CN103521248A - Method for preparing graphene-based composite visible light catalysis material - Google Patents
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Abstract
The invention relates to a light catalysis material, and in particular relates to a method for preparing a graphene-based composite visible light catalysis material. The method comprises the following steps: dissolving graphene oxide into water, so as to obtain a graphene oxide dispersion liquid in an ultrasonic mode; dropping a silver nitrate solution into the graphene oxide dispersion liquid under a stirring condition, and stirring for a certain time to obtain a mixed pecursor solution A; slowly dropping a prepared titanium dioxide solution into the mixed pecursor solution A to obtain a mixed solution B; slowly dropping a prepared phosphate solution into the mixed solution B to obtain a mixed solution C, continuously stirring the mixed solution C for a certain time, subsequently transferring the mixed solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at certain temperature, and cooling to be the room temperature; subsequently carrying out centrifuging, washing and vacuum drying on a product so as to ultimately obtain the composite material. The material shows super-high degradation activity to organic dye Rhodamine B under the action of visible light excitation.
Description
Technical field
the present invention relates to catalysis material, refer in particular to a kind of preparation method of graphene-based composite visible light catalysis material, refer to that especially a kind of hydro-thermal legal system of using, for the method for the graphene-based three-system composite visible light of micro-nano structure catalysis material, belongs to composite, photocatalysis technology and water pollution control field.
Background technology
As everyone knows, titanium dioxide has obtained widely and has paid close attention to as conductor photocatalysis material, but titanium dioxide light abstraction width narrower (only limiting to ultraviolet region), quantum efficiency are lower, particularly low its photocatalytic activity under radiation of visible light that causes of its visible light-responded degree is limited; Research shows, has at high proportion and pattern is controlled that { 001} face titanium dioxide nanoplate shows excellent photocatalysis performance under UV-irradiation.
Silver orthophosphate, as a kind of novel catalysis material, under excited by visible light, has the band structure of dispersion, energy gap relative narrower, the recombination rate of photo-generated carrier is reduced greatly, and quantum efficiency is greatly improved, thereby shows excellent visible light photocatalysis active; But, to prepare the compound that silver orthophosphate used argentiferous and make preparation cost higher, the size of the silver orthophosphate material of preparing in addition all bigger than normal and pattern is difficult to control, and the chemical stability of silver orthophosphate material is poor.
Graphene is a kind of allotrope of having of material with carbon element, is a kind of good carrier material, and loaded with nano particle can obtain good dispersiveness in the above; What is more important, Graphene or a kind of electron acceptor material, Graphene and titanium dioxide is compound, and at the interface of bi-material, the optical excitation electrons on titanium dioxide conduction band is transferred to being with of Graphene, thereby greatly reduce the recombination rate of electron-hole pair, be that titanium dioxide has higher catalytic activity, due to the adjustment that can be with, Graphene can also be brought into play the effect of sensitising agent, the light abstraction width that is titanium dioxide expands visible region to, has effectively improved the utilization rate to solar energy.
The compound prepared composite photo-catalyst of Graphene and titanium dioxide has shown excellent performance, researcher has synthesized Graphene/silver orthophosphate/titanic oxide composite photochemical catalyst material by hydro-thermal method again, profit has obtained the bifunctional visible-light photocatalysis material that specific area is large, heat endurance is high in this way, and this material also has the performance of stronger photocatalytic activity and good degradable organic pollutant; But, this method is in finely dispersed liquor argenti nitratis ophthalmicus, directly to drip sodium hydrogen phosphate, be swift in response and generate silver orthophosphate yellow mercury oxide, and carry out compoundly with graphene oxide and titanium dioxide, because the excessive velocities of reaction can cause the large-area gathering of silver orthophosphate particle, thereby generate the larger spherical silver orthophosphate structure of particle, and, the structure of this material is also uncontrollable, and pattern is also irregular, can affect to a certain extent the ability of photocatalysis performance and the degradable organic pollutant of material; Take titanium dioxide nanoplate, silver nitrate, phosphate and graphene oxide at present as raw material, utilize the cooperative effect of controlling between silver orthophosphate and titanium dioxide nanoplate to improve the photocatalytic activity of composite, by hydro-thermal method, prepare and there is micro-nano structure three-system composite visible light catalysis material, and be applied to photocatalysis degradation organic contaminant and have no report.
Summary of the invention
The object of the present invention is to provide that a kind of flow process is simple, the method for the micro-nano structure composite visible light catalysis material of environmental friendliness, preparation with low cost, the composite photocatalyst material of preparation has visible light-responded characteristic and excellent Photocatalytic Activity for Degradation pollutant performance widely.
Realizing the technical solution adopted in the present invention is: take graphene oxide as precursor material, by hydro-thermal method by titanium dioxide nanoplate and silver orthophosphate uniform particles be compounded on Graphene matrix, its concrete preparation method's step is as follows:
(1) graphene oxide is dissolved in deionized water, ultrasonic being uniformly dispersed obtains the graphene oxide dispersion liquid that concentration is 0.06-0.6 wt%;
(2) silver nitrate is dissolved in deionized water, obtains liquor argenti nitratis ophthalmicus; Under stirring condition, liquor argenti nitratis ophthalmicus is joined in above-mentioned graphene oxide dispersion liquid, stir 6-12h, obtain mixing precursor solution A, in mixed solution, the concentration of silver nitrate is 0.15 mol/L;
(3) titanium dioxide nanoplate is dissolved in to deionized water for ultrasonic and disperses, obtain titanium oxide dispersion; Under stirring condition, be added drop-wise in above-mentioned mixing precursor solution A, obtain mixed solution B, in mixed solution B, the concentration of titanium dioxide is 0.48-1.8 wt%;
(4) phosphate is dissolved in deionized water, obtains the phosphate solution that concentration is 0.15 mol/L;
(5) under stirring condition, phosphate solution prepared by step (4) dropwise adds in the prepared mixed solution B of step (3), reaction system occurs that celadon is muddy, the volume ratio of phosphate solution and mixed solution B is 1: 4, the mixed solution obtaining after dropwising is transferred in polytetrafluoroethylliner liner after continuing to stir 30-60 min, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160-200 ° of C condition, react 20-30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Phosphate described in step 3 is sodium hydrogen phosphate, sodium dihydrogen phosphate or sodium phosphate.
Described titanium dioxide nanoplate preparation process is as follows:
(1) hydrofluoric acid is added in deionized water, obtain hydrofluoric acid solution, in solution, the mass ratio of hydrofluoric acid is 50%;
(2) under magnetic agitation condition, butyl titanate is dropwise slowly added in the prepared hydrofluoric acid solution of step (1), in reaction system, there is white opacity, the volume ratio of butyl titanate and hydrofluoric acid solution is 5:8;
(3) dropwise after rear mixed solution continues to stir and transfer in polytetrafluoroethylliner liner, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
The present invention has the following advantages compared with prior art:
A) titanium dioxide and silver orthophosphate have the band structure matching, and they are compounded to form the separation that 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 efficient efficiency of light energy utilization.
C) 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.
D) technique prepared is simple, with low cost, the superior performance of energy-conserving and environment-protective and material.
E) titanium dioxide nanoplate has better visible absorption effect than titanium dioxide granule, for composite, can improve the response of composite to visible ray, thereby the visible light photocatalysis effect of composite is improved.
Accompanying drawing explanation
Fig. 1 is the surface sweeping Electronic Speculum figure of prepared titanium dioxide nanoplate material, visible a large amount of thin plate-like titanium dioxide materials in figure; The size of resulting titanium dioxide nanoplate is between 50-70 nm;
In Fig. 2, the high-resolution-ration transmission electric-lens figure of titanium dioxide nanoplate material shows, the thickness of resulting titanium dioxide nanoplate is between 4-5 nm;
Fig. 3 is the scanning electron microscope diagram of micro-nano structure composite visible light catalysis material;
Fig. 4 is the X ray diffracting spectrum of micro-nano structure composite visible light catalysis material;
Fig. 5 is the UV-vis DRS spectrogram of micro-nano structure composite visible light catalysis material;
Fig. 6 is the Photocatalytic Activity for Degradation curve map of micro-nano structure composite visible light catalysis material to rhodamine B.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate content of the present invention, but these embodiment do not limit the scope of the invention.
Embodiment 1
20 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 300 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30 min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
50 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 240 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 3
100 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 600 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 4
200 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 900 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 5
20 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 300 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 6
50 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 240 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 7
100 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 600 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 8
200 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 900 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 9
20 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 300 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
50 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 240 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
Embodiment 11
100 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 600 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
Embodiment 12
200 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 900 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
Fig. 3 is the scanning electron microscope (SEM) photograph of prepared micro-nano structure composite visible light catalysis material, and from figure, we can see tiny silver orthophosphate spheric granules and titanium dioxide lamellar structure; Fig. 4 is the X-ray diffractogram of prepared micro-nano structure three compound catalyze materials, diffraction maximums all in diffraction pattern are all well corresponding to the silver orthophosphate and the titanium dioxide that respond, owing to adding in reactant, graphene oxide amount is less, so the Graphene content obtaining after reduction is also lower, the silver orthophosphate of the relative crystallization of diffraction peak intensity of Graphene and titanium dioxide diffraction maximum are very weak in addition, so fail to observe the diffraction maximum that derives from Graphene in X ray diffracting spectrum; Fig. 5 is the UV-vis DRS spectrogram of prepared micro-nano structure composite visible light catalysis material, and from figure, we can find out, this composite has good absorption in the ultraviolet-visible district of 200-800 nm, and absorbance is all greater than 0.4.
In addition, the prepared micro-nano structure three-system composite visible light catalysis material of the present invention is used to the photocatalytic degradation experiment of organic dyestuff rhodamine B, and detailed process and step are as follows:
Micro-nano structure silver orthophosphate based composites prepared by 100 mg is ultrasonic be scattered in the rhodamine B solution of 100 milliliter of 10 mg/L after ultrasonic 10 minutes, the dispersion liquid mixing is transferred in the quartzy bottle in xenon lamp catalytic reactor, under dark condition, stir after within 30 minutes, making it reach adsorption equilibrium and open xenon source, every 5 minutes, with syringe, extracting the postradiation mixed dispersion liquid of 4 mL transfers in the centrifuge tube of mark, the radiation of visible light of 400-800 nm is after half an hour, by the sample centrifugation in all centrifuge tubes, centrifugal rear resulting supernatant liquor is further transferred to and in quartz colorimetric utensil, on ultraviolet-visible spectrophotometer, is measured the absorbance under the different photocatalysis time, thereby obtain micro-nano structure phosphoric acid money base composite visible light catalysis material photocatalytic degradation curve map to rhodamine B under the radiation of visible light of 400-800 nm under each time period.
Fig. 6 is prepared micro-nano structure phosphoric acid money base composite visible light catalysis material photocatalytic degradation curve map to rhodamine B under visible ray condition, as can be seen from Figure 4, this composite under dark condition to the adsorption rate of rhodamine B 22%, reach after adsorption-desorption balance, turn on light radiation of visible light rhodamine B degraded in 30 minutes completely; Photocatalytic degradation curve map shows that micro-nano structure silver orthophosphate based composites has certain adsorption effect to rhodamine B, has good photocatalytic degradation effect to rhodamine B under radiation of visible light.
Claims (6)
1. a preparation method for graphene-based composite visible light catalysis material, is characterized in that preparation process is as follows:
(1) graphene oxide is dissolved in deionized water, ultrasonic being uniformly dispersed obtains the graphene oxide dispersion liquid that concentration is 0.06-0.6 wt%;
(2) silver nitrate is dissolved in deionized water, obtains liquor argenti nitratis ophthalmicus; Under stirring condition, liquor argenti nitratis ophthalmicus is joined in above-mentioned graphene oxide dispersion liquid, stir 6-12h, obtain mixing precursor solution A, in mixed solution, the concentration of silver nitrate is 0.15 mol/L;
(3) titanium dioxide nanoplate is dissolved in to deionized water for ultrasonic and disperses, obtain titanium oxide dispersion; Under stirring condition, be added drop-wise in above-mentioned mixing precursor solution A, obtain mixed solution B, in mixed solution B, the concentration of titanium dioxide is 0.48-1.8 wt%;
(4) phosphate is dissolved in deionized water, obtains the phosphate solution that concentration is 0.15 mol/L;
(5) under stirring condition, phosphate solution prepared by step (4) dropwise adds in the prepared mixed solution B of step (3), reaction system occurs that celadon is muddy, the volume ratio of phosphate solution and mixed solution B is 1: 4, the mixed solution obtaining after dropwising is transferred in polytetrafluoroethylliner liner after continuing to stir 30-60 min, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160-200 ° of C condition, react 20-30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
2. the preparation method of a kind of graphene-based composite visible light catalysis material 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.
3. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, is characterized in that described titanium dioxide nanoplate preparation process is as follows:
(1) hydrofluoric acid is added in deionized water, obtain hydrofluoric acid solution, in solution, the mass ratio of hydrofluoric acid is 50%;
(2) under magnetic agitation condition, butyl titanate is dropwise slowly added in the prepared hydrofluoric acid solution of step (1), in reaction system, there is white opacity, the volume ratio of butyl titanate and hydrofluoric acid solution is 5:8;
(3) dropwise after rear mixed solution continues to stir and transfer in polytetrafluoroethylliner liner, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
4. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 3, is characterized in that: the size of described titanium dioxide nanoplate is between 50-70 nm, and thickness is between 4-5 nm.
5. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, it is characterized in that: described graphene-based composite visible light catalysis material has good absorption in the ultraviolet-visible district of 200-800 nm, and absorbance is all greater than 0.4.
6. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, it is characterized in that: described graphene-based composite visible light catalysis material under dark condition to the adsorption rate of the rhodamine B in the rhodamine B solution of 10 mg/L 22%, reach after adsorption-desorption balance, under the radiation of visible light of 400-800 nm, rhodamine B degraded in 30 minutes completely.
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| CN104826639A (en) * | 2015-04-03 | 2015-08-12 | 浙江理工大学 | Silver phosphate/reduction graphene/titanium dioxide nanometer composite material and preparation method thereof |
| CN105540733A (en) * | 2016-01-26 | 2016-05-04 | 浙江工商大学 | TiO2-reduced graphene composite and preparation method thereof and application of TiO2-reduced graphene composite to artificial sea water system |
| CN105771980A (en) * | 2016-04-27 | 2016-07-20 | 吉首大学 | Graphene/silver/mesoporous titanium dioxide nanometer composite photocatalyst and preparation technology thereof |
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| CN103877694B (en) * | 2014-03-13 | 2016-05-25 | 江苏大学 | A kind of TiO2The method of the organic pollution visible ray anaerobic degradation of nano material mediation |
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| CN105540733A (en) * | 2016-01-26 | 2016-05-04 | 浙江工商大学 | TiO2-reduced graphene composite and preparation method thereof and application of TiO2-reduced graphene composite to artificial sea water system |
| CN105833865B (en) * | 2016-04-11 | 2017-12-26 | 河南科技学院 | A kind of preparation method of the graphene-supported Ag photochemical catalysts with concave surface cube pattern |
| CN105833865A (en) * | 2016-04-11 | 2016-08-10 | 河南科技学院 | A preparing method of a graphene-loaded Ag photocatalyst having a cubic morphology |
| CN105771980A (en) * | 2016-04-27 | 2016-07-20 | 吉首大学 | Graphene/silver/mesoporous titanium dioxide nanometer composite photocatalyst and preparation technology thereof |
| CN110639514A (en) * | 2019-10-30 | 2020-01-03 | 武汉低维材料研究院有限公司 | High-stability silver oxide-graphene composite material and preparation method and application thereof |
| CN110743585A (en) * | 2019-11-20 | 2020-02-04 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
| CN111313043A (en) * | 2020-02-20 | 2020-06-19 | 中国科学技术大学 | Graphene-supported phosphate catalyst, and preparation method and application thereof |
| CN111313043B (en) * | 2020-02-20 | 2021-07-06 | 中国科学技术大学 | Graphene-supported phosphate catalyst, and preparation method and application thereof |
| CN113004888A (en) * | 2021-02-24 | 2021-06-22 | 青岛大学 | Europium complex doped TiO2Nano particle fluorescence sensing material, preparation method and application |
| CN113004888B (en) * | 2021-02-24 | 2023-06-06 | 青岛大学 | Europium complex doped TiO 2 Nanoparticle fluorescent sensing material, preparation method and application |
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