CN103586051A - Composite metal sulfide photocatalyst, and preparation method and application thereof - Google Patents

Composite metal sulfide photocatalyst, and preparation method and application thereof Download PDF

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CN103586051A
CN103586051A CN201310613579.4A CN201310613579A CN103586051A CN 103586051 A CN103586051 A CN 103586051A CN 201310613579 A CN201310613579 A CN 201310613579A CN 103586051 A CN103586051 A CN 103586051A
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metal sulfide
agins
presoma
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CN103586051B (en
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安长华
王淑涛
姜雯
刘俊学
张军
张钦辉
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China University of Petroleum East China
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Abstract

The invention provides a composite metal sulfide photocatalyst, and a preparation method and an application thereof, and belongs to the technical field of new energy materials. A technical scheme adopted in the invention is characterized in that the expression formula of the composite metal sulfide photocatalyst is AgInS2-xAg2S-yZnS-zIn6S7, and each of x, y and z is 0 or 1. The invention also provides the preparation method of the catalyst, and the application of the catalyst. The structural composition of the catalyst (the concrete values of x, y and z) changes with the change of a ratio of reaction predecessors in an ordered manner; and the catalyst has an excellent solar reduction performance of water-to-hydrogen, and is suitable for the new energy exploitation field.

Description

A kind of composition metal sulfide photocatalyst and its preparation method and application
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Technical field
The invention belongs to new energy materials technical field, relate in particular to a kind of composition metal sulfide photocatalyst that is applied to the hydrogen manufacturing of sunlight catalytic reductive water and its preparation method and application.
Background technology
Mankind's activity causes energy resource consumption to present explosive growth, however fossil energy (oil, natural gas, coal) available quantity seriously reduce, be tending towards gradually exhausted.Solar energy inexhaustible, nexhaustible, economic environmental protection is comparatively desirable energy sources.Photocatalysis technology is with its room temperature deep reaction and can directly utilize the characteristics such as solar energy, becomes a kind of desirable clear energy sources production technology.Since Fujishima in 1972 and professor Honda find to utilize titanium dioxide electrodes can decomposition water under ultraviolet lighting to generate hydrogen and oxygen, photocatalysis technology has just caused various countries scientists' extensive concern.
Through the research of decades, this technology makes important progress aspect photolysis water hydrogen, and wide spectrum, to absorb the development that sunshine drives photochemical catalyst be by force to promote one of its practical key factor.Compound heterogeneous type semiconductor catalyst, as a kind of important means that regulates and controls sunshine response and promote catalytic performance, embodies its potential superiority day by day.Metal sulfide semiconductor is showing good activity as CdS etc. aspect photolysis water hydrogen, yet its photetching is serious, has limited it and has further applied.The utilization high temperature sintering technology such as Japan scientist Kudo have been prepared AgInS 2-ZnS photochemical catalyst, but its reaction condition is comparatively harsh.Therefore, research and development mild condition is prepared novel composite highly effective hydrogen manufacturing photochemical catalyst and is seemed particularly necessary.
Summary of the invention
The invention provides a kind of composition metal sulfide photocatalyst and its preparation method and application, solved the efficiency of composition metal sulfide aspect sunshine hydrogen manufacturing.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A sulfide photocatalyst, the expression formula of described photochemical catalyst is AgInS 2- xag 2s- yznS- zin 6s 7 x, y, zget respectively 0 or 1, when x, y, zwhen different, be 0 o'clock, the Heterogeneous Composite structure that described catalyst is sulfide.
If x, y, zall getting 0, is AgInS 2pure phase photochemical catalyst, one-component AgInS 2still there is photocatalysis performance, but no longer include heterojunction structure, and photocatalysis performance is lower than having xag 2s- yznS- zin 6s 7the composite photo-catalyst of heterojunction structure, as long as x, y, zwhen different, get 0, this catalyst is exactly the Heterogeneous Composite structure of sulfide.
The preparation method of above-mentioned composition metal sulfide photocatalyst, comprises the steps:
(1) utilize the synthetic diethyldithiocar bamic acid indium (In (DDTC) of the deposition-precipitation method 3) presoma;
(2) by appropriate zinc acetate and above-mentioned In (DDTC) 3presoma and AgI join polytetrafluoroethyllining lining autoclave, and under hydro-thermal pressurized conditions, photochemical catalyst AgInS is prepared in reaction 2- xag 2s- yznS- zin 6s 7.
Further, In (DDTC) 3the synthetic method of presoma is as follows:
Hydration indium trichloride (InCl 34H 2o) with sodium diethyldithiocarbamate ((C 2h 5) 2nCSSNa3H 2o) alcohol mixed solution stirring reaction, can make diethyldithiocar bamic acid indium (In (DDTC) 3) presoma, wherein, the concentration of indium trichloride solution is 0.09-0.12 molL -1, the concentration of sodium diethyldithiocarbamate solution is 0.25-0.35 molL -1.
Further, described hydrothermal reaction process is as follows: by AgI and In (DDTC) 3presoma is transferred in the teflon-lined reactor that fills the deionized water that accounts for its volume 70-80%, by the 0.15-8 of the amount of Ag elemental substance, doubly add zinc acetate, then reactor is put to 160-250 ℃ of baking ovens and reacted 6-48 h, product, through centrifugal and deionized water washing, obtains AgInS after completion of the reaction 2- xag 2s- yznS- zin 6s 7compound heterogeneous photochemical catalyst.
The application of above-mentioned composition metal sulfide photocatalyst aspect the hydrogen manufacturing of sunshine reductive water.
Concrete, heterojunction structure metal sulfide AgInS 2- xag 2s- yznS- zin 6s 7the material preparation of photochemical catalyst, comprises the following steps:
(1) In (DDTC) 3synthesizing of presoma: prepare respectively InCl 34H 2o and (C 2h 5) 2nCSSNa3H 2the ethanolic solution of O, then, by above-mentioned two kinds of solution hybrid reaction a period of time under agitation, can make In (DDTC) 3presoma.Wherein, InCl 34H 2the concentration of O solution is 0.09-0.12 mol/L, (C 2h 5) 2nCSSNa3H 2the concentration of O solution is 0.25-0.35 mol/L.
(2) AgI's is synthetic: polyvinylpyrrolidone (PVP) and silver acetate (AgAc) are joined in the round-bottomed flask that deionized water and ethylenediamine are housed, and stirring and dissolving at 30 ℃, then slowly injects KI (I -: Ag +=1.2:1) solution, makes AgI presoma after reacting 10 min, and wherein, PVP concentration is 0.03-0.05 mol/L, and the concentration of AgAc is 0.02-0.03 mol/L.
(3) by AgI and In (DDTC) 3transfer to and fill in 25 mL deionized water teflon-lined reactors, add zinc acetate Zn (CHCOO) 2(0.01-0.5 g), after reactor sealing 180 0under C, react 24-36 h, product is through centrifugal and deionized water washing after completion of the reaction.
It is simple that the method for the invention has technique, with low cost, and reproducible feature can be used for preparation and forms controlled, the efficient sunshine hydrogen manufacturing of performance photochemical catalyst.
Therefore, the present invention is based on hydro-thermal integrated reacting, by regulating the additional proportion of different presomas, realized the composition regulation and control of hetero-junctions complex sulfide photochemical catalyst.The preparation of catalyst adopts the integrated synthetic technology of hydro-thermal method: be about to pre-synthesis AgI nano particle and In (DDTC) 3together join in water heating kettle, then add a certain amount of Zn (CH 3cOO) 2, after directly being sealed, be placed on 180 0under C, react 24-36 h, obtain AgInS 2- xag 2s- yznS- zin 6s 7composite photo-catalyst.
Metal sulfide AgInS 2- xag 2s- yznS- zin 6s 7the hydrogen manufacturing of heterojunction structure photochemical catalyst sunshine
Take 20 mg AgInS 2- xag 2s- yznS- zin 6s 7photochemical catalyst, is dispersed in 50 mL deionized waters, then adds respectively 2.5 mL ammonium chloroplatinate solution (1mg/mL), 2.6 g Na 2sO 3, 3.6 g Na 2s9H 2o, under magnetic stirs, with 300 W xenon lamps (adding ultraviolet filter), as visible light source, light source and liquid level distance 25 cm, carry out the experiment of photo-reduction water, and reacting space 1 h carries out test sample one time, by gas-chromatography, carries out qualitative analysis, determines the content of product.Reaction finish after by catalyst recovery.
The catalyst A gInS that adopts above-mentioned preparation method to make 2- xag 2s- yznS- zin 6s 7it is a kind of composite photo-catalyst with heterojunction structure.This catalyst, in conjunction with integrated various semi-conductive photoelectric characteristics, has visible light intensity absorption characteristic, has increased substantially solar energy utilization ratio, shows very high activity and stability in sunshine hydrogen production process.These features show that this catalyst has higher using value in new energy development field.The preferred group of described heterojunction structure composition metal sulfide becomes AgInS 2-Ag 2s-ZnS-In 6s 7.
Above-mentioned visible light catalyst is having good effect aspect simulated solar irradiation hydrogen manufacturing, be the novel photocatalysis material that meets new forms of energy demand.
Compared with prior art, advantage of the present invention and good effect are: the present invention prepares heterojunction structure metal sulfide composite Nano photochemical catalyst by an easy step hydro-thermal reaction, and can be used in the hydrogen manufacturing of sunshine reductive water, enrich the technology of preparing of metal sulfide catalysis material, widened its using value.
Accompanying drawing explanation
Fig. 1: heterojunction structure metallic sulfide nano-particle AgInS prepared by embodiment 1-5 2- xag 2s- yznS- zin 6s 7eSEM picture and hydrogen manufacturing design sketch (in figure, scale is 400 nm);
The heterojunction structure metallic sulfide nano-particle AgInS of Fig. 2: embodiment 3 preparations 2-Ag 2the TEM-HRTEM spectrogram of S-ZnS;
Fig. 3: heterojunction structure metallic sulfide nano-particle AgInS prepared by embodiment 1-5 2- xag 2s- yznS- zin 6s 7xRD spectra;
Fig. 4: the heterojunction structure metal sulfide AgInS that embodiment 1-5 is synthetic 2- xag 2s- yznS- zin 6s 7photoelectric current curve;
Fig. 5: the heterojunction structure metal sulfide AgInS that embodiment 1-5 is synthetic 2- xag 2s- yznS- zin 6s 7impedance curve;
Fig. 6: the heterojunction structure metal sulfide AgInS that embodiment 2-5 is synthetic 2- xag 2s- yznS- zin 6s 7energy dispersive spectrogram (EDAX);
As shown in Figure 1, the scanning electron microscope sem photo of embodiment 1-5 gained catalyst, the nano flower that embodiment 1 gained photochemical catalyst is assembled into by nanometer sheet, pattern is regular; Embodiment 2 gained photochemical catalysts are mainly nanometer sheet, and pattern is regular; Embodiment 3 gained photochemical catalysts are mainly mixed and are formed by bulky grain, nanometer sheet; Embodiment 4 gained photochemical catalysts are mainly the oarse-grained mixing patterns of various bulks; Embodiment 5 gained photochemical catalysts are mainly that particle not of uniform size mixes.As shown in Fig. 1 F, the sunshine hydrogen manufacturing successful of embodiment 3,4,5 gained photochemical catalysts is better than embodiment 1 and 2, and wherein embodiment 3 gained photochemical catalyst effects are best.
As shown in Figure 2, the TEM-HRTEM photo of the photochemical catalyst that embodiment 3 obtains, the lattice proof AgInS in figure 2, Ag 2the existence of S and ZnS.
As shown in Figure 3, the XRD spectra of the resulting photochemical catalyst of embodiment 1-5, proves that embodiment 1 gained photochemical catalyst consists of AgInS 2, embodiment 2 gained photochemical catalysts consist of AgInS 2-Ag 2s, embodiment 3 gained photochemical catalysts consist of AgInS 2-Ag 2s-ZnS, embodiment 4 gained photochemical catalysts consist of AgInS 2-Ag 2s-ZnS-In 6s 7, embodiment 5 gained photochemical catalysts consist of AgInS 2-Ag 2s-ZnS-In 6s 7.
As shown in Figure 4, the photoelectric current spectrogram of the resulting photochemical catalyst of embodiment 1-5, wherein the photoelectric current of embodiment 1 is maximum, shows that embodiment 1 photoelectron of generation and the photoelectron number of transfer are maximum.
As shown in Figure 5, the impedance spectrogram of the resulting photochemical catalyst of embodiment 1-5, wherein the impedance ring of embodiment 3 is minimum, shows embodiment 3(AgInS 2-Ag 2s-ZnS) there is best electronics transfer effect, consistent with hydrogen manufacturing effect.
As shown in Figure 6, the EDAX analysis result of the resulting photochemical catalyst of embodiment 2-5, the photochemical catalyst Ag:Zn=2:1 that embodiment 2 obtains, the photochemical catalyst Ag:Zn=1:1 that embodiment 3 obtains, the photochemical catalyst Ag:Zn=1:1 that embodiment 4 obtains, the photochemical catalyst Ag:Zn=1:5 that embodiment 5 obtains.
The specific embodiment
The present invention is directed to the deficiencies in the prior art, heterojunction structure metal sulfide AgInS is provided 2-xAg 2s-yZnS-zIn 6s 7the preparation method of sunshine hydrogen manufacturing nano-photocatalyst.
Photochemical catalyst of the present invention is by AgInS 2, Ag 2s, ZnS, In 6s 7form, directly that these several heterogeneous semiconductors are compound by hydro-thermal method, its composition can be by adding material rate to regulate and control.
Experimental procedure is:
(1) In (DDTC) 3synthesizing of presoma: prepare respectively InCl 34H 2o, (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then, by above-mentioned two kinds of solution hybrid reaction a period of time under agitation, can make In (DDTC) 3presoma.Wherein, InCl 34H 2the concentration of O solution is 0.09-0.12 mol/L, (C 2h 5) 2nCSSNa 3H 2the concentration of O solution is 0.25-0.35 mol/L.
(2) AgI's is synthetic: polyvinylpyrrolidone (PVP) and silver acetate (AgAc) are joined in the round-bottomed flask that deionized water and ethylenediamine are housed, and stirring and dissolving at 30 ℃, so slowly injects KI (I -: Ag +=1.2:1) solution, makes AgI presoma after reacting 10 min, and wherein, PVP concentration is 0.03-0.05 mol/L, and the concentration of AgAc is 0.02-0.03 mol/L.
(3) by AgI and In (DDTC) 3transfer in the teflon-lined reactor that fills 25 mL deionized waters, add zinc acetate Zn (CHCOO) 2(0.01-0.5 g), after reactor sealing 180 0under C, react 24 h, product, through centrifugal and deionized water washing, obtains AgInS after completion of the reaction 2- xag 2s- yznS- zin 6s 7composite photo-catalyst.After having reacted, reactor is taken out and naturally cools to room temperature, through centrifugal and deionized water washing, obtain metal sulfide photocatalyst as above, this catalyst adopts visible ray to drive, and is a kind of nano-photocatalyst.
(4) heterojunction structure metal sulfide AgInS 2- xag 2s- yznS- zin 6s 7the hydrogen manufacturing of photochemical catalyst simulated solar irradiation
Take 20 mg AgInS 2- xag 2s- yznS- zin 6s 7photochemical catalyst, is dispersed in 50 mL deionized waters, then adds respectively 2.5 mL ammonium chloroplatinate solution (1mg/mL), 2.6 g Na 2sO 3, 3.6 g Na 2s9H 2o, under magnetic stirs, with 300 W xenon lamps (adding ultraviolet filter), as visible light source, light source and liquid level distance 25 cm, carry out the experiment of photo-reduction water, and reacting space 1 h carries out test sample one time, by gas-chromatography, carries out qualitative analysis, determines the content of product.Reaction finish after by catalyst recovery.Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Embodiment 1
Nano-photocatalyst AgInS 2preparation and produce hydrogen
Prepare respectively the four water indium trichloride InCl of 50 mL 0.1 mol/L 34H 2o, 0.3 mol/L sodium diethyldithiocarbamate (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then until precipitation is complete, through three filtration washings, can make In (DDTC) by above-mentioned two kinds of solution hybrid reaction under strong magnetic agitation 3presoma.
0.05 g polyvinylpyrrolidone and 0.06 g silver acetate are joined in the round-bottomed flask that 10 mL deionized waters and 1 mL ethylenediamine are housed, at 30 ℃, stir 30 min until dissolve, then by the liquor kalii iodide of 5 mL 0.084mol/L, the speed of dripping with 1 mL/min splashes in round-bottomed flask, continues reaction 10 min and makes AgI presoma.
AgI is transferred to autoclave, takes 0.3 g In (DDTC) 3, 0.016 g Zn (CH 3cOO) 2, measure 25 mL deionized waters and add in still, then still is transferred in the baking oven of 180 ℃, react 24 h.Product after having reacted, through centrifugal and deionized water washing, obtains metal sulfide AgInS 2photochemical catalyst.
Take 20 mg photochemical catalysts, be dispersed in 50 mL deionized waters, then add respectively 2.5 mL ammonium chloroplatinate solution (1mg/mL), 2.6 g Na 2sO 3, 3.6 g Na 2s9H 2o, under magnetic stirs, with 300 W xenon lamps (adding ultraviolet filter), as visible light source, light source and liquid level distance 25 cm, carry out the experiment of photo-reduction water, and reacting space 1 h carries out test sample one time, by gas-chromatography, carries out qualitative analysis, determines the content of product.Reaction finish after by catalyst recovery.
Embodiment 2
Nano heterogeneous photochemical catalyst AgInS 2-Ag 2the preparation of S
Prepare respectively the four water indium trichloride InCl of 50 mL 0.1mol/L 34H 2o ethanolic solution, 0.3mol/L sodium diethyldithiocarbamate (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then until precipitation is complete, through three filtration washings, can make In (DDTC) by above-mentioned two kinds of solution hybrid reaction under strong magnetic stirs 3presoma.
0.05 g polyvinylpyrrolidone and 0.06 g silver acetate are joined in the round-bottomed flask that 10 mL deionized waters and 1 mL ethylenediamine are housed, at 30 ℃, stir 30 min until dissolve, then by the liquor kalii iodide of 5 mL 0.084mol/L, the speed of dripping with 1 mL/min splashes in round-bottomed flask, continues reaction 10 min and makes AgI presoma.
AgI presoma is transferred to water heating kettle, takes 0.3 g In (DDTC) 3, 0.04 g Zn (CH 3cOO) 2, measure 25 mL deionized waters in water heating kettle, then water heating kettle is transferred in the baking oven of 180 ℃, react 24 h.Product after having reacted, through centrifugal and deionized water washing, obtains metal sulfide AgInS 2-Ag 2s photochemical catalyst.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
Embodiment 3
Nano-photocatalyst AgInS 2-Ag 2the preparation of S-ZnS:
Prepare respectively the four water indium trichloride InCl of 50 mL 0.1mol/L 34H 2o ethanolic solution, 0.3mol/L sodium diethyldithiocarbamate (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then until precipitation is complete, through three filtration washings, can make In (DDTC) by above-mentioned two kinds of solution hybrid reaction under strong magnetic stirs 3presoma.
0.05 g polyvinylpyrrolidone and 0.06 g silver acetate are joined in the round-bottomed flask that 10 mL deionized waters and 1 mL ethylenediamine are housed, at 30 ℃, stir 30 min until dissolve, then by the liquor kalii iodide of 5 mL 0.084mol/L, the speed of dripping with 1 mL/min splashes in round-bottomed flask, continues reaction 10 min and makes AgI presoma.
AgI presoma is transferred to water heating kettle, takes 0.3 g In (DDTC) 3, 0.08 g Zn (CH 3cOO) 2, measure 25 mL deionized waters in water heating kettle, then water heating kettle is transferred in the baking oven of 180 ℃, react 24 h.Product after having reacted, through centrifugal and deionized water washing, obtains metal sulfide AgInS 2photochemical catalyst.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
Embodiment 4
Nano-photocatalyst AgInS 2-Ag 2s-ZnS-In 6s 7preparation:
Prepare respectively the four water indium trichloride InCl of 50 mL 0.1mol/L 34H 2o ethanolic solution, 0.3mol/L sodium diethyldithiocarbamate (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then until precipitation is complete, through three filtration washings, can make In (DDTC) by above-mentioned two kinds of solution hybrid reaction under strong magnetic stirs 3presoma.
0.05 g polyvinylpyrrolidone and 0.06 g silver acetate are joined in the round-bottomed flask that 10 mL deionized waters and 1 mL ethylenediamine are housed, at 30 ℃, stir 30 min until dissolve, then by the liquor kalii iodide of 5 mL 0.084mol/L, the speed of dripping with 1 mL/min splashes in round-bottomed flask, continues reaction 10 min and makes AgI presoma.
AgI presoma is transferred to water heating kettle, takes 0.3 g In (DDTC) 3, 0.16 g Zn (CH 3cOO) 2, measure 25 mL deionized waters in water heating kettle, then water heating kettle is transferred in the baking oven of 180 ℃, react 24 h.Product after having reacted, through centrifugal and deionized water washing, obtains metal sulfide AgInS 2photochemical catalyst.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
Embodiment 5
Nano-photocatalyst AgInS 2-Ag 2s-ZnS-In 6s 7preparation:
Prepare respectively the four water indium trichloride InCl of 50 mL 0.1mol/L 34H 2o ethanolic solution, 0.3mol/L sodium diethyldithiocarbamate (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then until precipitation is complete, through three filtration washings, can make In (DDTC) by above-mentioned two kinds of solution hybrid reaction under strong magnetic stirs 3presoma.
0.05 g polyvinylpyrrolidone and 0.06 g silver acetate are joined in the round-bottomed flask that 10 mL deionized waters and 1 mL ethylenediamine are housed, at 30 ℃, stir 30 min until dissolve, then by the liquor kalii iodide of 5 mL 0.084mol/L, the speed of dripping with 1 mL/min splashes in round-bottomed flask, continues reaction 10 min and makes AgI presoma.
AgI presoma is transferred to water heating kettle, takes 0.3 g In (DDTC) 3, 0.4 g Zn (CH 3cOO) 2, measure 25 mL deionized waters in water heating kettle, then water heating kettle is transferred in the baking oven of 180 ℃, react 24 h.Product after having reacted, through centrifugal and deionized water washing, obtains metal sulfide AgInS 2photochemical catalyst.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.

Claims (5)

1. a composition metal sulfide photocatalyst, is characterized in that: the expression formula of described photochemical catalyst is AgInS 2- xag 2s- yznS- zin 6s 7, x, y, zget respectively 0 or 1.
2. a preparation method for composition metal sulfide photocatalyst described in claim 1, is characterized in that comprising the steps:
(1) utilize the synthetic diethyldithiocar bamic acid indium presoma of the deposition-precipitation method;
(2) zinc acetate and above-mentioned presoma and AgI are joined to polytetrafluoroethyllining lining autoclave, under hydro-thermal pressurized conditions, photochemical catalyst AgInS is prepared in reaction 2- xag 2s- yznS- zin 6s 7.
3. the preparation method of composition metal sulfide photocatalyst according to claim 2, is characterized in that the synthetic method of diethyldithiocar bamic acid indium presoma is as follows:
The alcohol mixed solution stirring reaction of hydration indium trichloride and sodium diethyldithiocarbamate, can make diethyldithiocar bamic acid indium presoma, and wherein, the concentration of indium trichloride solution is 0.09-0.12 molL -1, the concentration of sodium diethyldithiocarbamate solution is 0.25-0.35 molL -1.
4. the preparation method of composition metal sulfide photocatalyst as claimed in claim 2, is characterized in that hydrothermal reaction process is as follows: by AgI and In (DDTC) 3presoma is transferred in the teflon-lined reactor that fills the deionized water that accounts for its volume 70-80%, by the 0.15-8 of the amount of Ag elemental substance, doubly add zinc acetate, then reactor is put to 160-250 ℃ of baking ovens and reacted 6-48 h, product, through centrifugal and deionized water washing, obtains AgInS after completion of the reaction 2- xag 2s- yznS- zin 6s 7composite photo-catalyst.
5. the application of above-mentioned composition metal sulfide photocatalyst aspect the hydrogen manufacturing of sunshine reductive water.
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CN104263362A (en) * 2014-09-17 2015-01-07 重庆大学 Ag-In-Zn-S quaternary alloy nanorod and preparation method thereof
CN104263362B (en) * 2014-09-17 2016-04-27 重庆大学 A kind of Ag-In-Zn-S quad alloy nanometer rod and preparation method thereof
CN105800670A (en) * 2016-03-21 2016-07-27 内江师范学院 Preparation method of ZnS/Ag2S heterojunction hollow micro-nanospheres
CN105800670B (en) * 2016-03-21 2017-06-23 内江师范学院 A kind of ZnS/Ag2The preparation method of the hollow micro-nano ball of S hetero-junctions
CN107029755A (en) * 2017-04-16 2017-08-11 桂林理工大学 A kind of heterojunction photocatalyst and preparation method thereof
CN107029755B (en) * 2017-04-16 2019-07-23 桂林理工大学 A kind of heterojunction photocatalyst and preparation method thereof

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