorption preferably in the ultraviolet-visible district of 200-800 nm, absorbance surpasses 0.8; Described composite visible light catalysis material has efficient photocatalytic degradation effect to the organic dyestuff rhodamine B under the UV, visible light optical excitation of 200-800 nm: the 30 minutes degradation rates of rhodamine B solution to 25 mg/L reach 100% over 80%, 40 minute degradation rate.
2. the preparation method of the graphene-based composite visible light catalysis material of a kind of micro-nano structure as claimed in claim 1, is characterized in that comprising the steps:
(1) graphene oxide is dissolved in to deionized water for ultrasonic and disperses, the graphene oxide dispersion liquid that to obtain concentration be 0.02-0.2 wt%;
(2) silver nitrate and zinc oxide are dissolved in deionized water, obtain the mixing precursor solution A of silver nitrate and zinc oxide after ultrasonic processing, the concentration of mixing silver nitrate in precursor solution A is 0.09 mol/L, and the oxidation zinc concentration is 0.2-0.8 wt%; To mix precursor solution A is added drop-wise in above-mentioned graphene oxide dispersion liquid under the magnetic agitation condition, the volume ratio of mixing precursor solution A and graphene oxide dispersion liquid 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) in the mixing precursor solution B that the phosphate solution prepared by step (3) under the condition of magnetic agitation dropwise slowly adds step (2) to prepare, phosphate solution is 1:5 with the volume ratio of mixing precursor solution B, until occur the celadon muddiness in reaction system, mixed solution is transferred in polytetrafluoroethylliner liner after continuing to stir 30-60min, and inner bag is sealed in the stainless steel hydrothermal reaction kettle, reaction 20-30 h under 160-200 ° of C condition, after reaction finishes, reactor naturally cools to room temperature, wash respectively the final vacuum drying with deionized water and absolute ethyl alcohol after resulting product centrifugation.
3. the preparation method of the graphene-based composite visible light catalysis material of a kind of micro-nano structure as claimed in claim 1, is characterized in that described mixed solution in step (2) at room temperature continues to stir 6-12h and refers to that the speed with 100 rev/mins continues to stir 6-12h.
4. the preparation method of the graphene-based composite visible light catalysis 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.
5. the preparation method of the graphene-based composite visible light catalysis material of a kind of micro-nano structure as claimed in claim 1, is characterized in that transferring to the polytetrafluoroethylliner liner middle finger after mixed solution continuation stirring 30min-60min in step (4) stirs 30min-60min with the speed continuation of 200 rev/mins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310429025.9A CN103480398B (en) | 2013-09-22 | 2013-09-22 | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310429025.9A CN103480398B (en) | 2013-09-22 | 2013-09-22 | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103480398A true CN103480398A (en) | 2014-01-01 |
| CN103480398B CN103480398B (en) | 2015-07-08 |
Family
ID=49821184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310429025.9A Expired - Fee Related CN103480398B (en) | 2013-09-22 | 2013-09-22 | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103480398B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759282A (en) * | 2014-12-01 | 2015-07-08 | 青岛科技大学 | Novel method for microwave-assisted preparation of zinc oxide/graphene/silver nano-composite photocatalyst |
| CN106084687A (en) * | 2016-08-29 | 2016-11-09 | 佛山市高明区尚润盈科技有限公司 | A kind of except the preparation method of formaldehyde PET/PTT alloy |
| CN106084688A (en) * | 2016-08-29 | 2016-11-09 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of radioprotective PET/PTT alloy |
| CN106084704A (en) * | 2016-08-29 | 2016-11-09 | 佛山市高明区尚润盈科技有限公司 | A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch |
| CN106189124A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of the PET/PTT alloy with antibacterial effect |
| CN106182807A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates |
| CN106182808A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of antibacterial glass reinforced plastic packing crates |
| CN106220831A (en) * | 2016-08-29 | 2016-12-14 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of poly-lactic acid material |
| CN106221150A (en) * | 2016-08-29 | 2016-12-14 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of PET/PTT alloy capable of purifying air |
| 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 |
| CN106336628A (en) * | 2016-08-29 | 2017-01-18 | 佛山市高明区尚润盈科技有限公司 | Preparation method of PET-PPT alloy |
| CN106349663A (en) * | 2016-08-29 | 2017-01-25 | 佛山市高明区尚润盈科技有限公司 | Preparing method for polylactic acid antibacterial radiation-resistant masterbatch |
| CN106363931A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Manufacturing method for glass fiber reinforced plastic packaging box |
| CN106366591A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336627A (en) * | 2016-08-29 | 2017-01-18 | 佛山市高明区尚润盈科技有限公司 | Method for preparing antibacterial PET/PTT alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631939A (en) * | 2012-03-28 | 2012-08-15 | 江苏大学 | Graphene/silver phosphate composite visible light photocatalyst and preparation method thereof |
| CN102921416A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nano composite photocatalytic material and method for preparing same |
-
2013
- 2013-09-22 CN CN201310429025.9A patent/CN103480398B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631939A (en) * | 2012-03-28 | 2012-08-15 | 江苏大学 | Graphene/silver phosphate composite visible light photocatalyst and preparation method thereof |
| CN102921416A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nano composite photocatalytic material and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| WEI LIU ET AL: ""Ag3PO4/ZnO:An efficient visible-light-sensitized composite with its application in photocatalytic degradation of Rhodamine B"", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759282A (en) * | 2014-12-01 | 2015-07-08 | 青岛科技大学 | Novel method for microwave-assisted preparation of zinc oxide/graphene/silver nano-composite photocatalyst |
| CN106084687A (en) * | 2016-08-29 | 2016-11-09 | 佛山市高明区尚润盈科技有限公司 | A kind of except the preparation method of formaldehyde PET/PTT alloy |
| CN106084688A (en) * | 2016-08-29 | 2016-11-09 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of radioprotective PET/PTT alloy |
| CN106084704A (en) * | 2016-08-29 | 2016-11-09 | 佛山市高明区尚润盈科技有限公司 | A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch |
| CN106189124A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of the PET/PTT alloy with antibacterial effect |
| CN106182807A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates |
| CN106182808A (en) * | 2016-08-29 | 2016-12-07 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of antibacterial glass reinforced plastic packing crates |
| CN106220831A (en) * | 2016-08-29 | 2016-12-14 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of poly-lactic acid material |
| CN106221150A (en) * | 2016-08-29 | 2016-12-14 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of PET/PTT alloy capable of purifying air |
| 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 |
| CN106336628A (en) * | 2016-08-29 | 2017-01-18 | 佛山市高明区尚润盈科技有限公司 | Preparation method of PET-PPT alloy |
| CN106349663A (en) * | 2016-08-29 | 2017-01-25 | 佛山市高明区尚润盈科技有限公司 | Preparing method for polylactic acid antibacterial radiation-resistant masterbatch |
| CN106363931A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Manufacturing method for glass fiber reinforced plastic packaging box |
| CN106366591A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103480398B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103480398B (en) | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof | |
| CN103480399B (en) | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof | |
| CN103480400B (en) | A kind of silver phosphate/zinc oxide composite photocatalyst material and preparation method thereof | |
| Guo et al. | Highly efficient visible-light-driven photo-Fenton catalytic performance over FeOOH/Bi2WO6 composite for organic pollutant degradation | |
| Wang et al. | Preparation of p–n junction Cu2O/BiVO4 heterogeneous nanostructures with enhanced visible-light photocatalytic activity | |
| Shi et al. | Magnetically retrievable CdS/reduced graphene oxide/ZnFe2O4 ternary nanocomposite for self-generated H2O2 towards photo-Fenton removal of tetracycline under visible light irradiation | |
| CN102580736B (en) | Grapheme / silver vanadium oxide nanometer composite visible light catalyst and preparation method thereof | |
| Zhu et al. | Construction of 2D/2D TiO2/g-C3N4 nanosheet heterostructures with improved photocatalytic activity | |
| Xin et al. | Synthesis of ZnS@ CdS–Te composites with p–n heterostructures for enhanced photocatalytic hydrogen production by microwave-assisted hydrothermal method | |
| CN103521248A (en) | Method for preparing graphene-based composite visible light catalysis material | |
| CN102580714A (en) | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof | |
| CN106994360A (en) | A kind of preparation method of Z configurations visible light catalytic decomposition water composite | |
| Yang et al. | Preparation of TiO 2/SiO 2 composite oxide and its photocatalytic degradation of rhodamine B | |
| CN105148955A (en) | Preparation process of complex photocatalyst with multiwalled carbon nanotube loading silver/silver phosphate core-shell structure | |
| CN103785429B (en) | A kind of silver orthophosphate/Graphene/titanic oxide nano compound material and preparation method | |
| CN105709782A (en) | Preparing method and application of Ag/AgBr/BiOCl-(001) nanometer composite material | |
| CN104607228A (en) | Preparation method for alpha-Fe2O3 quantum dot/nitrogen-doped graphene composite material | |
| CN104128180B (en) | The method of Electron Beam Irradiation synthesis cuprous oxide/Graphene photocatalysis composite nano materials | |
| CN105858632A (en) | Cobaltous phosphate nanotube material, preparation method thereof and application of cobaltous phosphate nanotube material in photosplitting water into oxygen | |
| Zhang et al. | Enhanced visible-light photocatalytic H2 production of hierarchical g-C3N4 hexagon by one-step self-assembly strategy | |
| CN107790129A (en) | Preparation method of cuprous oxide/graphene visible-light photocatalyst and products thereof and application | |
| Tang et al. | Facile ultrasonic synthesis of novel zinc sulfide/carbon nanotube coaxial nanocables for enhanced photodegradation of methyl orange | |
| Zhang et al. | Synthesis of butterfly-like BiVO4/RGO nanocomposites and their photocatalytic activities | |
| Dong et al. | Sulfur nanoparticles in situ growth on TiO 2 mesoporous single crystals with enhanced solar light photocatalytic performance | |
| CN103157495A (en) | Au/BiOBr0.2I0.8 visible-light-induced catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150708 Termination date: 20150922 |
|
| EXPY | Termination of patent right or utility model |