CN105126907A - Organic microsphere-supported three-dimensional graphene-loaded cadmium sulfide composite catalyst and preparation method thereof - Google Patents
Organic microsphere-supported three-dimensional graphene-loaded cadmium sulfide composite catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic microsphere-supported three-dimensional graphene-loaded cadmium sulfide composite catalyst and a preparation method thereof. The catalyst comprises a styrene organic microsphere, graphene oxide and a cadmium sulfide particle, wherein the styrene organic microsphere is used as a carrier, graphene oxide is loaded on the microsphere, and the cadmium sulfide particle is produced by cadmium acetate and dimethyl sulfoxide and grows on the surface layer of graphene oxide. According to the invention, graphene oxide is loaded on the surface of the styrene organic microsphere, and then cadmium sulfide grows on the surface of graphene; graphene is used as an acceptor of photoelectrons, inhibits compounding of photo-induced carriers and can improve the efficiency of a photocatalysis reaction between the photoelectrons and holes; a heterojunction generated in the catalyst promotes transfer of the photoelectrons from the cadmium sulfide catalyst to graphene; thus, a styrene organic microsphere-graphene-cadmium sulfide composite catalyst system for hydrogen production through photolysis of water is eventually constructed and effective utilization of visible light is realized. The catalyst is simple to prepare, does not need any precious metal cocatalyst and has good application values in the field of hydrogen production through photolysis of water.
Description
Technical field
The present invention relates to catalyst field, particularly relate to photochemical catalyst, specifically refer to three-dimensional grapheme sulfur loaded cadmium composite catalyst that a kind of organic micro-spheres supports and preparation method thereof.
Background technology
The consumption of fossil fuel causes energy crisis and the large global problem of environmental pollution two, is also two large problems in the urgent need to address in the world at present.Hydrogen energy source is a kind of clean, non-carbon-emitting, the new forms of energy of high fuel value, and the universal of this new forms of energy form will be very helpful to the above two large global problems of alleviation.Photocatalytic hydrogen production by water decomposition technology is a kind of use semiconductor light-catalyst, and convert solar energy into chemical energy, catalytic decomposition water generates the technology of hydrogen.Renewable energy conversion the abundantest on the earth is that chemical energy is stored in hydrogen by this technology, is the potential hydrogen producing technology of a kind of tool.But easily there is compound in the light induced electron produced by optical excitation due to single semiconductor catalyst and hole, causes single semiconductor catalyst photocatalytic activity low.The present invention is intended to the separative efficiency being improved semiconductor catalyst light induced electron and hole by complex technique, active to the Photocatalyzed Hydrogen Production improving catalyst.
Grapheme material at room temperature has excellent carrier mobility ability, and has high-specific surface area characteristic.It can not only suppress the compound of photo-generated carrier as the acceptor of light induced electron, can also improve the efficiency that light-catalyzed reaction occurs for light induced electron and hole.In addition, Graphene can improve the visible absorption ability of catalyst and suppress the photoetch of catalyst to react.In its preparation process, carry out suitable modification to Graphene makes it be more suitable for the preparation of composite catalyst.Cooperative effect is there is between Graphene composition and the catalyst of load in graphene-based composite catalyst.In view of Graphene These characteristics, grapheme material is introduced photocatalysis field as photochemical catalyst carrier use extensively imitated.But because grapheme material is individual layer laminated structure, the strong π-π effect between lamella often causes the reunion between graphene sheet layer, reduces the utilization rate of Graphene.
The visible light response catalyst of cadmium sulfide (CdS) catalyst to be a kind of energy gap be 2.4eV, is paid close attention to widely because it has good visible light-responded ability.Independent CdS catalyst can produce a large amount of light induced electrons and hole by optical excitation, but light induced electron and hole be easy to CdS body mutually in generation compound, cause catalyst photocatalytic activity low.And this catalyst easily photoetch occurs, photocatalysis stability is low.These two shortcomings greatly limit the further application of CdS catalyst.
Summary of the invention
The object of the invention is the shortcoming overcoming above-mentioned prior art, provide a kind of can realize utilize graphene oxide can load on amidized organic micro-spheres, the hetero-junctions produced in the three-dimensional composite catalyst of preparation facilitates light induced electron from cadmium sulfide catalyst to the transfer of Graphene, Photocatalyzed Hydrogen Production reaction can be there is, three-dimensional grapheme sulfur loaded cadmium composite catalyst that the organic micro-spheres effectively improving the separative efficiency in light induced electron and hole supports and preparation method thereof after photogenerated electrons migrate to Graphene.
To achieve these goals, the present invention has following formation:
The three-dimensional grapheme sulfur loaded cadmium composite catalyst that this organic micro-spheres supports, its main feature is, described catalyst comprises: styrene organic micro-spheres is carrier, graphene oxide-loaded on microballoon, and cadmium acetate and dimethyl sulfoxide (DMSO) generate cadmium sulfide nanoparticles and grow on Graphene top layer.
Preferably, described graphene oxide is carried on microballoon by ethylenediamine coupling agent.
More preferably, described cadmium acetate is cadmium source, and dimethyl sulfoxide (DMSO) is solvent, sulphur source and reducing agent, is grown cadmium sulfide nanoparticles on Graphene top layer by solvent-thermal method.
Further preferably, the particle diameter of described organic micro-spheres is 2 ~ 10 μm, and described cadmium sulfide nanoparticles particle size is 5 ~ 200nm, and described cadmium sulfide nanoparticles grows uniformly on described organic micro-spheres surface.
Most preferably, described organic micro-spheres is polymerized preparation by styrene and GMA monomer dispersion.
According to the preparation method of the three-dimensional grapheme sulfur loaded cadmium composite catalyst that organic micro-spheres supports, its main feature is, described method comprises the following steps:
(1) ethanol polyethylene dissolving pyrrolidones, adds styrene, GMA, passes into nitrogen, discharges air, then adds azodiisobutyronitrile, pass into nitrogen, discharges air, obtains organic micro-spheres after water-bath concussion cleaning eccentric cleaning;
(2) in described organic micro-spheres, add graphene oxide, after stirring in water bath, obtain load three-dimensional graphene oxide styrene organic micro-spheres;
(3) be scattered in dimethyl sulphoxide solution by three-dimensional for described load graphene oxide microballoon and cadmium acetate, magnetic agitation makes dispersion liquid mix;
(4) above-mentioned mixed liquor is joined in water heating kettle, and water heating kettle is put into baking oven, isothermal reaction after oven temperature raises;
(5) product is cooled to room temperature after terminating by reaction, uses washes of absolute alcohol suction filtration product, air-dryly at normal temperatures obtains composite catalyst.
Preferably, described step (1) is specially:
(1.1) taking polyvinylpyrrolidone joins in triangular flask, adds absolute ethyl alcohol and makes it fully dissolve, get styrene, GMA is dissolved in absolute ethyl alcohol and adds triangular flask, passes into nitrogen 5 ~ 20min and discharges air; Take azodiisobutyronitrile to be dissolved in ethanol and to add triangular flask, then after passing into nitrogen 5 ~ 20min, cover lid, uses raw material band sealing; The triangular flask of good seal is put into shaking bath, and shaking speed is set as 100 ~ 300rpm, reacts 6 ~ 24h after being warming up to 50 ~ 80 DEG C; Reaction terminates rear first stopping and heating, the taking-up triangular flask that stops operating to room temperature to be cooled; Reactant liquor is centrifugal, re-use after organic micro-spheres cleans by absolute ethyl alcohol and water, at room temperature dry.
More preferably, described step (2) is specially:
(2.1) organic micro-spheres joins in deionized water, and stir and make it be uniformly dispersed, then add ethylenediamine coupling agent in above-mentioned dispersion liquid, beaker is put into water-bath and is warming up to 50 ~ 80 DEG C, magnetic agitation 3 ~ 24h; Reaction terminates rear cooling naturally, by water and ethanol eccentric cleaning, dry after cleaning; Then the organic micro-spheres after coupling is dispersed in deionized water, adds appropriate graphene oxide dispersion, be warming up to 50 ~ 80 DEG C, stir 1 ~ 12h; Centrifugal after cooling, use deionized water and washes of absolute alcohol, dry after cleaning up.
Further preferably, described step (3) is specially:
(3.1) be that the three-dimensional graphene oxide microballoon of 1wt% ~ 10wt% and the cadmium acetate of 50mg ~ 200mg are scattered in dimethyl solution by load capacity, magnetic agitation makes dispersion liquid mix.
Most preferably, described step (4) is specially:
(4.1) above-mentioned mixed liquor is joined in polytetrafluoroethylliner liner stainless steel water heating kettle, and water heating kettle is put into baking oven, isothermal reaction 3 ~ 24h after oven temperature is elevated to 100 ~ 180 DEG C.
Have employed three-dimensional grapheme sulfur loaded cadmium composite catalyst of the organic micro-spheres support in this invention and preparation method thereof, test from the active testing of catalyst, CdS is carried on the redox graphene surface of organic micro-spheres support by the present invention by solvent-thermal method, effectively can improve the product hydrogen activity of CdS catalyst using Graphene as electron acceptor, can be used for photolysis water hydrogen.The reason that catalytic activity of the present invention is high is the reunion effectively controlling graphene film interlayer, improves the separative efficiency in CdS catalyst light induced electron and hole, reduces the photoetch of CdS catalyst, the final Photocatalyzed Hydrogen Production efficiency improving CdS catalyst.The present invention utilizes at styrene organic micro-spheres area load graphene oxide, by solvent-thermal method, cadmium sulfide is grown at graphenic surface, Graphene as light induced electron acceptor and suppress the compound of photo-generated carrier, the efficiency of light induced electron and hole generation light-catalyzed reaction can also be improved, the hetero-junctions produced in catalyst facilitates light induced electron from CdS catalyst to the transfer of Graphene, finally constructs phenylethylene micro ball-graphene-sulfur cadmium photolysis water hydrogen complex catalyst system.Hydrogen manufacturing experiment shows, this photolysis water hydrogen system exist vulcanized sodium/sodium sulfite or lactic acid as the condition of sacrifice agent under for generating hydrogen by visible light photocatalytic reduction of water reaction, there is very high catalytic activity, solve the defect be used alone of semiconductor catalyst and Graphene, and achieve effective utilization of visible ray.This method for preparing catalyst is simple, and does not need noble metal promoted agent, has very strong using value in photolysis water hydrogen field.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the sample that catalyst different time of the present invention obtains.
The pattern SEM spectrogram of Fig. 2 catalyst that to be catalyst of the present invention prepare in the 6h reaction time.
Fig. 3 is the product hydrogen curve map of catalyst different time of the present invention.
Fig. 4 is the average hydrogen-producing speed figure of the sample that catalyst different time of the present invention obtains.
Detailed description of the invention
In order to more clearly describe technology contents of the present invention, conduct further description below in conjunction with specific embodiment.
Embodiment 1:
The preparation of styrene organic micro-spheres: take 2.0g polyvinylpyrrolidone (PVP) and join in triangular flask, add 20ml absolute ethyl alcohol and make it fully dissolve.Take 12.0g styrene, 3.0g GMA (GMA) is dissolved in 40ml absolute ethyl alcohol and adds triangular flask.Pass into nitrogen 5 ~ 20min and discharge air.Take 0.2g azodiisobutyronitrile (AIBN) to be dissolved in 30ml ethanol and to add triangular flask.After passing into nitrogen 5 ~ 20min again, cover lid, uses raw material band sealing.The triangular flask of good seal is put into shaking bath, and shaking speed is set as 100 ~ 300rpm, reacts 6 ~ 24h after being warming up to 50 ~ 80 DEG C.Reaction terminates rear first stopping and heating, the taking-up triangular flask that stops operating to room temperature to be cooled.Reactant liquor is centrifugal, re-use absolute ethyl alcohol and water by product cleaning to after clean, at room temperature naturally dry.
Embodiment 2:
Prepare graphene oxide-loaded organic micro-spheres: take 9gPSGM organic micro-spheres, join in 60ml deionized water, stir and make it be uniformly dispersed.In above-mentioned dispersion liquid, slowly add 9ml ethylenediamine coupling agent again, beaker is put into water-bath and is warming up to 50 ~ 80 DEG C, magnetic agitation 3 ~ 24h.Reaction terminates rear cooling naturally, by water and ethanol eccentric cleaning, dry after cleaning.Then the organic micro-spheres taken after 100mg coupling is dispersed in deionized water, adds appropriate graphene oxide dispersion, is warming up to 50 ~ 80 DEG C, stirs 1 ~ 12h.Naturally centrifugal after cooling, use deionized water and washes of absolute alcohol, clean up and naturally to dry afterwards.
Embodiment 3:
The preparation of the graphene-supported organic micro-spheres of cadmium sulfide load (PSGM/rGO/CdS): get the PSGM/GO microballoon that 100mg load capacity is 1wt% ~ 10wt%, 50 ~ 200mg cadmium acetate (Cd (CH
3cOO)
22H
2o) dispersing and dissolving is in 60ml dimethyl sulfoxide (DMSO) (DMSO) solvent, is transferred to by solution in 100ml polytetrafluoroethylene (PTFE) water heating kettle inner bag after magnetic agitation 1h.Baking oven is put into, isothermal reaction 3 ~ 24h after oven temperature is elevated to 100 ~ 180 DEG C after installing water heating kettle.Open baking oven after reaction terminates and be cooled to room temperature, use ethanol suction filtration to clean three times, naturally dry, obtain PSGM/rGO/CdS.
Embodiment 4:
The present invention is based on the parallel check experiment whether forming hetero-junctions between catalyst and the impact of experimental result is designed, prepare independent graphene-supported organic micro-spheres and the experiment of simple sulfur cadmium: (1) gets 100mgPSGM/GO microballoon, be scattered in 60ml dimethyl sulfoxide (DMSO), stir 1h and be transferred in 100ml polytetrafluoroethylene (PTFE) water heating kettle inner bag.Put into baking oven after installing water heating kettle, after being warming up to 180 DEG C gradually, react 12h.Open baking oven after reaction terminates and be cooled to room temperature, use ethanol suction filtration wash products three times, naturally dry, obtain graphene-supported organic micro-spheres PSGM/rGO.(2) 150mgCd (CH is taken
3cOO)
22H
2o dispersing and dissolving, in 60ml dimethyl sulfoxide (DMSO) (DMSO) solvent, joins in 100ml polytetrafluoroethylene (PTFE) water heating kettle inner bag.Put into baking oven after installing water heating kettle, after being warming up to 180 DEG C gradually, react 12h.Open baking oven after reaction terminates and be cooled to room temperature, use ethanol suction filtration to clean three times, naturally dry, obtain CdS.
Embodiment 5:
Appropriate composite catalyst prepared by the present invention is applied in photolysis water hydrogen reaction system, it is characterized in that, under visible ray 300w (λ > 400nm) irradiation starts reaction, take in 0.1g catalyst and quartz glass reactor, add 100ml0.5MNa
2s/Na
2sO
3in sacrifice agent solution, ultrasonic disperse 5min after fully stirring.Quartz glass reactor is installed in photolysis water hydrogen reaction system after being uniformly dispersed, with 500r/min rotating speed magnetic agitation, guarantees the sealing that system is good.5h is carried out in experiment, carries out the detection of a hydrogen output in process every 1h, and the product hydrogen situation of record catalyst also calculates the average hydrogen-producing speed of catalyst.
Embodiment 6:
Invention has been different graphene oxide-loaded amount produces the impact of hydrogen activity mensuration on composite catalyst: 1wt% has been prepared in experiment, 2wt%, 3wt%, 4wt%, the PSGM/GO microballoon 100mg of the difference graphene oxide-loaded amount of 5wt% with 10wt% six, uses 150mgCd (CH
3cOO)
22H
2o reacts 12h under 180 DEG C of solvent heat conditions, the CdS in microsphere surface load.After the light-catalyzed reaction of 5h, the average hydrogen-producing speed of the PSGM/rGO/CdS composite catalyst of 5wt%GO load capacity is the highest, is 594.0 μm of olg
-1h
-1.
Embodiment 7:
This experiment also using different cadmium acetate addition on the impact of catalyst activity as examination object: test with different cadmium acetate addition (50,100,150,200mg), under 180 DEG C of solvent heat conditions, 12h is reacted, the PSGM/rGO/CdS composite catalyst of preparation with 100mg5wt%PSGM/GO.When using 150mg cadmium acetate, catalytic activity is the highest, and the average hydrogen-producing speed after 5h is 1262.8 μm of olg
-1h
-1.
Embodiment 8:
Meanwhile, the impact of different solvents hot temperature degree on catalyst pattern is also examined or check: test with 100mg5wt%PSGM/GO microballoon, 150mg cadmium acetate, at differential responses temperature (100,140,180 DEG C) reaction 12h prepared PSGM/rGO/CdS composite catalyst.Experimental result shows, and 180 DEG C time under solvent heat condition, organic micro-spheres surface has many CdS to generate, and microballoon also majority is fold morphology.For ensureing the yield of CdS catalyst, final selective temperature be 180 DEG C as solvent heat temperature.As shown in Figure 1, in this XRD spectra, be respectively the organic micro-spheres (PSGM/GO) of load graphene oxide from top to bottom, catalyst prepared by 24h reaction time catalyst, the 12h reaction time of preparing catalyst, the 6h reaction time of preparing catalyst, the 3h reaction time of preparing catalyst, the 0h reaction time of preparing and CdS catalyst prepared by 12h solvent heat.
Embodiment 9:
This experiment also with the different solvents heat time on the impact of catalyst activity and mechanism for research object: by GO load capacity, the screening of cadmium acetate addition and different reaction temperatures, the reaction condition that we determine is 100mg5wt%PSGM/GO, 150mg cadmium acetate, Kaolinite Preparation of Catalyst at 180 DEG C.We are by research under different reaction time (0h, 3h, 6h, 12h, 24h) conditions now, and what change obtained catalyst has.XRD spectra as shown in Figure 1; SEM figure as shown in Figure 2; Catalysis produces hydrogen curve as shown in Figure 3; Average hydrogen-producing speed as shown in Figure 4.It is the highest that the composite catalyst prepared under the 3h reaction time produces hydrogen activity, and average hydrogen-producing speed reaches 11.3mmolg
-1h
-1.
Have employed three-dimensional grapheme sulfur loaded cadmium composite catalyst of the organic micro-spheres support in this invention and preparation method thereof, test from the active testing of catalyst, CdS is carried on the redox graphene surface of organic micro-spheres support by the present invention by solvent-thermal method, effectively can improve the product hydrogen activity of CdS catalyst using Graphene as electron acceptor, can be used for photolysis water hydrogen.The reason that catalytic activity of the present invention is high is the reunion effectively controlling graphene film interlayer, improves the separative efficiency in CdS catalyst light induced electron and hole, reduces the photoetch of CdS catalyst, the final Photocatalyzed Hydrogen Production efficiency improving CdS catalyst.The present invention utilizes at styrene organic micro-spheres area load graphene oxide, by solvent-thermal method, cadmium sulfide is grown at graphenic surface, Graphene as light induced electron acceptor and suppress the compound of photo-generated carrier, the efficiency of light induced electron and hole generation light-catalyzed reaction can also be improved, the hetero-junctions produced in catalyst facilitates light induced electron from CdS catalyst to the transfer of Graphene, finally constructs phenylethylene micro ball-graphene-sulfur cadmium photolysis water hydrogen complex catalyst system.Hydrogen manufacturing experiment shows, this photolysis water hydrogen system exist vulcanized sodium/sodium sulfite or lactic acid as the condition of sacrifice agent under for generating hydrogen by visible light photocatalytic reduction of water reaction, there is very high catalytic activity, solve the defect be used alone of semiconductor catalyst and Graphene, and achieve effective utilization of visible ray.This method for preparing catalyst is simple, and does not need noble metal promoted agent, has very strong using value in photolysis water hydrogen field.
In this description, the present invention is described with reference to its specific embodiment.But, still can make various amendment and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, description and accompanying drawing are regarded in an illustrative, rather than a restrictive.
Claims (10)
1. the three-dimensional grapheme sulfur loaded cadmium composite catalyst of an organic micro-spheres support, it is characterized in that, described catalyst comprises: styrene organic micro-spheres is carrier, graphene oxide-loaded on microballoon, and cadmium acetate and dimethyl sulfoxide (DMSO) generate cadmium sulfide nanoparticles and grow on Graphene top layer.
2. the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 1, it is characterized in that, described graphene oxide is carried on microballoon by ethylenediamine coupling agent.
3. the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 1, it is characterized in that, described cadmium acetate is cadmium source, and dimethyl sulfoxide (DMSO) is solvent, sulphur source and reducing agent, is grown cadmium sulfide nanoparticles on Graphene top layer by solvent-thermal method.
4. the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 1, it is characterized in that, the particle diameter of described organic micro-spheres is 2 ~ 10 μm, described cadmium sulfide nanoparticles particle size is 5 ~ 200nm, and described cadmium sulfide nanoparticles grows uniformly on described organic micro-spheres surface.
5. the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 1, is characterized in that, described organic micro-spheres is polymerized preparation by styrene and GMA monomer dispersion.
6. a preparation method for the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 1, it is characterized in that, described method comprises the following steps:
(1) ethanol polyethylene dissolving pyrrolidones, adds styrene, GMA, passes into nitrogen, discharges air, then adds azodiisobutyronitrile, pass into nitrogen, discharges air, obtains organic micro-spheres after water-bath concussion cleaning eccentric cleaning;
(2) in described organic micro-spheres, add graphene oxide, after stirring in water bath, obtain the three-dimensional graphene oxide styrene organic micro-spheres of load oxidation;
(3) be scattered in dimethyl sulphoxide solution by three-dimensional for described load graphene oxide microballoon and cadmium acetate, magnetic agitation makes dispersion liquid mix;
(4) above-mentioned mixed liquor is joined in water heating kettle, and water heating kettle is put into baking oven, isothermal reaction after oven temperature raises;
(5) product is cooled to room temperature after terminating by reaction, uses washes of absolute alcohol suction filtration product, air-dryly at normal temperatures obtains composite catalyst.
7. the preparation method of the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 6, it is characterized in that, described step (1) is specially:
(1.1) taking polyvinylpyrrolidone joins in triangular flask, adds absolute ethyl alcohol and makes it fully dissolve, get styrene, GMA is dissolved in absolute ethyl alcohol and adds triangular flask, passes into nitrogen 5 ~ 20min and discharges air; Take azodiisobutyronitrile to be dissolved in ethanol and to add triangular flask, then after passing into nitrogen 5 ~ 20min, cover lid, uses raw material band sealing; The triangular flask of good seal is put into shaking bath, and shaking speed is set as 100 ~ 300rpm, reacts 6 ~ 24h after being warming up to 50 ~ 80 DEG C; Reaction terminates rear first stopping and heating, the taking-up triangular flask that stops operating to room temperature to be cooled; Reactant liquor is centrifugal, re-use after organic micro-spheres cleans by absolute ethyl alcohol and water, at room temperature dry.
8. the preparation method of the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 6, it is characterized in that, described step (2) is specially:
(2.1) organic micro-spheres joins in deionized water, and stir and make it be uniformly dispersed, then add ethylenediamine coupling agent in above-mentioned dispersion liquid, beaker is put into water-bath and is warming up to 50 ~ 80 DEG C, magnetic agitation 3 ~ 24h; Reaction terminates rear cooling naturally, by water and ethanol eccentric cleaning, dry after cleaning; Then the organic micro-spheres after coupling is dispersed in deionized water, adds appropriate graphene oxide dispersion, be warming up to 50 ~ 80 DEG C, stir 1 ~ 12h; Centrifugal after cooling, use deionized water and washes of absolute alcohol, dry after cleaning up.
9. the preparation method of the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 6, it is characterized in that, described step (3) is specially:
(3.1) be that the three-dimensional graphene oxide microballoon of 1wt% ~ 10wt% and the cadmium acetate of 50mg ~ 200mg are scattered in dimethyl solution by load capacity, magnetic agitation makes dispersion liquid mix.
10. the preparation method of the three-dimensional grapheme sulfur loaded cadmium composite catalyst of organic micro-spheres support according to claim 6, it is characterized in that, described step (4) is specially:
(4.1) above-mentioned mixed liquor is joined in polytetrafluoroethylliner liner stainless steel water heating kettle, and water heating kettle is put into baking oven, isothermal reaction 3 ~ 24h after oven temperature is elevated to 100 ~ 180 DEG C.
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