CN104801317A - Photocatalytic water splitting hydrogen production catalyst responding to visible light and preparation method of catalyst - Google Patents

Photocatalytic water splitting hydrogen production catalyst responding to visible light and preparation method of catalyst Download PDF

Info

Publication number
CN104801317A
CN104801317A CN201510138426.8A CN201510138426A CN104801317A CN 104801317 A CN104801317 A CN 104801317A CN 201510138426 A CN201510138426 A CN 201510138426A CN 104801317 A CN104801317 A CN 104801317A
Authority
CN
China
Prior art keywords
catalyst
compound
hydrogen production
source compound
chalcopyrite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510138426.8A
Other languages
Chinese (zh)
Other versions
CN104801317B (en
Inventor
王志明
张平安
林越来
周志华
牛晓滨
巫江
李含冬
姬海宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN201510138426.8A priority Critical patent/CN104801317B/en
Publication of CN104801317A publication Critical patent/CN104801317A/en
Application granted granted Critical
Publication of CN104801317B publication Critical patent/CN104801317B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a photocatalytic water splitting hydrogen production catalyst and a preparation method of the catalyst and belongs to the technical field of photocatalysis. The catalyst is prepared from a precious metal M and a chalcopyrite quaternary compound Cu2ZnSnX4 through composition, wherein the precious metal M refers to Au or Pt, the chalcopyrite quaternary compound Cu2ZnSnX4 refers to Cu2ZnSnS4 or Cu2ZnSnSe4, and the molar ratio of M to Cu2ZnSnX4 is 0.001:0.1. During preparation of the chalcopyrite quaternary compound Cu2ZnSnX4, a mixed liquid is heated with a microwave method for a reaction at the temperature ranging from 160 DEG C to 200 DEG C under the power of 400 W for 5-15 min. The catalyst is prepared with the microwave method, the preparation cycle is short, the repeatability is good, the obtained catalyst can respond to both visible light and ultraviolet light to excite electrons and holes, the utilization efficiency and the hydrogen production rate of solar light are increased, and the photocatalytic activity is high.

Description

Photolytic hydrogen production catalyst of a kind of responding to visible light and preparation method thereof
Technical field
The present invention relates to photolytic hydrogen production catalyst of a kind of responding to visible light and preparation method thereof, belong to photocatalyst technology field.
Background technology
Along with the fast development of economy, energy shortage and environmental problem are subject to concern and the attention of people day by day.Hydrogen Energy, as a kind of energy of clean, efficient, green non-pollution, is considered to one of most effectual way solving the energy and environmental problem.And in the method preparing hydrogen, utilizing solar source to adopt conductor photocatalysis hydrogen production by water decomposition, solar energy being changed into Hydrogen Energy, is a kind of effective hydrogen production process.
TiO 2be a kind of conventional progress of hydrogen production from water by photodecomposition catalyst, there is due to it advantages such as photocatalytic activity is high, stable chemical performance, safety non-toxic and be widely studied and applied.But, TiO 2band gap be about 3.2eV, namely can only be excited generation photocatalytic hydrogen production activity by the ultraviolet portion less than 4% in sunshine, which greatly limits TiO 2in the extensive use in photolytic hydrogen production catalyst field.
At present, in raising sunshine photon utilization ratio, morely adopt transient metal doped, semiconductors coupling, semiconductor light sensitization and widen the photoresponse scope of catalyst with the means such as noble metal compound.Wherein, a kind of efficient, easy method with noble metal compound, because the driving of the free electron near Fermi level in metal surface by electromagnetic field collective oscillation can occur, the energy conversion of electric field is made to be the free electron collective vibration energy of metal surface, enhance the electric field of metal nanoparticle surf zone, thus strengthen the absorption to photon near noble metal nano particles.
Summary of the invention
The object of the present invention is to provide a kind of noble metal composite brass ore deposit quaternary compound photolytic hydrogen production catalyst and preparation method thereof, solve the problem that existing photolytic hydrogen production catalyst sunshine utilization rate is low, product hydrogen rate is low.
Technical scheme of the present invention is as follows:
The photolytic hydrogen production catalyst of a kind of responding to visible light provided by the invention, by noble metal M and chalcopyrite quaternary compound Cu 2znSnX 4compound obtains, and described noble metal M is Au or Pt, described chalcopyrite quaternary compound Cu 2znSnX 4for Cu 2znSnS 4or Cu 2znSnSe 4, described M and Cu 2znSnX 4mol ratio be 0.001 ~ 0.1.
A preparation method for the photolytic hydrogen production catalyst of responding to visible light, comprises the following steps:
Step 1: with copper source compound, zinc source compound, tin source compound, X source compound for raw material, according to chalcopyrite quaternary compound molecular formula Cu 2znSnX 4in the ratio conversion copper source compound of each element, zinc source compound, tin source compound, X source compound mass percent, take raw material, add in organic solvent, stir and make raw material Homogeneous phase mixing;
Step 2: microwave chemical reactor put into by mixed liquor step 1 obtained, reacts 5 ~ 15min under 160 ~ 200 DEG C of temperature, 400W power condition;
Step 3: after the mixed liquor cooling obtained until step 2, decompress filter, the product that suction filtration obtains is scattered in deionized water, then adds gold chloride or chloroplatinic acid, is uniformly mixed, wherein, described gold chloride or chloroplatinic acid and chalcopyrite quaternary compound Cu 2znSnX 4mol ratio be 0.001 ~ 0.1;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds sodium citrate aqueous solution under the irradiation of 500W xenon lamp, wherein, natrium citricum and chalcopyrite quaternary compound Cu 2znSnX 4mol ratio be 0.08 ~ 0.1; After being added dropwise to complete, close xenon lamp, after solution is cooled to room temperature, repeated centrifugation separation, washing step 3 ~ 5 times, by the drying precipitate obtained, namely obtain photolytic hydrogen production catalyst of the present invention.
Further, the source compound of copper described in step 1 is copper chloride, copper sulphate, copper acetate, copper nitrate etc.; Described zinc source compound zinc chloride, zinc sulfate, zinc nitrate, zinc acetate etc.; Described tin source compound is stannous chloride, stannous sulfate, stannous acetate etc.; Described X source compound is sulphur source or selenium source, and sulphur source is thiocarbamide, vulcanized sodium etc., and selenium source is selenourea etc.
Further, organic solvent described in step 1 is ethylene glycol etc.
Beneficial effect of the present invention is:
1, the preparation technology of noble metal composite brass ore deposit provided by the invention quaternary compound photolytic hydrogen production catalyst is simple, energy consumption is low, strong operability, safe, reproducible; The response range of the catalyst obtained to sunshine spectrum is wide, can produce response inspire electronics and hole to the visible ray in sunshine and ultraviolet portion, and improve the utilization ratio of sunshine and produce hydrogen rate, photocatalytic activity is high.
2, the present invention adopts microwave method Kaolinite Preparation of Catalyst sample, manufacturing cycle catalyst purity that is short, that obtain is high, good stability, reproducible, the average grain diameter of the catalyst sample obtained is about 35nm, increases specific area, improves the activity of catalyst.
Accompanying drawing explanation
Fig. 1 is the Au composite Cu that the embodiment of the present invention 1 obtains 2znSnS 4the scanning electron microscopic picture of catalyst.
Fig. 2 is the Au composite Cu that the embodiment of the present invention 1 obtains 2znSnS 4the hydrogen-producing speed figure of catalyst.
Fig. 3 is the Pt composite Cu that the embodiment of the present invention 2 obtains 2znSnS 4the scanning electron microscopic picture of catalyst.
Fig. 4 is the Au composite Cu that the embodiment of the present invention 3 obtains 2znSnSe 4the scanning electron microscopic picture of catalyst.
Fig. 5 is the Pt composite Cu that the embodiment of the present invention 4 obtains 2znSnSe 4the scanning electron microscopic picture of catalyst.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further and introduce.
A preparation method for the photolytic hydrogen production catalyst of responding to visible light, comprises the following steps:
Step 1: with copper source compound, zinc source compound, tin source compound, X source compound for raw material, according to described chalcopyrite quaternary compound molecular formula Cu 2znSnX 4in the ratio conversion copper source compound of each element, zinc source compound, tin source compound, X source compound mass percent, take raw material, add in ethylene glycol, stir and make raw material Homogeneous phase mixing;
Step 2: microwave chemical reactor put into by mixed liquor step 1 obtained, reacts 5 ~ 15min under 160 ~ 200 DEG C of temperature, 400W power condition;
Step 3: after the mixed liquor that step 2 obtains is cooled to room temperature, decompress filter, the solid obtained adopts absolute ethanol washing 3 ~ 5 times, obtains black solid; The black solid obtained is scattered in deionized water, then adds gold chloride or chloroplatinic acid, stir 2 ~ 5min and make it mix, wherein, described gold chloride or chloroplatinic acid and chalcopyrite quaternary compound Cu 2znSnX 4mol ratio be 0.001 ~ 0.1;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds sodium citrate aqueous solution under the irradiation of 500W xenon lamp, wherein, natrium citricum and chalcopyrite quaternary compound Cu 2znSnX 4mol ratio be 0.08 ~ 0.1, after being added dropwise to complete, close xenon lamp; After liquid to be mixed naturally cools to room temperature, carry out centrifugation, washing, repeat above-mentioned centrifugation, washing step 3 ~ 5 times, by the sediment that obtains dry 20 ~ 24h at 60 ~ 80 DEG C in vacuum drying chamber, namely obtain noble metal composite brass ore deposit of the present invention quaternary compound photolytic hydrogen production catalyst.
Embodiment 1
Au composite Cu 2znSnS 4the preparation method of photolytic hydrogen production catalyst, comprises the following steps:
Step 1: add in 70mL ethylene glycol solvent by 2mmol copper acetate, 1mmol zinc acetate, 1mmol stannous acetate and 4mmol thiocarbamide, stirs 5min, mixes;
Step 2: mixed liquor step 1 obtained is put into microwave chemical reactor and carried out adding thermal response, and temperature is 160 DEG C, and power is 400W, and the time is 15min;
Step 3: step 2 heats after reacted mixed liquor is cooled to room temperature, and decompress filter, the solid obtained adopts absolute ethanol washing 5 times, obtains Cu 2znSnS 4black solid; By the Cu obtained 2znSnS 4black solid is scattered in 100mL deionized water, and adds 0.001mmol gold chloride in deionized water, stirs 2min and makes it mix;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds 0.08mmol sodium citrate aqueous solution under the irradiation of 500W xenon lamp, the concentration of natrium citricum is 0.02mol/L; After being added dropwise to complete, close xenon lamp, after liquid to be mixed naturally cools to room temperature, carry out centrifugation, deionized water washing, after repeating above-mentioned centrifugation, deionized water washing step 5 times, by the sediment that obtains dry 24h at 60 DEG C in vacuum drying chamber, obtain Au composite Cu 2znSnS 4photolytic hydrogen production catalyst.
Fig. 1 is the Au composite Cu that the embodiment of the present invention 1 obtains 2znSnS 4the scanning electron microscopic picture of catalyst.As shown in Figure 1, the catalyst surface that embodiment 1 obtains is spherical, and the Au crystal grain of wherein taking measurements greatly less is compounded in Cu 2znSnS 4surface, such structure considerably increases Au and Cu 2znSnS 4contact surface, compare the shelly composite catalyst that existing method prepares, catalyst A u and the Cu that the present invention obtains 2znSnS 4composite surface at catalyst surface, binding site is more, and contact surface is larger, contributes to the activity promoting catalyst.
Fig. 2 is the Au-Cu that embodiment 1 obtains 2znSnS 4the hydrogen-producing speed figure of catalyst.The Au composite Cu that embodiment 1 is obtained 2znSnS 4catalyst, under 300W xenon lamp irradiates, adds 0.35mol/LNa 2s and 0.25mol/L Na 2sO 3in the aqueous solution, in gas chromatograph, detect the generation of hydrogen.Under the irradiation of simulated solar irradiation, the Au composite Cu that embodiment 1 obtains 2znSnS 4the product hydrogen rate of catalyst reaches 110umol/h/g.
Embodiment 2
Pt composite Cu 2znSnS 4the preparation method of photolytic hydrogen production catalyst, comprises the following steps:
Step 1: add in 70mL ethylene glycol solvent by 2mmol copper acetate, 1mmol zinc acetate, 1mmol stannous acetate and 4mmol thiocarbamide, stirs 5min, mixes;
Step 2: mixed liquor step 1 obtained is put into microwave chemical reactor and carried out adding thermal response, and temperature is 200 DEG C, and power is 400W, and the time is 5min;
Step 3: step 2 heats after reacted mixed liquor is cooled to room temperature, and decompress filter, the solid obtained adopts absolute ethanol washing 5 times, obtains Cu 2znSnS 4black solid; By the Cu obtained 2znSnS 4black solid is scattered in 100mL deionized water, and adds 0.1mmol chloroplatinic acid in deionized water, stirs 3min and makes it mix;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds 0.08mmol sodium citrate aqueous solution under the irradiation of 500W xenon lamp, the concentration of natrium citricum is 0.02mol/L; After being added dropwise to complete, close xenon lamp, after liquid to be mixed naturally cools to room temperature, carry out centrifugation, deionized water washing, after repeating above-mentioned centrifugation, deionized water washing step 5 times, by the sediment that obtains dry 24h at 60 DEG C in vacuum drying chamber, obtain Pt composite Cu 2znSnS 4photolytic hydrogen production catalyst.
Fig. 3 is the Pt composite Cu that the embodiment of the present invention 2 obtains 2znSnS 4the scanning electron microscopic picture of catalyst.As shown in Figure 3, the catalyst surface that embodiment 2 obtains is still for spherical, and contact area is large, and the activity of catalyst is higher.Adopt the product hydrogen rate of the method identical with embodiment 1 to the catalyst that embodiment 2 obtains to test, the product hydrogen rate of the catalyst that embodiment 2 obtains is close with the product hydrogen rate of embodiment 1 catalyst.
Embodiment 3
Au composite Cu 2znSnSe 4the preparation method of photolytic hydrogen production catalyst, comprises the following steps:
Step 1: add in 70mL ethylene glycol solvent by 2mmol copper acetate, 1mmol zinc acetate, 1mmol stannous acetate and 4mmol selenourea, stirs 5min, mixes;
Step 2: mixed liquor step 1 obtained is put into microwave chemical reactor and carried out adding thermal response, and temperature is 160 DEG C, and power is 400W, and the time is 15min;
Step 3: step 2 heats after reacted mixed liquor is cooled to room temperature, and decompress filter, the solid obtained adopts absolute ethanol washing 5 times, obtains Cu 2znSnSe 4black solid; By the Cu obtained 2znSnSe 4black solid is scattered in 100mL deionized water, and adds 0.001mmol gold chloride in deionized water, stirs 5min and makes it mix;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds 0.08mmol sodium citrate aqueous solution under the irradiation of 500W xenon lamp, the concentration of natrium citricum is 0.02mol/L; After being added dropwise to complete, close xenon lamp, after liquid to be mixed naturally cools to room temperature, carry out centrifugation, deionized water washing, after repeating above-mentioned centrifugation, deionized water washing step 5 times, by the sediment that obtains dry 20h at 80 DEG C in vacuum drying chamber, obtain Au composite Cu 2znSnSe 4photolytic hydrogen production catalyst.
Fig. 4 is the Au composite Cu that the embodiment of the present invention 3 obtains 2znSnSe 4the scanning electron microscopic picture of catalyst.As shown in Figure 4, the catalyst surface that embodiment 3 obtains is still for spherical, and contact area is large, and the activity of catalyst is higher.Adopt the product hydrogen rate of the method identical with embodiment 1 to the catalyst that embodiment 3 obtains to test, the product hydrogen rate of the catalyst that embodiment 3 obtains is close with the product hydrogen rate of embodiment 1 catalyst.
Embodiment 4
Pt composite Cu 2znSnSe 4the preparation method of photolytic hydrogen production catalyst, comprises the following steps:
Step 1: add in 70mL ethylene glycol solvent by 2mmol copper acetate, 1mmol zinc acetate, 1mmol stannous acetate and 4mmol selenourea, stirs 5min, mixes;
Step 2: mixed liquor step 1 obtained is put into microwave chemical reactor and carried out adding thermal response, and temperature is 200 DEG C, and power is 400W, and the time is 5min;
Step 3: step 2 heats after reacted mixed liquor is cooled to room temperature, and decompress filter, the solid obtained adopts absolute ethanol washing 5 times, obtains Cu 2znSnSe 4black solid; By the Cu obtained 2znSnSe 4black solid is scattered in 100mL deionized water, and adds 0.1mmol chloroplatinic acid in deionized water, stirs 2min and makes it mix;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds 0.08mmol sodium citrate aqueous solution under the irradiation of 500W xenon lamp, the concentration of natrium citricum is 0.02mol/L; After being added dropwise to complete, close xenon lamp, after liquid to be mixed naturally cools to room temperature, carry out centrifugation, deionized water washing, after repeating above-mentioned centrifugation, deionized water washing step 5 times, by the sediment that obtains dry 24h at 60 DEG C in vacuum drying chamber, obtain Pt composite Cu 2znSnSe 4photolytic hydrogen production catalyst.
Fig. 5 is the Pt composite Cu that the embodiment of the present invention 4 obtains 2znSnSe 4the scanning electron microscopic picture of catalyst.As shown in Figure 5, the catalyst surface that embodiment 4 obtains is still for spherical, and contact area is large, and the activity of catalyst is higher.Adopt the product hydrogen rate of the method identical with embodiment 1 to the catalyst that embodiment 4 obtains to test, the product hydrogen rate of the catalyst that embodiment 4 obtains is close with the product hydrogen rate of embodiment 1 catalyst.

Claims (4)

1. a photolytic hydrogen production catalyst for responding to visible light, by noble metal M and chalcopyrite quaternary compound Cu 2znSnX 4compound obtains, and described noble metal M is Au or Pt, described chalcopyrite quaternary compound Cu 2znSnX 4for Cu 2znSnS 4or Cu 2znSnSe 4, described M and Cu 2znSnX 4mol ratio be 0.001 ~ 0.1.
2. a preparation method for the photolytic hydrogen production catalyst of responding to visible light, comprises the following steps:
Step 1: with copper source compound, zinc source compound, tin source compound, X source compound for raw material, according to chalcopyrite quaternary compound molecular formula Cu 2znSnX 4in the ratio conversion copper source compound of each element, zinc source compound, tin source compound, X source compound mass percent, take raw material, add in organic solvent, stir and make raw material Homogeneous phase mixing;
Step 2: microwave chemical reactor put into by mixed liquor step 1 obtained, reacts 5 ~ 15min under 160 ~ 200 DEG C of temperature, 400W power condition;
Step 3: after the mixed liquor cooling obtained until step 2, decompress filter, the product that suction filtration obtains is scattered in deionized water, then adds gold chloride or chloroplatinic acid, is uniformly mixed, wherein, described gold chloride or chloroplatinic acid and chalcopyrite quaternary compound Cu 2znSnX 4mol ratio be 0.001 ~ 0.1;
Step 4: the mixed liquor obtained after step 3 being processed dropwise adds sodium citrate aqueous solution under the irradiation of 500W xenon lamp, wherein, natrium citricum and chalcopyrite quaternary compound Cu 2znSnX 4mol ratio be 0.08 ~ 0.1; After being added dropwise to complete, close xenon lamp, after solution is cooled to room temperature, repeated centrifugation separation, washing step 3 ~ 5 times, by the drying precipitate obtained, namely obtain photolytic hydrogen production catalyst of the present invention.
3. the preparation method of the photolytic hydrogen production catalyst of responding to visible light according to claim 2, is characterized in that, the source compound of copper described in step 1 is copper chloride, copper sulphate, copper acetate, copper nitrate; Described zinc source compound zinc chloride, zinc sulfate, zinc nitrate, zinc acetate; Described tin source compound is stannous chloride, stannous sulfate, stannous acetate; Described X source compound is sulphur source or selenium source, and sulphur source is thiocarbamide, vulcanized sodium, and selenium source is selenourea.
4. the preparation method of the photolytic hydrogen production catalyst of responding to visible light according to claim 2, is characterized in that, organic solvent described in step 1 is ethylene glycol.
CN201510138426.8A 2015-03-27 2015-03-27 A kind of photolytic hydrogen production catalyst of responding to visible light and preparation method thereof Active CN104801317B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510138426.8A CN104801317B (en) 2015-03-27 2015-03-27 A kind of photolytic hydrogen production catalyst of responding to visible light and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510138426.8A CN104801317B (en) 2015-03-27 2015-03-27 A kind of photolytic hydrogen production catalyst of responding to visible light and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104801317A true CN104801317A (en) 2015-07-29
CN104801317B CN104801317B (en) 2017-06-16

Family

ID=53686761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510138426.8A Active CN104801317B (en) 2015-03-27 2015-03-27 A kind of photolytic hydrogen production catalyst of responding to visible light and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104801317B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105032451A (en) * 2015-08-03 2015-11-11 广东工业大学 Application of tin selenide nanometer material in photocatalysis aspect
CN109453794A (en) * 2018-11-12 2019-03-12 国家***第海洋研究所 A kind of Cu2ZnSn(SxSe1-x)4Application of the alloy nano-material as analogue enztme
CN110013844A (en) * 2019-04-23 2019-07-16 武汉科技大学 A kind of reduction-state MoO3-xPhotochemical catalyst and its preparation method and application
CN110711589A (en) * 2019-09-23 2020-01-21 惠州学院 Au-Cu3BiS3Catalyst, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101565313A (en) * 2009-05-21 2009-10-28 上海交通大学 Method for preparing copper-zinc-tin-sulfur photoelectric material
US20120238054A1 (en) * 2009-11-25 2012-09-20 Alex Sergey Ionkin Screen-printable quaternary chalcogenide compositions
CN103611549A (en) * 2013-11-21 2014-03-05 电子科技大学 Preparation method of copper zinc tin sulfide/graphene oxide composite semiconductor photocatalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101565313A (en) * 2009-05-21 2009-10-28 上海交通大学 Method for preparing copper-zinc-tin-sulfur photoelectric material
US20120238054A1 (en) * 2009-11-25 2012-09-20 Alex Sergey Ionkin Screen-printable quaternary chalcogenide compositions
CN103611549A (en) * 2013-11-21 2014-03-05 电子科技大学 Preparation method of copper zinc tin sulfide/graphene oxide composite semiconductor photocatalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MIN-LING LIU等: "A wide-band-gap p-type thermoelectric material based on quaternary chalcogenides of Cu2ZnSnQ4（Q=S,Se）", 《APPLIED PHYSICS LETTERS》 *
林晓静: "Cu2ZnSnS4及其氧化物复合纳米材料的制备与光电性能研究", 《中国硕士学位论文全文数据库工程科技I辑》 *
白雪莲等: "Au/ZnS复合颗粒的制备及其光催化性能", 《现代化工》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105032451A (en) * 2015-08-03 2015-11-11 广东工业大学 Application of tin selenide nanometer material in photocatalysis aspect
CN109453794A (en) * 2018-11-12 2019-03-12 国家***第海洋研究所 A kind of Cu2ZnSn(SxSe1-x)4Application of the alloy nano-material as analogue enztme
CN109453794B (en) * 2018-11-12 2021-04-09 国家***第一海洋研究所 Cu2ZnSn(SxSe1-x)4Application of alloy nano material as mimic enzyme
CN110013844A (en) * 2019-04-23 2019-07-16 武汉科技大学 A kind of reduction-state MoO3-xPhotochemical catalyst and its preparation method and application
CN110711589A (en) * 2019-09-23 2020-01-21 惠州学院 Au-Cu3BiS3Catalyst, preparation method and application thereof

Also Published As

Publication number Publication date
CN104801317B (en) 2017-06-16

Similar Documents

Publication Publication Date Title
CN101347725B (en) Carbon nano-tube/titanic oxide nano compound photocatalyst and preparation method and application thereof
CN103599800B (en) The preparation method of glass fiber loaded silver-silver bromide-titanium oxide composite material
CN101347724B (en) Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof
CN103506142B (en) A kind of Molybdenum disulfide/silver phosphate composite visible light photocatalytic material and preparation method thereof
CN103406159B (en) Photochemical preparation method of tin dioxide/graphene oxide composite photocatalyst
CN103990474A (en) Preparation method of 3D-shaped silver/silver bromide/titanium dioxide catalyst
CN108404960B (en) Preparation method of sulfur-indium-zinc-gold carbon nitride two-dimensional layered composite photocatalyst
CN102008959B (en) Method for preparing nano-silver loaded tungsten trioxide with high photocatalytic activity
CN105214689A (en) A kind of TiO 2/ CdS/ Graphene composite photocatalyst material and preparation method thereof
CN104722298A (en) Method for preparing titania composite nano-gold photocatalyst
CN106513020A (en) Preparation method of bismuth tungstate-molybdenum disulfide/graphene composite
CN105562040B (en) A kind of preparation and application of BiOCl- (001)/GO nano composite photo-catalysts
CN105312088B (en) Fe2O3 doping covalent triazine organic polymer visible light catalyst and its preparation and application
CN104801317A (en) Photocatalytic water splitting hydrogen production catalyst responding to visible light and preparation method of catalyst
CN103182307B (en) Cu-doped ZnO/graphene composite photocatalyst and preparation method thereof
CN105709782A (en) Preparing method and application of Ag/AgBr/BiOCl-(001) nanometer composite material
CN105879884A (en) One-dimensional ZnS (zinc sulfide)/CdS-C nanocomposite material and preparation method thereof
CN106975497A (en) Titanium dioxide nanoplate and copper-zinc-tin-sulfur nano particle hetero-junctions preparation method and application
CN101966450A (en) High-efficiency composite photocatalyst and preparation method thereof
CN106362742A (en) Ag/ZnO nano-composite, preparation method thereof and application of composite
CN103934005B (en) A kind of zinc sulphide copper nano-wire visible light catalyst of cuprous ion doping and preparation established law and application
CN108144599A (en) A kind for the treatment of process of bismuthino composite photocatalyst for degrading dyeing waste water
CN104857975A (en) Preparation method and application of CdIn2S4-graphene composite photocatalyst
CN107362792A (en) A kind of preparation method of strontium titanates/niobic acid tin composite nano materials
CN109382088A (en) SnO2/ α~Bi2O3/ β~Bi2O3Composite material and preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant