CN115282986A - Two-dimensional sulfur indium zinc photocatalyst doped with-vacancy double sites as well as preparation method and application thereof - Google Patents
Two-dimensional sulfur indium zinc photocatalyst doped with-vacancy double sites as well as preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 150000002471 indium Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims 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 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 description 19
- 125000004429 atom Chemical group 0.000 description 18
- 239000000243 solution Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
- C01—INORGANIC CHEMISTRY
- 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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- 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 discloses a two-dimensional sulfur indium zinc photocatalyst doped with-vacancy double sites, and a preparation method and application thereof 2 S 4 Noble metal monoatomic ions are doped in the (ZIS), and S vacancies can be generated in the ZIS when the noble metal monoatomic atoms are introduced, and the doping-vacancy double-site structure can not only effectively improve the separation efficiency of photo-generated electrons and holes, but also activate the original inert (001) crystal face to ensure that the crystal face has hydrogen evolution reaction activity, thereby promoting the thermodynamics and kinetics of the photocatalytic hydrogen evolution reaction; the doping-vacancy dual-site photocatalyst obtained by the invention has good stability and higher utilization rate of noble metal, and simultaneously has excellent photocatalytic hydrogen evolution reaction rate under the irradiation of real sunlight; therefore, the catalyst has good development and application prospects.
Description
Technical Field
The invention belongs to the field of photocatalysis, and relates to a two-dimensional sulfur indium zinc (ZnIn) doped with-vacancy double sites 2 S 4 ) A photocatalyst and a preparation method and application thereof.
Background
In the face of the increasingly severe environmental energy crisis, the development and utilization of clean renewable energy has become one of the most pressing challenges in modern society. Hydrogen is a new green energy source, has higher energy density and is an environment-friendly combustion product, and is one of new energy carriers with development prospects, so that the hydrogen production by utilizing solar energy to spontaneously decompose water is considered to be a method with great attractiveness for solving energy problems and environmental crisis.
Two-dimensional hexagonal ZnIn consisting of S-Zn-S-In-S layer stack 2 S 4 The (ZIS) nanosheet is considered to be a promising photocatalyst due to the narrow forbidden band width (2.06-2.85 eV), the proper energy band structure and the good light stability. However, as the charge separation efficiency of ZIS is low, photogenerated carriers are easy to recombine, and sufficient reactive sites are lacked, the catalytic hydrogen evolution activity of ZIS is still low, and an application of ZIS in hydrogen evolution under real sunlight is rarely reported.
Previous literature reports demonstrate Gibbs free energy of adsorption of a sulfur atom to a hydrogen atom in the (110) crystal plane of ZIS, the sulfur atom being bonded to both an indium atom and a zinc atom
Is-0.16 eV and has sulfur atom on (001) crystal face
Is-1.58 eV. In general,
approaching 0eV indicates that the site can be used as a reactive center for hydrogen evolution. Therefore, the main hydrogen evolution reaction in ZIS is concentrated on the (110) crystal plane. However, as a two-dimensional layered material, ZIS has more (001) crystal planes. Therefore, the preparation of a proper reaction site and the activation of the (001) crystal face which does not have catalytic activity originally are important ways for greatly improving the ZIS photocatalytic hydrogen evolution activity.
The current research mainly promotes the separation of electron-hole pairs by doping metal atoms or generating vacancies to change the surface electronic structure of ZIS and activates the (001) crystal face. If the two methods are combined, the metal atoms are doped, and meanwhile, vacancies are generated around the metal atoms to form a doping-vacancy double-site structure, so that whether the migration of photogenerated carriers can be effectively regulated and controlled, and more excellent catalytic active sites are generated, thereby greatly improving the photocatalytic performance of the ZIS and enabling the ZIS to have the application prospect of hydrogen evolution under real sunlight. Although there have been reports on the preparation of doping-vacancy double defects, the synthesis method mainly focuses on the generation of vacancies after doping metal atoms, and the two defects are not spatially connected. The invention generates vacancy beside the noble metal atom by a one-step synthesis method, and two adjacent defects are positioned in space.
The invention intends to introduce a trace amount of noble metal monoatomic atoms into a ZIS crystal structure and simultaneously generate S vacant sites around the ZIS crystal structure. The formed doping-vacancy double-site structure not only activates an inert (001) crystal face and provides more reaction sites, but also effectively regulates and controls the migration of photo-generated electrons, so that the photo-generated electrons are quickly transferred to a catalytic active center to participate in hydrogen evolution reaction. Therefore, the photocatalytic hydrogen evolution rate and the quantum efficiency of the catalyst are greatly improved, and the catalyst also shows excellent photocatalytic hydrogen evolution performance under real sunlight.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a two-dimensional ZnIn doped with a vacancy double site 2 S 4 Photocatalyst, and a preparation method and application thereof. The invention introduces noble metal monoatomic with high activity into ZnIn 2 S 4 Photocatalyst and generation of sulfur vacancies at its neighboring sites, thereby forming ZnIn in two dimensions 2 S 4 To obtain a doping-vacancy double-site structure. The catalyst prepared by the invention can be applied to the catalytic hydrogen evolution reaction of real sunlight.
In the catalyst, the introduction of noble metal monoatomic atoms can generate S vacant sites around the noble metal monoatomic atoms, so that the effective separation of photogenerated electrons and holes in the ZIS material can be realized, and the charge transfer efficiency is improved. Meanwhile, the (001) crystal face which is originally inert also has good hydrogen evolution reaction activity after being doped with the noble metal single atom. Therefore, even under the condition of very low content of noble metal, the hydrogen production efficiency of the photocatalyst can be obviously improved due to the combined action of doping and vacancy. The photocatalyst prepared by the invention can effectively solve the problems of high content and low utilization rate of noble metal and realize the maximization of catalytic efficiency.
The technical scheme of the invention is as follows:
two-dimensional ZnIn doped with-vacancy double sites 2 S 4 The preparation method of the photocatalyst comprises the following steps:
dissolving indium salt, zinc salt and sodium citrate in a mixed solvent of Ethylene Glycol (EG) -deionized water, then adding noble metal salt, stirring at room temperature for 20-40 min (preferably 30 min), then adding a sulfur source, and continuously stirring for 20-40 min (preferably 30 min) to obtain a mixed solution; then heating the mixed solution to 100-150 ℃ (preferably 120 ℃) to react for 10-15 h (preferably 12 h), and then centrifuging, washing and freeze-drying to obtain the two-dimensional ZnIn doped with the vacancy double sites 2 S 4 A photocatalyst;
the indium salt is indium trichloride, indium nitrate or indium sulfate;
the zinc salt is zinc chloride, zinc sulfate, zinc nitrate or zinc perchlorate;
the noble metal salt is H 2 PtCl 6 、(NH 4 ) 2 PtCl 6 Or H 2 PdCl 4 Preferably H 2 PtCl 6 (ii) a Preferably the noble metal salt is dosed in the form of an aqueous solution thereof;
the sulfur source is sodium sulfide, thioacetamide or thiourea;
in the mixed solvent of ethylene glycol and deionized water, the volume ratio of ethylene glycol to deionized water is 1:3 to 8, preferably 1:5;
in the mixed solution, the concentration of indium salt is 20-60mmol L -1 The zinc salt concentration is 10-50mmol L -1 The concentration of sodium citrate is 20-60mmol L -1 The concentration of the noble metal salt is 0.08-3mmol L -1 The concentration of the sulfur source is 60-160mmol L -1 ；
The resulting doped-vacancy bi-site two-dimensional ZnIn 2 S 4 In the photocatalyst, the doping amount of the noble metal single atom is 0.1-3wt%.
The invention relates to a two-dimensional ZnIn doped with vacancy double sites prepared by the preparation method 2 S 4 A photocatalyst.
The invention also relates to a photocatalyst film which is prepared from the two-dimensional ZnIn with the doping-vacancy double sites 2 S 4 Photocatalyst and substrate conductive glass; the preparation method comprises the following steps:
the two-dimensional ZnIn with the doping-vacancy double sites is formed 2 S 4 The photocatalyst is prepared into 10-15mg mL -1 The ethanol solution is dropped on the conductive glass (FTO), and then is dried, so as to obtain the photocatalyst film.
The invention relates to a two-dimensional ZnIn doped with a vacancy double site 2 S 4 The photocatalyst or photocatalyst film can be applied to the fields of hydrogen production by photolysis water, CO oxidation and selective oxidation, oxidation reduction synthesis reaction of organic matters, NO reduction or oxidation, biomass material degradation and the like, and particularly has excellent performance in the reaction of hydrogen analysis by photolysis water.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a doping-vacancy dual-site catalyst, which is characterized in that a noble metal atom is introduced into ZIS, and meanwhile, sulfur vacancies are generated around the ZIS, so that a catalyst material with extremely low noble metal atom content and excellent photocatalytic activity is finally obtained. The introduction of the noble metal monoatomic atom can generate an S vacancy in ZIS, and the doping-vacancy double-site structure can effectively improve the separation efficiency of photo-generated electrons and holes, and can activate the original inert (001) crystal face to ensure that the crystal face has hydrogen evolution reaction activity, thereby promoting the thermodynamics and dynamics of the photocatalytic hydrogen evolution reaction.
2. According to the preparation method of the doping-vacancy dual-site photocatalyst, provided by the invention, ZIS nano materials with different morphologies (the morphology of the ZIS nano materials can be regulated and controlled by changing the amount of sodium citrate) and different noble metal sources can be adopted, and the photocatalyst with less noble metal content can be prepared by regulating different raw material ratios.
3. The invention provides a doping-vacancy double-site ZIS photocatalyst, the catalytic performance of the catalyst is superior to that of the existing photocatalytic material, and when the catalyst is applied to photocatalytic hydrogen evolution, the photocatalytic hydrogen evolution rate of the catalyst can reach 163.73μmol h -1 It is 25 times more efficient than ZIS catalysis.
4. The preparation method has the advantages of simple process, low cost, environmental friendliness and the like. The photocatalyst prepared by the invention has the advantages of high utilization rate of noble metal, good stability, high efficiency of catalyzing water to decompose and separate hydrogen, no pollution, recycling and the like, and more importantly, the photocatalyst can also show excellent hydrogen separation activity under real sunlight.
Drawings
FIG. 1: transmission electron micrographs of the photocatalysts prepared in examples 1 and 2; wherein (a) is a transmission electron micrograph of ZIS nanomaterial, and (b) is a transmission electron micrograph of 0.3wt% Pt/ZIS photocatalyst.
FIG. 2: 0.3wt% prepared in example 2 the spherical aberration corrected TEM dark field pattern of the Pt/ZIS photocatalyst.
FIG. 3: electron spin resonance diagrams of the photocatalysts prepared in examples 1 and 2.
FIG. 4: the X-ray photoelectron spectra of the photocatalysts prepared in example 1 and example 2.
FIG. 5: x-ray diffraction patterns of the photocatalysts prepared in examples 1 and 2; wherein (a) is an XPS spectrum of Pt as a simple substance, and (b) is an XPS spectrum of Pt in 0.3wt% Pt/ZIS photocatalyst.
FIG. 6: uv-vis absorption spectra of the photocatalysts prepared in examples 1 and 2.
FIG. 7 is a schematic view of: the photocatalytic water splitting hydrogen analysis effect of the ZIS and Pt/ZIS photocatalysts with different loading amounts is shown in the figure.
FIG. 8: the photocatalytic water splitting hydrogen evolution cycle effect diagram of the photocatalyst prepared in example 2.
FIG. 9: scanning electron micrographs of the thin film photocatalyst obtained in example 3; wherein (a) is a top view and (b) is a side view.
FIG. 10: a real view of hydrogen evolution effect before and after the reaction of the thin film photocatalyst obtained in example 3; wherein (a) is before testing and (b) is under testing.
FIG. 11: the hydrogen evolution performance diagram of the thin film photocatalyst obtained in the embodiment 3 under different periods of sunlight; wherein (a) is the measured performance map for month April and (b) is the measured performance map for month November.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Example 1: preparation of ZIS nano material and photocatalytic hydrogen evolution rate test thereof
ZIS is synthesized by a hydrothermal method. Firstly ZnCl is put into 2 (0.068g，0.5mmol)、InCl 3 . 4H 2 O (0.293g, 1.0 mmol) and sodium citrate (0.300g, 1.0 mmol) were dissolved in a mixed solution containing 5mL of ethylene glycol and 25mL of deionized water, and stirred for 30min. Thioacetamide (TAA, 0.150g,2.0 mmol) was then added to the solution and stirring was continued for 30min. After the mixed solution is completely dissolved, the mixed solution is transferred to a lining of 50mL polytetrafluoroethylene, and then the mixed solution is put into a stainless steel reaction kettle and reacts in an oven at a constant temperature of 120 ℃ for 12 hours. And after the autoclave is naturally cooled, centrifuging, washing, freezing and drying to obtain 200mg of ZIS nano material.
Putting 20mg of ZIS nanosheet into a 300mL reactor, then adding 45mL of deionized water and 5mL of triethanolamine, ultrasonically dispersing until the solution is uniformly mixed, and then degassing for about 30min by using nitrogen to remove oxygen in the reaction system. After degassing was complete, the reactor was placed under a 300W xenon lamp for 3h. Sampling once per hour by using gas chromatography, recording peak area, and calculating hydrogen yield and hydrogen evolution rate. In the invention, the hydrogen evolution rate of the ZIS photocatalyst is 6.56 mu mol h -1 。
Example 2: preparation of monatomic Pt-doped ZIS photocatalyst, structural analysis of Pt/ZIS photocatalyst and photocatalytic hydrogen evolution rate test of Pt/ZIS photocatalyst
And preparing the Pt atom doped ZIS by a hydrothermal method. In the synthesis process, firstly ZnCl is put into 2 (0.068g，0.5mmol)、InCl 3 . 4H 2 O (0.293g, 1.0 mmol) and sodium citrate (0.3000 mmol) were dissolved in a mixed solution containing 5mL of ethylene glycol and 24.58mL of deionized water, and 0.42mL of 4.0mg mL was added to the solution -1 H 2 PtCl 6 . 6H 2 O solutionThe mixture was stirred at room temperature for 30 minutes. Then thioacetamide (TAA, 0.150g,2.0 mmol) was added, and after stirring was continued for 30 minutes, the mixed solution having been completely dissolved was transferred to a 50mL reaction vessel, and the reaction vessel was placed in an oven at 120 ℃ for 12 hours with the parameters set. After the autoclave was naturally cooled, after centrifugation, washing and freeze-drying, 200mg of the Pt/ZIS sample was obtained, which was 0.3wt%.
Putting a 20mg Pt/ZIS sample into a 300mL reactor, then adding 45mL deionized water and 5mL triethanolamine, ultrasonically dispersing until the solution is uniformly mixed, and then degassing for about 30min by using nitrogen to remove oxygen in the reaction system. After degassing was complete, the reactor was placed under a 300W xenon lamp for 3h. Sampling once per hour by using gas chromatography, recording peak area, and calculating hydrogen yield and hydrogen evolution rate. In the present invention, the hydrogen evolution rate of 0.3wt% Pt/ZIS photocatalyst was 163.73. Mu. Mol h -1 。
FIG. 1 is a TEM image of ZIS and 0.3wt% Pt/ZIS. It can be seen that 0.3wt% Pt/ZIS retains the two-dimensional morphology after the incorporation of Pt atoms in ZIS.
FIG. 2 is a dark-field high-resolution transmission electron micrograph of 0.3wt% Pt/ZIS photocatalyst taken under a spherical aberration-corrected projection electron microscope, with the circled portion representing a Pt monoatomic atom.
FIG. 3 is an ESR graph of 0.3wt% Pt/ZIS photocatalyst. 0.3wt% Pt/ZIS has a signal peak much stronger than ZIS, indicating that doping of Pt atoms into ZIS can create S vacancies therearound.
FIG. 4 is an XRD pattern of 0.3wt% Pt/ZIS photocatalyst. By comparison with the standard card, it can be seen that the diffraction peaks of the ZIS and 0.3wt% pt/ZIS photocatalyst substantially coincide with those of the ZIS standard card, and the corresponding diffraction peaks belong to the diffraction of the ZIS (006), (102) and (110) crystal planes, respectively. In addition, XRD did not detect the presence of Pt diffraction peaks due to the lower Pt loading and successful doping into the ZIS lattice.
Fig. 5 is an XPS chart of the photocatalyst. FIG. 5a is an XPS spectrum of elemental Pt with peaks at 71.1eV, 71.6eV, and 73.0eV of Pt 0 4f of 7/2 Orbitals, and the peaks at 74.3eV, 75.0eV, and 76.4eV are Pt 0 4f of 5/2 A track. FIG. 5b is an XPS spectrum of Pt at 72% wt/Pt/ZIS photocatalystPeaks at 2eV and 75.6eV are Pt δ+ 4f of 7/2 And 4f 5/2 Orbital, elemental Pt is not found 0 The presence of peaks.
FIG. 6 is a graph of UV-visible absorption spectra of ZIS and 0.3wt% Pt/ZIS photocatalyst.
FIG. 7 is a graph of water decomposition hydrogen evolution performance of photocatalysts with different Pt doping contents. The hydrogen evolution rate of the photocatalyst ZIS is 6.560 mu mol h -1 0.3wt% Pt/ZIS has a hydrogen evolution rate of 163.7. Mu. Mol h -1 The hydrogen evolution rate of the ZIS nano material is 25 times that of the ZIS nano material singly used.
FIG. 8 is a graph showing the performance of five photocatalytic water splitting hydrogen cycle experiments conducted successively on a 0.3wt% Pt/ZIS photocatalyst. The results confirm that the catalyst has better stability of single atom loading in 0.3wt% Pt/ZIS photocatalyst, and the catalyst can be recycled for a plurality of times.
Example 3: preparation of monatomic Pt-doped ZIS film and hydrogen evolution effect diagram of monatomic Pt-doped ZIS film under sunlight at different time periods
After the preparation of 0.3wt% Pt/ZIS composite material in example 2 above, a predetermined amount of ethanol was added to prepare 12.5mg mL -1 Ethanol solution of (2). After stirring uniformly, 200. Mu.L of a 0.3wt% Pt/ZIS solution was uniformly dropped on 1.5 cm. Times.5 cm of FTO, followed by placing it in a vacuum oven at 60 ℃ for drying treatment to obtain a photocatalyst film.
For testing, 13.5mL of deionized water, 1.5mL of triethanolamine were first added to the reactor. And (3) carrying out ultrasonic dispersion to uniformly mix the solution, putting the prepared film into the solution, and then introducing nitrogen for 30min to remove air in the reaction system. The reactor is placed in an outdoor environment and reacts under the irradiation of real sunlight. Sampling once per hour by using gas chromatography, recording peak area, calculating hydrogen yield and hydrogen evolution rate,
FIG. 9 is a scanning electron microscope image of 0.3wt% Pt/ZIS thin film photocatalyst. It can be seen that the photocatalyst is distributed on the surface of the FTO more uniformly, and the film has better flatness.
FIG. 10 is a real view showing the hydrogen evolution effect before and after 0.3wt% Pt/ZIS thin film photocatalyst reaction. It can be seen that after the light is applied, the hydrogen bubbles generated by the photocatalyst film are uniform and compact, and show better hydrogen evolution performance.
FIG. 11 is a graph of reaction hydrogen evolution performance of 0.3wt% Pt/ZIS thin film photocatalyst under different periods of solar light irradiation in April and November.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention. Are intended to be included within the scope of the present invention.
Claims (10)
1. Two-dimensional ZnIn doped with-vacancy double sites 2 S 4 The preparation method of the photocatalyst is characterized by comprising the following steps:
dissolving indium salt, zinc salt and sodium citrate in a mixed solvent of ethylene glycol-deionized water, then adding noble metal salt, stirring for 20-40 min at room temperature, then adding a sulfur source, and continuously stirring for 20-40 min to obtain a mixed solution; then heating the mixed solution to 100-150 ℃ for reaction for 10-15 h, and then centrifuging, washing, freezing and drying to obtain the two-dimensional ZnIn doped with vacancy double sites 2 S 4 A photocatalyst.
2. The two-dimensional ZnIn doped with-vacancy bi-sites of claim 1 2 S 4 The preparation method of the photocatalyst is characterized in that the indium salt is indium trichloride, indium nitrate or indium sulfate.
3. The two-dimensional ZnIn doped-vacancy dual site of claim 1 2 S 4 The preparation method of the photocatalyst is characterized in that the zinc salt is zinc chloride, zinc sulfate, zinc nitrate or zinc perchlorate.
4. The two-dimensional ZnIn doped-vacancy dual site of claim 1 2 S 4 The preparation method of the photocatalyst is characterized in that the noble metal salt is H 2 PtCl 6 、(NH 4 ) 2 PtCl 6 Or H 2 PdCl 4 。
5. The two-dimensional ZnIn doped-vacancy dual site of claim 1 2 S 4 The preparation method of the photocatalyst is characterized in that the sulfur source is sodium sulfide, thioacetamide or thiourea.
6. The two-dimensional ZnIn doped-vacancy dual site of claim 1 2 S 4 The preparation method of the photocatalyst is characterized in that in the mixed solvent of ethylene glycol and deionized water, the volume ratio of ethylene glycol to deionized water is 1:3 to 8.
7. The two-dimensional ZnIn doped with-vacancy bi-sites of claim 1 2 S 4 The preparation method of the photocatalyst is characterized in that the concentration of indium salt in the mixed solution is 20-60mmol L -1 The zinc salt concentration is 10-50mmol L -1 The concentration of sodium citrate is 20-60mmol L -1 The concentration of the noble metal salt is 0.08-3mmol L -1 The concentration of the sulfur source is 60-160mmol L -1 。
8. The two-dimensional ZnIn doped with a vacancy and having two sites obtained by the process according to any one of claims 1 to 7 2 S 4 A photocatalyst.
9. A photocatalyst film comprising the two-dimensional ZnIn doped with the vacancy double site as defined in claim 8 2 S 4 Photocatalyst and substrate conductive glass.
10. The two-dimensional ZnIn doped-vacancy dual site of claim 8 2 S 4 Use of a photocatalyst or the photocatalyst thin film according to claim 9 for photolysis of water for hydrogen production, CO oxidation and selective oxidation, redox synthesis reaction of organic matter, NO reduction or oxidation, and degradation of biomass material.
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