CN108479810A - A kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof - Google Patents
A kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 239000003426 co-catalyst Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000001257 hydrogen Substances 0.000 abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000013459 approach Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 10
- 239000011941 photocatalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- 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
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Abstract
The invention belongs to Photocatalitic Technique of Semiconductor fields, and in particular to a kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof.The present invention provides a kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof, it is characterised in that:Co-catalyst WS2Nanometer sheet passes through hydro-thermal reaction and ZnIn2S4Particle is closely linked, and forms WS2/ZnIn2S4Composite visible light catalyst.Relative to simple ZnIn2S4For photochemical catalyst, the WS of preparation2/ZnIn2S4Composite visible light catalyst is due to foring semiconductor heterostructure, can effectively promote the separation of photogenerated charge and reducing the compound of photo-generate electron-hole pair, so as to greatly improve Photocatalyzed Hydrogen Production performance.WS provided by the invention2/ZnIn2S4Composite visible light catalyst and preparation method thereof, the visible light catalyst to design and develop new and effective provide new approaches and new way.
Description
Technical field
The invention belongs to Photocatalitic Technique of Semiconductor fields, and in particular to a kind of WS2/ZnIn2S4Composite visible light catalyst
And preparation method thereof.
Background technology
Today's society, constantly exhausted fossil energy and worsening problem of environmental pollution force the mankind urgently to look for
And develop new cleaning fuel.Hydrogen Energy due to have the characteristics that high-energy, cleanliness without any pollution and as substitute conventional fossil fuel
Clean energy resource.In recent years, photocatalytic hydrogen production by water decomposition technology because its can using one solar energy of regenerative resource and water come
Hydrogen is obtained, the extensive concern by various countries is started.For photocatalytic hydrogen production by water decomposition technology, highly effective hydrogen yield efficiency is obtained
Key is photochemical catalyst, but most common photochemical catalyst TiO at present2The purple for accounting for sunlight total amount 3%-5% can only be absorbed
Outer light, solar energy utilization ratio are low, it is difficult to industrial applications.Since visible light accounts for about the 45% of sunlight total amount, exploitation
Visible light-responded, high efficiency photocatalyst has become the research hotspot of recent photocatalysis research field.
Ternary metal sulfide ZnIn2S4Because having unique six sides layer structure, suitable energy gap (energy gap
About 2.43eV), visible region have it is stronger absorb etc. series of advantages, cause the pole of photocatalysis field researcher in recent years
Big interest.Studies have shown that ZnIn2S4Presented in terms of the photocatalytic degradation of photocatalysis hydrolytic hydrogen production and organic pollution compared with
High catalytic activity, and with binary metal testing sulphide ratio, have better photochemical stability.However, single
ZnIn2S4Photogenerated charge be easy compound, quantum efficiency is relatively low.Therefore, it is necessary to ZnIn2S4It is modified to improve its light
Catalytic performance.
In recent years, with MoS2、WS2Etc. stratiforms disulphide be the non-platinum co-catalyst of representative because it is cheap and higher property
Extensive concern can be caused in photocatalysis field.The study found that in TiO2, the semiconductor light-catalysts area load MoS such as CdS2
Or WS2After co-catalyst, its photocatalytic hydrogen production by water decomposition efficiency can be largely improved, shows MoS2Or WS2Etc. stratiforms
Disulphide is a kind of novel cocatalyst materials for being expected to substitute noble metal.Therefore, the present invention proposes a kind of improvement
ZnIn2S4The method of photocatalytic activity is exactly by WS2Nanometer sheet is as co-catalyst and ZnIn2S4Nano particle is combined to make
It is standby to obtain WS2/ZnIn2S4Composite photo-catalyst, to largely improve ZnIn2S4Photocatalysis Decomposition aquatic products hydrogen live
Property.
Invention content
The purpose of the present invention is by WS2Nanometer sheet is as co-catalyst and ZnIn2S4Photochemical catalyst is combined, and preparation obtains
Obtain a kind of efficient WS2/ZnIn2S4Composite visible light catalyst.The present invention is realized by hydro-thermal method by WS2Nanometer sheet, which helps, urges
Agent and ZnIn2S4Effective combination of both photochemical catalysts, largely solves ZnIn2S4Photochemical catalyst light induced electron-
Hole has also properly increased ZnIn to the higher problem of recombination rate2S4The spectral absorption performance of photochemical catalyst, to improve
ZnIn2S4The Photocatalyzed Hydrogen Production efficiency of photochemical catalyst.
The present invention provides a kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof, it is characterised in that be logical
Cross following technical scheme realization:
(1) WS is prepared by hydro-thermal method first2Two-dimensional nano piece, detailed process are:The WCl for being 1: 10 by molar ratio6
(tungsten chloride) and CH3CSNH2(thioacetamide) dissolves together forms precursor solution in deionized water, then goes to hydro-thermal
Reaction kettle, the hydro-thermal reaction 24 hours under the conditions of 265 DEG C;It is cooled to room temperature after reaction, by water after precipitated product collection
WS can be prepared after 24 hours with freeze-drying process by washing2Nanometer sheet;
(2) above-mentioned WS is being obtained2Under the premise of two-dimensional nano piece, is further prepared by hydro-thermal reaction and obtain WS2/
ZnIn2S4Composite visible light catalyst, the reaction process are specially:By the WS of a certain amount of above-mentioned synthesis2According to different moles hundred
Divide and be distributed in deionized water than (1%~10%), strength ultrasonic disperse 1 hour forms WS2Suspension;Then, by ZnCl2、
In(NO3)3And CH3CSNH2Stoichiometrically molar ratio is 1: 2: 4 WS for being dissolved into above-mentioned configuration successively2In suspension, at ultrasound
Reason 30 minutes, prepares precursor solution;Later, precursor solution is transferred in hydrothermal reaction kettle, is reacted under 160 degree
6~12 hours;After reaction, it is cooled to room temperature, collected by suction reaction product cleans number with absolute ethyl alcohol and deionized water
Secondary, vacuum drying oven can prepare different WS after being dried overnight2The WS of molar percentage (1%~10%)2/ZnIn2S4It is compound
Visible light catalyst.
The invention has the advantages and positive effects that:
The present invention prepares WS using two one-step hydrothermals2/ZnIn2S4Composite visible light catalyst has preparation method phase
To the advantages that simple, of low cost.Compared to other synthetic methods, substep hydrothermal synthesis process can ensure to the full extent
WS2The microscopic appearance structure of nanometer sheet is not destroyed, and realizes ZnIn2S4With WS2Nanometer sheet good combination between the two, can be with
Obtain better photocatalysis performance.Relative to simple ZnIn2S4For photochemical catalyst, the WS that is prepared2/ZnIn2S4It is compound
Visible light catalyst is due to foring semiconductor heterostructure, can effectively promote the separation of photogenerated charge and reducing photoproduction electricity
Son-hole pair it is compound, so as to greatly improve Photocatalyzed Hydrogen Production performance.WS prepared by the present invention2/ZnIn2S4Complex light
In catalyst, WS2Mole percent level in the composite photocatalyst is controlled 1%~10%, works as WS2When content is 3%,
WS2/ZnIn2S4Composite photo-catalyst shows best Photocatalyzed Hydrogen Production activity.
Description of the drawings
Fig. 1 is the simple ZnIn prepared by comparative example2S4Different WS prepared by photochemical catalyst and Examples 1 to 32/
ZnIn2S4The XRD spectra of composite visible light catalyst;
Fig. 2 is (A) ZnIn prepared by comparative example2S4(B) 3%WS prepared by photochemical catalyst and embodiment 22/ZnIn2S4
Scanning electron microscope (SEM) figure of composite visible light catalyst;
Fig. 3 is (A) ZnIn prepared by comparative example2S4(B) 3%WS prepared by photochemical catalyst and embodiment 22/ZnIn2S4
Transmission electron microscope (TEM) figure of composite visible light catalyst;
Fig. 4 is the simple ZnIn prepared by comparative example2S4Different WS prepared by photochemical catalyst and Examples 1 to 32/
ZnIn2S4Photocatalyzed Hydrogen Production efficiency chart of the composite visible light catalyst under visible light (λ >=420nm) irradiation;
Fig. 5 is the 3%WS prepared by embodiment 22/ZnIn2S4Composite visible light catalyst shines at visible light (λ >=420nm)
Photocatalyzed Hydrogen Production stability loop test figure under penetrating;
Specific implementation mode
Below by specific embodiment, the present invention is described in further detail, and following embodiment can make this profession
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1:
(1) WS is prepared by hydro-thermal method first2Two-dimensional nano piece, detailed process are:11.897 grams of WCl are weighed respectively6
With 22.767 grams of thioacetamide (CH3CSNH2) be dissolved in 400 ml deionized waters and stir 1 hour after formed presoma it is molten
Then liquid goes to 500 milliliters of hydrothermal reaction kettles, the hydro-thermal reaction 24 hours under the conditions of 265 degree;It is cooled to room after reaction
Temperature, precipitated product collect after by washing and freeze-drying process is after 24 hours can prepare WS2Nanometer sheet;
(2) by the WS of the 5mg of above-mentioned synthesis2Nanometer sheet is distributed in 50 ml deionized waters, and strength ultrasonic disperse 1 is small
When, form WS2Suspension;Then, by the ZnCl of 2mmol2, the In (NO of 4mmol3)3·H2The CH of O and 8mmol3CSNH2By change
It is 1: 2: 4 WS for being dissolved into above-mentioned configuration successively to learn stoichiometric mole ratio2In suspension, it is ultrasonically treated 30 minutes, before preparing
Drive liquid solution;Later, precursor solution is transferred in hydrothermal reaction kettle, is reacted 8 hours under 160 degree;After reaction, cold
But to room temperature, collected by suction reaction product is cleaned for several times with absolute ethyl alcohol and deionized water, after vacuum drying oven is dried overnight, most
The WS containing 1% molar percentage is prepared eventually2/ZnIn2S4Composite visible light catalyst, be labeled as 1%WS2/
ZnIn2S4。
Embodiment 2:
(1)WS2The preparation process of two-dimensional nano piece is the same as embodiment one;
(2) by the WS of the 15mg of above-mentioned synthesis2Nanometer sheet is distributed in 50 ml deionized waters, and strength ultrasonic disperse 1 is small
When, form WS2Suspension;Then, by the ZnCl of 2mmol2, the In (NO of 4mmol3)3·H2The CH of O and 8mmol3CSNH2By change
It is 1: 2: 4 WS for being dissolved into above-mentioned configuration successively to learn stoichiometric mole ratio2In suspension, it is ultrasonically treated 30 minutes, before preparing
Drive liquid solution;Later, precursor solution is transferred in hydrothermal reaction kettle, is reacted 8 hours under 160 degree;After reaction, cold
But to room temperature, collected by suction reaction product is cleaned for several times with absolute ethyl alcohol and deionized water, after vacuum drying oven is dried overnight, most
The WS containing 3% molar percentage is prepared eventually2/ZnIn2S4Composite visible light catalyst, be labeled as 3%WS2/
ZnIn2S4。
Embodiment 3:
(1)WS2The preparation process of two-dimensional nano piece is the same as embodiment one;
(2) by the WS of the 25mg of above-mentioned synthesis2Nanometer sheet is distributed in 50 ml deionized waters, and strength ultrasonic disperse 1 is small
When, form WS2Suspension;Then, by the ZnCl of 2mmol2, the In (NO of 4mmol3)3·H2The CH of O and 8mmol3CSNH2By change
It is 1: 2: 4 WS for being dissolved into above-mentioned configuration successively to learn stoichiometric mole ratio2In suspension, it is ultrasonically treated 30 minutes, before preparing
Drive liquid solution;Later, precursor solution is transferred in hydrothermal reaction kettle, is reacted 8 hours under 160 degree;After reaction, cold
But to room temperature, collected by suction reaction product is cleaned for several times with absolute ethyl alcohol and deionized water, after vacuum drying oven is dried overnight, most
The WS containing 5% molar percentage is prepared eventually2/ZnIn2S4Composite visible light catalyst, be labeled as 5%WS2/
ZnIn2S4。
Comparative example:
It studies as a contrast, we are prepared for simple ZnIn using hydro-thermal method2S4Photochemical catalyst, detailed process are as follows:It will
The ZnC l of 2mmol2, the In (NO of 4mmol3)3·H2The CH of O and 8mmol3CSNH2Stoichiometrically molar ratio is 1: 2: 4 successively
It is dissolved in 50ml deionized waters, is ultrasonically treated 30 minutes, prepares precursor solution;Later, precursor solution is shifted
Into hydrothermal reaction kettle, reacted 8 hours under 160 degree;After reaction, it is cooled to room temperature, collected by suction reaction product, with nothing
Water-ethanol and deionized water cleaning for several times, after vacuum drying oven is dried overnight, finally prepare ZnIn2S4Photocatalyst powder.
Simple ZnIn prepared by the present invention2S4With different WS2/ZnIn2S4The photocatalysis performance of composite visible light catalyst
It is to test system using commercially available Photocatalyzed Hydrogen Production to test its photochemical catalyzing H2-producing capacity, detailed process and step are such as
Under:The Na of a concentration of 0.25mol/L of 200ml is added in light-catalyzed reaction vessel2SO3With the Na of a concentration of 0.35mol/L2S's
Mixed solution does sacrifice agent, adds the photochemical catalyst rear enclosed system of 0.2g preparations, vacuumizes, reach after certain vacuum degree with
Xenon lamp simulated visible light carries out illumination to it, and the concentration for producing hydrogen in different periods system is detected by gas chromatograph, is obtained not
With the volume of the decomposition aquatic products hydrogen of sample under visible light illumination, and then calculate its Photocatalyzed Hydrogen Production rate.
Fig. 1 is the simple ZnIn prepared by comparative example2S4Different WS prepared by photochemical catalyst and Examples 1 to 32/
ZnIn2S4The XRD spectra of composite visible light catalyst.It can be seen from the figure that the ZnIn2S4 photocatalysis prepared using hydro-thermal method
The characteristic diffraction peak of agent corresponds respectively to the crystal face (JCPDS card No.01 072 0773) of hexagonal phase indium sulfide zinc, says
Bright hydro-thermal method can prepare pure six sides ZnIn2S4Crystal phase structure;And introduce WS2After nanometer sheet, ZnIn2S4Characteristic diffraction peak
There is no apparent variation occurs, this illustrates WS2Introducing do not interfere with ZnIn2S4Crystal phase structure;It should be noted that for
WS2/ZnIn2S4For composite photo-catalyst, there is a WS for 12 ° or so in the angle of diffraction2Diffractive features peak, and with
WS2The increase of content, it can be seen that WS2Diffraction peak intensity also gradually increase, this also illustrates WS2/ZnIn2S4Composite photocatalyst
The successful preparation of agent.
Fig. 2 is the ZnIn prepared by comparative example2S43%WS prepared by photochemical catalyst and embodiment 22/ZnIn2S4It is compound can
Scanning electron microscope (SEM) figure of light-exposed catalyst.As seen from the figure, the ZnIn prepared using hydro-thermal method2S4Photochemical catalyst is not advise
Particle then, these particles are formed by numerous nanoparticle agglomerates;And WS2/ZnIn2S4Composite photo-catalyst can obviously be seen
It observes in two-dimentional WS2It distributed many irregular ZnIn on nanometer sheet surface2S4Particle.
Fig. 3 is the ZnIn prepared by comparative example2S43%WS prepared by photochemical catalyst and embodiment 22/ZnIn2S4It is compound can
Transmission electron microscope (TEM) figure of light-exposed catalyst.As seen from the figure, pure ZnIn2S4Sample is formed by numerous nanoparticle agglomerates
Irregular particle, and WS2/ZnIn2S4Composite photo-catalyst then can obviously observe ZnIn2S4Particle is attached to WS2Nanometer
On piece, the two are bound tightly together, and further demonstrate WS2/ZnIn2S4The successful preparation of composite photo-catalyst.
Fig. 4 is the simple ZnIn prepared by comparative example2S4Different WS prepared by photochemical catalyst and Examples 1 to 32/
ZnIn2S4Photocatalyzed Hydrogen Production efficiency chart of the composite visible light catalyst under visible light (λ >=420nm) irradiation.It can be seen by figure
Go out and pure ZnIn2S4The hydrogen generation efficiency of photochemical catalyst is compared, WS2/ZnIn2S4There is composite visible light catalyst better light to urge
Change H2-producing capacity;Work as WS2Content be 3% when, WS2/ZnIn2S4The hydrogen-producing speed of composite visible light catalyst reaches maximum, about
It is pure ZnIn for 199.12 μm of ol/h/g2S46 times of photochemical catalyst hydrogen generation efficiency (33.36 μm of ol/h/g).Photocatalyzed Hydrogen Production is surveyed
Test result shows by introducing suitable WS2Co-catalyst can largely improve ZnIn2S4Photocatalyzed Hydrogen Production
Energy.
Fig. 5 is the 3%WS prepared by embodiment 22/ZnIn2S4Composite visible light catalyst shines at visible light (λ >=420nm)
Photocatalyzed Hydrogen Production stability loop test figure under penetrating.As seen from the figure, under visible light illumination, 3%WS2/ZnIn2S4
Composite visible light catalyst sample carries out Photocatalyzed Hydrogen Production loop test (test 4 hours every time) three times, the photocatalysis production of sample
Hydrogen efficiency is reduced there is no apparent, is illustrated that this material has good photocatalysis stability, is conducive to WS2/ZnIn2S4It is multiple
The practical application of closing light catalyst.
Claims (5)
1. a kind of WS2/ZnIn2S4Composite visible light catalyst, it is characterised in that:Co-catalyst WS2Nanometer sheet passes through hydro-thermal reaction
With ZnIn2S4Particle is closely linked, and forms WS2/ZnIn2S4Composite visible light catalyst.
2. a kind of WS2/ZnIn2S4The preparation method of composite visible light catalyst, it is characterised in that include the following steps:
(1) WCl for being 1: 10 by molar ratio6(tungsten chloride) and CH3CSNH2(thioacetamide) dissolves in deionized water together
Precursor solution is formed, hydrothermal reaction kettle is transferred to and carries out hydro-thermal reaction for 24 hours at a certain temperature, it is dry through filtering, centrifugation, freezing
WS is obtained after dry2Nanometer sheet sample;
(2) a certain amount of WS for obtaining above-mentioned steps 12Sample strength ultrasonic disperse in deionized water, according to certain molar ratio
Example sequentially adds ZnCl2、In(NO3)3·H2O and CH3CSNH2, agitated to dissolve and be configured to after being ultrasonically treated 30 minutes suspended
Liquid;
(3) suspension that step (2) is prepared is transferred in hydrothermal reaction kettle, when carrying out one section of hydro-thermal reaction at a certain temperature
Between, obtain composite catalyst sample after filtering, centrifugation, drying.
3. WS according to claim 22/ZnIn2S4The preparation method of composite visible light catalyst, it is characterised in that:Step
(1) presoma WCl in6Solution concentration is 0.075M, and hydrothermal temperature is 265 DEG C.
4. WS according to claim 22/ZnIn2S4The preparation method of composite visible light catalyst, it is characterised in that:Step
(2) ZnCl in2、In(NO3)3·H2O and CH3CSNH2The molar ratio of addition is 1: 2: 4, WS2Addition is ZnIn in product2S4It rubs
The 1%~10% of that amount, strength ultrasonic disperse time are 1 hour.
5. WS according to claim 22/ZnIn2S4The preparation method of composite visible light catalyst, it is characterised in that:Step
(3) temperature of hydro-thermal reaction is 160 DEG C in, and the reaction time is 6~12 hours.
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