CN111790404A - Defective type sulfur indium zinc microsphere visible light catalyst, preparation method and application - Google Patents
Defective type sulfur indium zinc microsphere visible light catalyst, preparation method and application Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 65
- 230000002950 deficient Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 230000007547 defect Effects 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011941 photocatalyst Substances 0.000 claims description 17
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000004201 L-cysteine Substances 0.000 claims description 7
- 235000013878 L-cysteine Nutrition 0.000 claims description 7
- 150000002471 indium Chemical class 0.000 claims description 5
- 238000006303 photolysis reaction Methods 0.000 claims description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 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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- 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
- 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
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01—INORGANIC CHEMISTRY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- 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
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Abstract
The invention discloses a defect type sulfur indium zinc microsphere visible light catalyst, a preparation method and application thereof, wherein the preparation method comprises the step of mixing ZnIn2S4And heating the microspheres to 90-120 ℃ in a hydrogen atmosphere for heat treatment to obtain the defective S-in-Zn microsphere visible light catalyst. The defect type sulfur indium zinc microsphere visible light catalyst provided by the invention can widen the light absorption range of the catalyst, and improve the separation efficiency of photo-generated electrons and holes so as to improve the photocatalysis efficiency.
Description
Technical Field
The invention relates to a preparation method and a use method of a photocatalyst, in particular to a defect type sulfur indium zinc microsphere visible light photocatalyst, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The world is facing the crisis of energy shortage today, and environmental issues have become a barrier to further development of human civilization. In order to solve the energy problem, semiconductor photocatalysis is developed in recent years, and hydrogen production by decomposing water is a very promising technology. Among the numerous semiconductor photocatalysts, ZnIn2S4As a ternary metal chalcogenide, a typical visible light response type photocatalyst has the advantages of adjustable band gap and wider light absorption range, so that the ternary metal chalcogenide has wide application in the field of photocatalysis in recent years. The effective optical absorption of solar energy in the visible range also leads to ZnIn2S4Becomes a promising, environmentally friendly and visible light driven photocatalyst for cleaning energy conversion. ZnIn2S4The method has great advantages in hydrogen production, however, the research of the inventor of the invention finds that the ZnIn is existed2S4Has the defect of low hydrogen production efficiency.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a defect type sulfur indium zinc microsphere visible light catalyst, a preparation method and application thereof, which can widen the light absorption range of the catalyst, and improve the separation efficiency of photo-generated electron and hole pairs so as to improve the photocatalysis efficiency.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one hand, the preparation method of the defect type sulfur indium zinc microsphere visible light catalyst comprises the step of mixing ZnIn2S4And heating the microspheres to 90-120 ℃ in a hydrogen atmosphere for heat treatment to obtain the defective S-in-Zn microsphere visible light catalyst.
Experiments show that when hydrogen is adopted to react on ZnIn at 90-120 DEG C2S4After the microspheres are subjected to heat treatment, ZnIn is obtained2S4The specific surface area of the microspheres is enlarged, so that the active sites on the surface are increased, and the hydrogen production performance is improved, while ZnIn is treated at the temperature of 80 DEG C2S4The specific surface area of the microspheres becomes smaller, the hydrogen production performance is reduced, and when hydrogen is in the hydrogen production processZnIn is caused when the treatment is carried out at 120 ℃ or higher2S4The microspheres are decomposed, and thus ZnIn cannot be obtained2S4And (3) microspheres.
On the other hand, the defect type sulfur indium zinc microsphere visible light catalyst is obtained by the preparation method.
In a third aspect, the defect type sulfur indium zinc microsphere visible light catalyst is applied to photolysis of water to produce hydrogen.
In a fourth aspect, a method for preparing hydrogen by photolysis of water comprises adding the above-described defective S-in-Zn microspheres to a system containing water, lactic acid and chloroplatinic acid, and performing light irradiation treatment.
The invention has the beneficial effects that:
the defect ZnIn prepared by low-temperature surface hydrogenation2S4The microsphere visible-light-driven photocatalyst has good hydrogen production performance, while ZnIn prepared by the prior art2S4The photocatalyst has poor hydrogen production performance, can be improved by more than 2 times, and still has good stability through repeated tests. The catalyst with the microsphere structure has larger specific surface area and abundant surface active sites, generally shows better photocatalytic performance than bulk phase materials, and can generate surface defects after hydrogenation. In addition, the structure increases the contact area with the catalyst and greatly improves the hydrogen production performance.
The invention particularly adopts the strategies of hydrothermal and low-temperature surface hydrogenation to prepare ZnIn2S4The microsphere photocatalyst can better regulate and control the surface defects of the photocatalyst. Defective ZnIn prepared by the same2S4The microsphere photocatalyst has the advantages of good stability and high photocatalytic activity, and can be applied to the fields of energy, environmental protection and the like. The invention has the advantages of simple preparation process, simple experimental equipment, low cost, high benefit and easy realization of commercialization.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows the preparation of defective ZnIn in examples 1 to 3 of the present invention2S4Experimental flow diagrams of microspheres;
FIG. 2 shows the preparation of defective ZnIn in examples 1 to 3 of the present invention2S4XRD spectrum of microsphere;
FIG. 3 shows the preparation of defective ZnIn in examples 1 to 3 of the present invention2S4Nitrogen adsorption and desorption curves of the microspheres;
FIG. 4 shows the preparation of defective ZnIn in examples 1 to 3 of the present invention2S4Pore size distribution curve of the microspheres;
FIG. 5 shows defective ZnIn prepared in example 2 of the present invention2S4SEM image of microspheres.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the prior ZnIn2S4The invention provides a defect of low hydrogen production efficiency, and provides a defect type sulfur indium zinc microsphere visible light catalyst, a preparation method and an application thereof.
The invention provides a preparation method of a defect type sulfur indium zinc microsphere visible light catalyst, which is implemented by mixing ZnIn2S4And heating the microspheres to 90-120 ℃ in a hydrogen atmosphere for heat treatment to obtain the defective S-in-Zn microsphere visible light catalyst.
Experiments show that when the hydrogen is adopted at 90-120 DEG CFor ZnIn2S4After the microspheres are treated, ZnIn is obtained2S4The specific surface area of the microspheres is enlarged, so that the active sites on the surface are increased, and the hydrogen production performance is improved, while ZnIn is treated at the temperature of 80 DEG C2S4The specific surface area of the microspheres becomes smaller, the hydrogen production performance is reduced, and ZnIn is caused when the hydrogen is treated at the temperature of more than 120 DEG C2S4The microspheres are decomposed, and thus ZnIn cannot be obtained2S4And (3) microspheres.
In some examples of this embodiment, the heat treatment temperature is 99 to 101 ℃. Experiments prove that the hydrogen has better treatment effect on the sulfur indium zinc microspheres at the treatment temperature, larger specific surface area and stronger hydrogen production performance.
In some examples of this embodiment, the heat treatment time is 3 to 4 hours. The heat treatment time can ensure the treatment effect of the hydrogen on the sulfur indium zinc microspheres.
In some examples of this embodiment, the heating rate of the heat treatment is 1 to 2 ℃/min.
In some embodiments of this embodiment, ZnIn2S4The preparation method of the microsphere comprises the following steps: synthesizing zinc salt, indium salt and L-cysteine by a hydrothermal method.
The hydrothermal method is a chemical reaction which is carried out in a sealed pressure container by taking water as a solvent under the conditions of high temperature (100-370 ℃) and high pressure (the environmental pressure is 21.7 MPa).
The zinc salt in the invention refers to a compound which is soluble in water and has zinc ions as cations, such as zinc nitrate and the like.
The indium salt according to the present invention is a compound which is soluble in water and has an indium ion as a cation, and for example, indium nitrate and the like.
In one or more embodiments, the mass ratio of the total mass of the zinc salt, the indium salt and the L-cysteine to the water is 3-5: 5-10.
In one or more embodiments, the temperature of the hydrothermal process is 180 to 200 ℃.
In one or more embodiments, the hydrothermal treatment time is 16-20 hours.
In one or more embodiments, the hydrothermally treated material is washed with water and ethanol in sequence.
In another embodiment of the invention, the defect type sulfur indium zinc microsphere visible light catalyst is obtained by the preparation method.
The third embodiment of the invention provides an application of the defective S-in-Zn microsphere visible-light-induced photocatalyst in hydrogen production by photolysis of water.
In a fourth embodiment of the present invention, there is provided a method for preparing hydrogen by photolyzing water, wherein the defective S-in-Zn microspheres are added to a system containing water, lactic acid and chloroplatinic acid, and then subjected to light irradiation.
In some examples of the embodiment, the light irradiation treatment is performed by using a 200-400W xenon lamp and a power density of 50-150 mW cm-2The irradiation is carried out for 4-6 h under the condition of simulating sunlight.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
0.074g Zn (NO) is weighed out3)2·6H2O and 0.15g In (NO)3)3·H2O stirring (rotating speed 500r min)-1) Dissolved in 30mL of distilled water, and further added with 0.233g L-cysteine to continue stirring for 2 hours. The hydrothermal reaction was carried out at 200 ℃ for 18 h. After cooling, the solution was centrifuged (4000r min)-1And centrifuged for 3min), and the separated precipitate was washed three times with water and ethanol, respectively. Vacuum drying at 60 deg.C for 12h in drying oven, and grinding the dried powder to obtain ZnIn2S4And (3) powder materials. ZnIn is mixed with a solvent2S4Placing the powder material in a tubular furnace, introducing hydrogen into the tubular furnace, wherein the flow rate of the hydrogen is 40mL min-1Heating to 80 ℃ at the speed of 2 ℃/min, roasting for 3h, and cooling to room temperature to obtain the defective ZnIn2S4And (3) powder materials.
Example 2
0.074g Zn (NO) is weighed out3)2·6H2O and 0.15g In (NO)3)3·H2O stirring (rotating speed 500r min)-1) Dissolved in 30mL of distilled water, and further added with 0.233g L-cysteine to continue stirring for 2 hours. The hydrothermal reaction was carried out at 200 ℃ for 18 h. After cooling, the solution was centrifuged (4000r min)-1And centrifuged for 3min), and the separated precipitate was washed three times with water and ethanol, respectively. Vacuum drying at 60 deg.C for 12h in drying oven, and grinding the dried powder to obtain ZnIn2S4And (3) powder materials. ZnIn is mixed with a solvent2S4Placing the powder material in a tubular furnace, introducing hydrogen into the tubular furnace, wherein the flow rate of the hydrogen is 40mL min-1Heating to 100 ℃ at the speed of 2 ℃/min, roasting for 3h, and cooling to room temperature to obtain defective ZnIn2S4And (3) powder materials.
Example 3
0.074g Zn (NO) is weighed out3)2·6H2O and 0.15g In (NO)3)3·H2O stirring (rotating speed 500r min)-1) Dissolved in 30mL of distilled water, and further added with 0.233g L-cysteine to continue stirring for 2 hours. The hydrothermal reaction was carried out at 200 ℃ for 18 h. After cooling, the solution was centrifuged (4000r min)-1And centrifuged for 3min), and the separated precipitate was washed three times with water and ethanol, respectively. Vacuum drying at 60 deg.C for 12h in drying oven, and grinding the dried powder to obtain ZnIn2S4And (3) powder materials. ZnIn is mixed with a solvent2S4Placing the powder material in a tubular furnace, introducing hydrogen into the tubular furnace, wherein the flow rate of the hydrogen is 40mL min-1Heating to 120 ℃ at the speed of 2 ℃/min, roasting for 3h, and cooling to room temperature to obtain defective ZnIn2S4And (3) powder materials.
Examples 1 to 3 preparation of defective ZnIn2S4The experimental scheme for microspheres is shown in FIG. 1.
Examples 1 to 3 preparation of defective ZnIn2S4The XRD spectrum of the microsphere is shown in figure 2, the position of each diffraction peak is related to ZnIn2S4The major crystal planes substantially correspond. The characteristic diffraction peaks of the four samples do not change too much, the positions and peak widths are similar, and no obvious shift occurs. Only the diffraction peak of sulfur indium zinc after low-temperature hydrogenation reductionThe peak width is slightly increased, and the peak intensity is slightly weakened. The reason for this may be that the structure of the material crystals is slightly changed during the hydrogen calcination. The sample can keep the original structure after low-temperature hydrogenation reduction treatment, and has good stability.
Examples 1 to 3 preparation of defective ZnIn2S4The nitrogen adsorption and desorption curves and the pore size distribution curves of the microspheres are shown in figures 3-4, and the defective ZnIn prepared in examples 2 and 32S4The microspheres are improved compared to the as-is, wherein the specific surface area is highest at 100 ℃ of the hydrotreatment. The pore diameters of these samples are mostly concentrated around 10nm and thus belong to mesoporous materials. The larger the specific surface area of the sample, the more active sites are exposed on the surface of the sample, and the more sulfur vacancies are generated on the surface after the hydrotreating, and these sulfur vacancy defects contribute to the enhancement of the photocatalytic activity.
Example 2 defective ZnIn preparation2S4The SEM image of the microspheres is shown in FIG. 5, and it can be seen that the spherical structure is very obvious, the morphology is relatively uniform, and the diameter of the sphere is about 5 μm. Compared with other materials, the microsphere structure can provide more active sites, and the photocatalytic oxidation capacity is greatly improved.
The defective ZnIn prepared in example 2 is treated2S4A microspherical visible-light-driven photocatalyst is used for a photocatalytic hydrogen production test, and the method comprises the following steps: to a solution containing 90mL of water, 10mL of lactic acid and 0.1mL of 0.5 wt% chloroplatinic acid, 50mg of ZnIn was added2S4And (3) irradiating the microsphere photocatalyst for 5 hours under the condition of 300W simulated sunlight, and analyzing hydrogen generated in the device by using a gas chromatograph and calculating the hydrogen yield. Through calculation, the defective ZnIn prepared in the example 2 under the condition that the hydrogenation temperature is 100 DEG C2S4The microsphere visible-light-driven photocatalyst has good hydrogen production performance (2.15mmol h)-1g-1) Is improved by more than 2 times (0.99mmol h) than the performance before hydrogenation-1g-1) And has good stability through a cycle test. Due to the microsphere structure, the contact area of the microsphere structure and the catalyst is increased, and the photocatalytic hydrogen production performance is improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a defect type sulfur indium zinc microsphere visible light catalyst is characterized in that ZnIn is added2S4And heating the microspheres to 90-120 ℃ in a hydrogen atmosphere for heat treatment to obtain the defective S-in-Zn microsphere visible light catalyst.
2. The preparation method of the defective ZnSInZn microsphere visible light catalyst as claimed in claim 1, wherein the heat treatment temperature is 99-101 ℃.
3. The preparation method of the defective ZnS-InZn microsphere visible light catalyst as claimed in claim 1, wherein the heat treatment time is 3-4 h.
4. The preparation method of the defective ZnS-InZn microsphere visible light catalyst as claimed in claim 1, wherein the heating rate of the heat treatment is 1-2 ℃/min.
5. The method for preparing the defective ZnSInZn microsphere visible-light-induced photocatalyst as claimed in claim 1, wherein the ZnIn is2S4The preparation method of the microsphere comprises the following steps: synthesizing zinc salt, indium salt and L-cysteine by a hydrothermal method.
6. The preparation method of the defective S-in-Zn microsphere visible-light-induced photocatalyst as claimed in claim 5, wherein the mass ratio of the total mass of the zinc salt, the indium salt and the L-cysteine to the water is 3-5: 5-10;
or the temperature of the hydrothermal method is 180-200 ℃;
or the time for the hydrothermal method treatment is 16-20 h.
7. A defect type S-in-Zn microsphere visible light catalyst, which is characterized by being obtained by the preparation method of any one of claims 1 to 6.
8. The use of the defective ZnS-InZn microsphere visible-light-induced photocatalyst as claimed in claim 7 in the photolysis of water to produce hydrogen.
9. A method for preparing hydrogen by photolyzing water is characterized in that the defect type sulfur indium zinc microspheres are added into a system containing water, lactic acid and chloroplatinic acid, and light irradiation treatment is carried out.
10. The method for preparing hydrogen by water photolysis according to claim 9, wherein the light irradiation is performed by using a 200-400W xenon lamp and a power density of 50-150 mW cm-2The irradiation is carried out for 4-6 h under the condition of simulating sunlight.
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