CN103586051B - 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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CN103586051B
CN103586051B CN201310613579.4A CN201310613579A CN103586051B CN 103586051 B CN103586051 B CN 103586051B CN 201310613579 A CN201310613579 A CN 201310613579A CN 103586051 B CN103586051 B CN 103586051B
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presoma
metal sulfide
catalyst
agins
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CN103586051A (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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    • Y02E60/30—Hydrogen technology
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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
Technical field
The invention belongs to novel energy resource material technology field, relate in particular to and be a kind ofly applied to composition metal sulfide photocatalyst of sunlight catalytic reductive water hydrogen manufacturing and its preparation method and application.
Background technology
Mankind's activity causes energy resource consumption to present explosive growth, but fossil energy (oil, natural gas, coal) available quantity seriously reduces, and is tending towards exhausted gradually.The solar energy of inexhaustible, nexhaustible, economic environmental protection is ideal energy sources.Photocatalysis technology is with its room temperature deep reaction and directly can utilize the characteristics such as solar energy, becomes a kind of desirable clear energy sources production technology.Since Fujishima and Honda professor in 1972 finds to utilize titanium dioxide electrodes can since decomposition water generates hydrogen and oxygen under ultraviolet lighting, photocatalysis technology just causes the extensive concern of various countries scientist.
Through the research of decades, this technology makes important progress in photolysis water hydrogen, and wide spectral, the strong sunshine that absorbs drive the development of photochemical catalyst to be promote one of its practical key factor.Compound heterogeneous type semiconductor catalyst as a kind of regulate and control sunshine response and promote the important means of catalytic performance, day by day embody the superiority that it is potential.Metal sulfide semiconductor such as CdS etc. shows good activity in photolysis water hydrogen, but its photetching is serious, limits it and further applies.Japanese Scientists Kudo etc. use high temperature sintering technique to prepare 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 production photocatalyst 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, solve the efficiency of composition metal sulfide in sunshine hydrogen manufacturing.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of composition metal sulfide photocatalyst, the expression formula of described photochemical catalyst is AgInS 2- xag 2s- yznS- zin 6s 7 x, y, zget 0 or 1 respectively, when x, y, zwhen being asynchronously 0, described catalyst is the Heterogeneous Composite structure of sulfide.
If x, y, zall getting 0, is then 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, zasynchronously 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) deposition-precipitation is utilized to synthesize diethyldithiocar bamic acid indium (In (DDTC) 3) presoma;
(2) by proper amount of acetic acid zinc 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:
Trichloride hydrate indium (InCl 34H 2o) with sodium diethyldithiocarbamate ((C 2h 5) 2nCSSNa3H 2o) alcohol mixed solution stirring reaction, can obtain 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 filling the deionized water accounting for its volume 70-80%, doubly zinc acetate is added by the 0.15-8 of the amount of Ag elemental substance, then reactor is put and react 6-48 h to 160-250 DEG C of baking ovens, product is through centrifugal and deionized water washing after completion of the reaction, namely obtains AgInS 2- xag 2s- yznS- zin 6s 7the heterogeneous photochemical catalyst of compound.
The application of above-mentioned composition metal sulfide photocatalyst in 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) 3the synthesis of presoma: prepare InCl respectively 34H 2o and (C 2h 5) 2nCSSNa3H 2the ethanolic solution of O, then by above-mentioned two kinds of solution under agitation hybrid reaction a period of time, can obtain 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) synthesis of AgI: join in the round-bottomed flask that deionized water and ethylenediamine are housed by polyvinylpyrrolidone (PVP) and silver acetate (AgAc), stirring and dissolving at 30 DEG C, then slowly injects KI (I -: Ag +=1.2:1) solution, namely obtain AgI presoma after reacting 10 min, wherein, PVP concentration is the concentration of 0.03-0.05 mol/L, 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), 180 after reactor sealing 0react 24-36 h under C, 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, reproducible feature, can be used for preparing forming sunshine hydrogen production photocatalyst that is controlled, performance efficiency.
Therefore, the present invention is based on hydro-thermal integrated reacting, by regulating the additional proportion of different presoma, achieving the composition regulation and control of hetero-junctions complex sulfide photochemical catalyst.The preparation of catalyst adopts the technology of hydro-thermal method integration synthesis: by 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 0react 24-36 h under C, namely 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 2.5 mL ammonium chloroplatinate solution (1mg/mL), 2.6 g Na respectively 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, reacting space 1 h carries out a test sample, carries out qualitative analysis by gas-chromatography, determines the content of product.By catalyst recovery after reaction terminates.
Adopt the catalyst A gInS that above-mentioned preparation method obtains 2- xag 2s- yznS- zin 6s 7it is a kind of composite photo-catalyst with heterojunction structure.This catalyst combines the photoelectric characteristic being integrated with various semiconductor, has visible light intensity absorption characteristic, has increased substantially solar energy utilization ratio, show 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.Described heterojunction structure composition metal sulfide preferably consist of AgInS 2-Ag 2s-ZnS-In 6s 7.
Above-mentioned visible light catalyst has good effect in simulated solar irradiation hydrogen manufacturing, is the novel photocatalysis material meeting 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 compound nanometer photocatalyst 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, widen its using value.
Accompanying drawing explanation
Fig. 1: the embodiment 1-5 heterojunction structure metallic sulfide nano-particle AgInS prepared 2- xag 2s- yznS- zin 6s 7scanning electron microscopic picture and hydrogen manufacturing design sketch (in figure, scale is 400 nm);
Fig. 2: heterojunction structure metallic sulfide nano-particle AgInS prepared by embodiment 3 2-Ag 2the TEM-HRTEM spectrogram of S-ZnS;
Fig. 3: the embodiment 1-5 heterojunction structure metallic sulfide nano-particle AgInS prepared 2- xag 2s- yznS- zin 6s 7xRD spectra;
The heterojunction structure metal sulfide AgInS of Fig. 4: embodiment 1-5 synthesis 2- xag 2s- yznS- zin 6s 7photocurrent curve;
The heterojunction structure metal sulfide AgInS of Fig. 5: embodiment 1-5 synthesis 2- xag 2s- yznS- zin 6s 7impedance curve;
The heterojunction structure metal sulfide AgInS of Fig. 6: embodiment 2-5 synthesis 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, regular appearance; Embodiment 2 gained photochemical catalyst mainly nanometer sheet, regular appearance; Embodiment 3 gained photochemical catalyst is mainly mixed formed by bulky grain, nanometer sheet; Embodiment 4 gained photochemical catalyst is the oarse-grained mixing pattern of various bulk mainly; Embodiment 5 gained photochemical catalyst particle mainly not of uniform size mixes.As shown in fig. 1f, the sunshine hydrogen manufacturing successful of embodiment 3,4,5 gained photochemical catalyst is better than embodiment 1 and 2, and wherein embodiment 3 gained photochemical catalyst effect is best.
As shown in Figure 2, the TEM-HRTEM photo of the photochemical catalyst that embodiment 3 obtains, the lattice in figure proves AgInS 2, Ag 2the existence of S and ZnS.
As shown in Figure 3, the XRD spectra of the photochemical catalyst that embodiment 1-5 obtains, proves that embodiment 1 gained photochemical catalyst consists of AgInS 2, embodiment 2 gained photochemical catalyst consists of AgInS 2-Ag 2s, embodiment 3 gained photochemical catalyst consists of AgInS 2-Ag 2s-ZnS, embodiment 4 gained photochemical catalyst consists of AgInS 2-Ag 2s-ZnS-In 6s 7, embodiment 5 gained photochemical catalyst consists of AgInS 2-Ag 2s-ZnS-In 6s 7.
As shown in Figure 4, the photoelectric current spectrogram of the photochemical catalyst that embodiment 1-5 obtains, wherein the photoelectric current of embodiment 1 is maximum, shows that the photoelectron number of the photoelectron that embodiment 1 produces and transfer is maximum.
As shown in Figure 5, the impedance spectrogram of the photochemical catalyst that embodiment 1-5 obtains, wherein the impedance ring of embodiment 3 is minimum, shows embodiment 3(AgInS 2-Ag 2s-ZnS) best electro transfer effect is had, consistent with hydrogen manufacturing effect.
As shown in Figure 6, the EDAX analysis result of the photochemical catalyst that embodiment 2-5 obtains, 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.
Detailed description of the invention
The present invention is directed to the deficiencies in the prior art, provide heterojunction structure metal sulfide AgInS 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, by hydro-thermal method directly by this several heterogeneous semiconductor compound, its composition can by adding material rate.
Experimental procedure is:
(1) In (DDTC) 3the synthesis of presoma: prepare InCl respectively 34H 2o, (C 2h 5) 2nCSSNa 3H 2the ethanolic solution of O, then by above-mentioned two kinds of solution under agitation hybrid reaction a period of time, can obtain 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) synthesis of AgI: join in the round-bottomed flask that deionized water and ethylenediamine are housed by polyvinylpyrrolidone (PVP) and silver acetate (AgAc), stirring and dissolving at 30 DEG C, so slowly injects KI (I -: Ag +=1.2:1) solution, namely obtain AgI presoma after reacting 10 min, wherein, PVP concentration is the concentration of 0.03-0.05 mol/L, AgAc is 0.02-0.03 mol/L.
(3) by AgI and In (DDTC) 3transfer in the teflon-lined reactor filling 25 mL deionized waters, add zinc acetate Zn (CHCOO) 2(0.01-0.5 g), 180 after reactor sealing 0react 24 h under C, product is through centrifugal and deionized water washing after completion of the reaction, namely obtains AgInS 2- xag 2s- yznS- zin 6s 7composite photo-catalyst.Taken out by reactor after having reacted and naturally cool to room temperature, through centrifugal and deionized water washing, namely 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 2.5 mL ammonium chloroplatinate solution (1mg/mL), 2.6 g Na respectively 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, reacting space 1 h carries out a test sample, carries out qualitative analysis by gas-chromatography, determines the content of product.By catalyst recovery after reaction terminates.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 the four water indium trichloride InCl of 50 mL 0.1 mol/L respectively 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 obtain 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, 30 min are stirred until dissolve at 30 DEG C, then by the liquor kalii iodide of 5 mL 0.084mol/L dripping in speed instillation round-bottomed flask with 1 mL/min, continue reaction 10 min and obtain 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 DEG C, reacts 24 h.Product after having reacted, through centrifugal and deionized water washing, namely obtains metal sulfide AgInS 2photochemical catalyst.
Take 20 mg photochemical catalysts, be dispersed in 50 mL deionized waters, then add 2.5 mL ammonium chloroplatinate solution (1mg/mL), 2.6 g Na respectively 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, reacting space 1 h carries out a test sample, carries out qualitative analysis by gas-chromatography, determines the content of product.By catalyst recovery after reaction terminates.
Embodiment 2
Nano heterogeneous photochemical catalyst AgInS 2-Ag 2the preparation of S
Prepare the four water indium trichloride InCl of 50 mL 0.1mol/L respectively 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 obtain 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, 30 min are stirred until dissolve at 30 DEG C, then by the liquor kalii iodide of 5 mL 0.084mol/L dripping in speed instillation round-bottomed flask with 1 mL/min, continue reaction 10 min and obtain 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 DEG C, reacts 24 h.Product after having reacted, through centrifugal and deionized water washing, namely 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 the four water indium trichloride InCl of 50 mL 0.1mol/L respectively 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 obtain 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, 30 min are stirred until dissolve at 30 DEG C, then by the liquor kalii iodide of 5 mL 0.084mol/L dripping in speed instillation round-bottomed flask with 1 mL/min, continue reaction 10 min and obtain 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 DEG C, reacts 24 h.Product after having reacted, through centrifugal and deionized water washing, namely 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 the four water indium trichloride InCl of 50 mL 0.1mol/L respectively 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 obtain 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, 30 min are stirred until dissolve at 30 DEG C, then by the liquor kalii iodide of 5 mL 0.084mol/L dripping in speed instillation round-bottomed flask with 1 mL/min, continue reaction 10 min and obtain 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 DEG C, reacts 24 h.Product after having reacted, through centrifugal and deionized water washing, namely 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 the four water indium trichloride InCl of 50 mL 0.1mol/L respectively 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 obtain 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, 30 min are stirred until dissolve at 30 DEG C, then by the liquor kalii iodide of 5 mL 0.084mol/L dripping in speed instillation round-bottomed flask with 1 mL/min, continue reaction 10 min and obtain 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 DEG C, reacts 24 h.Product after having reacted, through centrifugal and deionized water washing, namely obtains metal sulfide AgInS 2photochemical catalyst.
Gained photochemical catalyst simulated solar irradiation hydrogen production process is identical with embodiment 1.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.

Claims (2)

1. a preparation method for composition metal sulfide photocatalyst, is characterized in that comprising the steps:
(1) deposition-precipitation is utilized to synthesize diethyldithiocar bamic acid indium presoma;
(2) zinc acetate and above-mentioned presoma and AgI are joined polytetrafluoroethyllining lining autoclave, under hydro-thermal pressurized conditions, photochemical catalyst AgInS is prepared in reaction 2- xag 2s- yznS- zin 6s 7, x, y, zget 0 or 1 respectively.
2. the preparation method of composition metal sulfide photocatalyst according to claim 1, is characterized in that the synthetic method of diethyldithiocar bamic acid indium presoma is as follows:
The alcohol mixed solution stirring reaction of trichloride hydrate indium and sodium diethyldithiocarbamate, can obtain 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.
3 .the preparation method of composition metal sulfide photocatalyst as claimed in claim 1, is characterized in that hydrothermal reaction process is as follows: by AgI and In (DDTC) 3presoma is transferred in the teflon-lined reactor filling the deionized water accounting for its volume 70-80%, doubly zinc acetate is added by the 0.15-8 of the amount of Ag elemental substance, then reactor is put and react 6-48 h to 160-250 DEG C of baking ovens, product is through centrifugal and deionized water washing after completion of the reaction, namely obtains AgInS 2- xag 2s- yznS- zin 6s 7composite photo-catalyst.
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