CN113559834A - Ti3C2MXene@TiO2/CuInS2Catalytic material, preparation method and application thereof - Google Patents
Ti3C2MXene@TiO2/CuInS2Catalytic material, preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002135 nanosheet Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims description 68
- 239000002131 composite material Substances 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910020808 NaBF Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 239000011941 photocatalyst Substances 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000004627 transmission electron microscopy Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000001255 X-ray photoelectron diffraction Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- B01J35/30—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
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- 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
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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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- 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 belongs to the technical field of photocatalyst material preparation, and particularly relates to Ti3C2MXene@TiO2/CuInS2A Schottky/S type integrated heterojunction photocatalytic material, a preparation method and application thereof. Ti prepared by the invention3C2MXene@TiO2/CuInS2The Schottky/S type integrated heterojunction photocatalytic material has accordion-shaped/nano-sheet/nano-particlesThe structure can be effectively applied to hydrogen production by photocatalytic water decomposition, and has high efficiency and stability.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalyst materials, and particularly relates to a Ti3C2MXene@TiO2/CuInS2Catalytic material, preparation method and application thereof.
Background
In recent years, due to the excessive consumption of non-renewable fossil fuels such as coal, oil, natural gas, etc., humans face increasingly serious energy crisis and pollution problems. Therefore, the development of sustainable, clean energy sources to replace traditional fossil fuels is at hand. As is well known, hydrogen (H)2) High energy density, combustion only producing H2And O, is an ideal clean alternative energy source of fossil fuel. Among various hydrogen production strategies, photocatalytic water-splitting hydrogen production is considered to be one of the most optimal and environmentally friendly practical application methods.
Fujishima and Honda in TiO since 19722Since water splitting is found on the photoelectric electrode for the first time, many semiconductor materials are used as the photocatalyst for photocatalytic hydrogen production, such as ZnO, CdS and Cu2O, and the like. However, TiO2Due to its low cost, availability, non-toxicity, appropriate band structure, strong chemical and thermal stability, it remains the most studied semiconductor material for photocatalytic hydrogen production. Unfortunately, TiO2Low light capturing power and H2The slow kinetics of the evolution reaction, the rapid recombination of the photo-generated electron-hole pairs and other inherent defects hinder the TiO2The practical application of (1). Therefore, to improve TiO2Based on the hydrogen production activity of the photocatalyst, a large number of strategies are proposed, which mainly comprise element doping, defect introduction, heterojunction construction and co-catalyst modification. Wherein the co-catalyst is supported and the heterojunction is constructed by improving TiO2Two effective methods of electron and hole separation. Titanium dioxide based photocatalysts often use noble metals as promoters, which results in a dramatic increase in cost. Therefore, a low-cost TiO has been developed2A cocatalyst is necessary.
MXenes is an emerging two-dimensional (2D) layered transition metal carbide material, typically by selective etching of the parent phase Mn+1AXn(MAX) wherein M, a and X represent a transition metal, a third or fourth main group element, nitrogen or carbon, respectively. As MXenes has high specific surface area,Metal conductivity and hydrophilicity, in TiO2Shows great potential in photocatalysis. MXenes can be used as TiO due to its good metal conductivity2The electronic reservoir of (3). Thus, when MXene is mixed with TiO2When hybridized, it is often between MXene and TiO2The interface of the Schottky barrier is in favor of transfer and separation of photoexcited carriers. In addition, MXene generally has abundant surface groups and abundant exposed metal sites, which also contribute to H2The precipitation reaction rate of (2). In particular Ti3C2MXene is the most studied TiO due to its excellent structural stability and high conductivity2And (3) co-catalyst. Further, Ti3C2MXene can be partially oxidized to TiO without addition of titanium2Form Ti3C2@TiO2A hybrid. At present there is Ti3C2@TiO2The use of base-mixed photocatalysts for hydrogen production has been reported, but activity is still not ideal due to poor visible light capturing capability.
Disclosure of Invention
The present invention is to solve the above problems of the prior art and to provide a Ti alloy with high efficiency and stability3C2 MXene@TiO2/CuInS2Schottky/S type integrated heterojunction photocatalytic material.
The purpose of the invention can be realized by the following technical scheme:
ti3C2 MXene@TiO2/CuInS2A catalytic material consisting of Ti3C2 MXene、TiO2And CuInS2Composed of an accordion/nanosheet/nanoparticle heterostructure in which CuInS2The loading of the nano particles is 4-18%.
CuInS2(CIS) is a ternary sulfide semiconductor that is an attractive visible light driven photocatalyst due to its narrow bandgap (-1.5 eV) and appropriate hydrogen evolution Conduction Band (CB) potential. In addition, CIS also exhibits significant stability during photocatalytic water splitting. The Valence Band (VB) of the CIS is close to TiO2CB of the present inventionMXene and TiO2The interface of the semiconductor substrate forms a Schottky barrier, which is beneficial to transfer and separate photoexcited carriers through CIS and TiO2The matched band gap structure exists, an effective step structure heterojunction is formed, and the utilization rate of the photo-induced carrier is improved to the maximum extent by constructing the S-shaped heterojunction.
The invention also provides Ti3C2 MXene@TiO2/CuInS2A method of preparing a catalytic material, the method comprising the steps of:
s1, mixing Ti3AlC2MAX is slowly added into hydrofluoric acid for etching to obtain Ti3C2Mxene, then centrifugally washing with ultrapure water, and then carrying out vacuum drying;
s2, mixing Ti3C2Mxene dispersed in HCl and NaBF4Is subjected to hydrothermal treatment in the aqueous solution of (1), and is dried to obtain Ti3C2 MXene@TiO2A composite material;
s3, adding InCl3·4H2O and CuCl2·2H2Dispersing O in ethylenediamine, and adding sulfur powder and Ti3C2 MXene@TiO2The composite material is subjected to heat treatment, cooled and cleaned and dried to obtain Ti3C2 MXene@TiO2/CuInS2Schottky/S type integrated heterojunction photocatalytic material.
In one of the above Ti3C2 MXene@TiO2/CuInS2In the preparation method of the catalytic material, the etching temperature of the step S1 is 35-45 ℃, the rotation speed is 250-360rpm, and the time is 20-30 h. The invention utilizes hydrofluoric acid to etch Ti3AlC2The Al layer in MAX is etched away.
In one of the above Ti3C2 MXene@TiO2/CuInS2In the preparation method of the catalytic material, HCl and NaBF are contained in the aqueous solution of the step S24The concentrations of (A) and (B) are all 0.8-1.2M.
In one of the above Ti3C2 MXene@TiO2/CuInS2In the preparation method of the catalytic material, the hydrothermal treatment temperature of the step S2 is 150-200 ℃, and the time is 20-30 h.
In one of the above Ti3C2 MXene@TiO2/CuInS2In the preparation method of the catalytic material, InCl is added in step S33·4H2O and CuCl2·2H2The mass ratio of O is 1 (1.4-2.1).
Preferably, in step S3, 12-15mg of InCl is added to 50ml of ethylenediamine3·4H2O and 22-25mg CuCl2·2H2O。
In one of the above Ti3C2 MXene@TiO2/CuInS2In the preparation method of the catalytic material, the sulfur powder and Ti in the step S33C2 MXene@TiO2The mass ratio of the composite material is (0.04-0.08): 1.
preferably, in step S3, 5-6mg of sulfur powder and 90-110mg of Ti are added to 50ml of ethylenediamine3C2 MXene@TiO2。
In one of the above Ti3C2 MXene@TiO2/CuInS2In the preparation method of the catalytic material, the heat treatment temperature of the step S3 is 160-.
The invention also provides Ti3C2 MXene@TiO2/CuInS2The application of the catalytic material in the catalytic hydrogen production.
In one kind of Ti mentioned above3C2 MXene@TiO2/CuInS2In the application of the catalytic material in the catalytic hydrogen production, Ti is added3C2MXene@TiO2/CuInS2The Schottky/S type integrated heterojunction photocatalytic material is ultrasonically dispersed in deionized water, and then a sacrificial agent is added to catalyze and produce hydrogen under the irradiation of a visible light source.
Preferably, the sacrificial agent is methanol.
Preferably, the visible light source is a xenon light source.
Compared with the prior art, the invention has the following beneficial effects:
1. ti prepared by the invention3C2 MXene@TiO2/CuInS2The catalytic material has accordion shape/nano sheet/nanoThe particle structure can be effectively applied to hydrogen production by photocatalytic water decomposition, and has high efficiency and stability.
2. Ti of the invention3C2 MXene@TiO2/CuInS2The preparation process of the catalytic material is simple, the conditions are mild, the reaction is easy to control, the repeatability is good, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 shows Ti obtained in example 1 of the present invention3C2Scanning Electron Microscope (SEM) images of MXene;
FIG. 2 shows Ti obtained in example 1 of the present invention3C2X-ray diffraction (XRD) pattern of MXene;
FIG. 3 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2Low power Scanning Electron Microscope (SEM) pictures of catalytic materials;
FIG. 4 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2High power Scanning Electron Microscope (SEM) pictures of catalytic materials;
FIG. 5 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2An X-ray diffraction (XRD) pattern of the catalytic material;
FIG. 6 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2High power Scanning Electron Microscope (SEM) pictures of catalytic materials;
FIG. 7 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2An X-ray diffraction (XRD) pattern of the catalytic material;
FIG. 8 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2Low power Transmission Electron Microscopy (TEM) pictures of catalytic materials;
FIG. 9 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2High power Transmission Electron Microscopy (TEM) pictures of catalytic materials;
FIG. 10 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2Selective area electrons of catalytic materialDiffraction (SAED) pictures;
FIG. 11 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2High Resolution Transmission Electron Microscopy (HRTEM) pictures of catalytic materials;
FIG. 12 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2High Resolution Transmission Electron Microscopy (HRTEM) pictures of catalytic materials;
FIG. 13 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2High Resolution Transmission Electron Microscopy (HRTEM) pictures of catalytic materials;
FIG. 14 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2Surface scanning energy spectrum of the catalytic material;
FIG. 15 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2/CuInS2An X-ray photoelectron diffraction (XPS) spectrum of the catalytic material;
FIG. 16 shows a precursor Ti used in example 1 of the present invention3AlC2A Scanning Electron Microscope (SEM) picture of MAX;
FIG. 17 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2Low power Transmission Electron Microscopy (TEM) pictures of catalytic materials;
FIG. 18 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2High power Transmission Electron Microscopy (TEM) pictures of catalytic materials;
FIG. 19 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2Selected Area Electron Diffraction (SAED) pictures of catalytic materials;
FIG. 20 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2High resolution electron microscope (TEM) pictures of catalytic materials;
FIG. 21 shows Ti obtained in example 1 of the present invention3C2 MXene@TiO2An X-ray photoelectron diffraction (XPS) spectrum of the catalytic material;
FIG. 22 shows Ti obtained in example 1 of the present invention3C2MXene scanningElectron Microscopy (SEM) pictures;
FIG. 23 shows Ti obtained in example 1 of the present invention3C2X-ray diffraction (XRD) pattern of MXene;
FIG. 24 shows CuInS obtained in example 1 of the present invention2An X-ray photoelectron diffraction (XPS) spectrum of the material;
FIG. 25 is a comparison graph of photocatalytic hydrogen production of the catalytic materials of example 1 and comparative examples 1 and 2 of the present invention under different illumination times;
fig. 26 is a graph comparing photocatalytic hydrogen production rates of the catalytic materials obtained in comparative example 1 and comparative example 2 of example 1 of the present invention.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
s1, mixing 3g Ti3AlC2MAX is slowly added into a polyethylene terephthalate (PET) plastic container containing 100ml of hydrofluoric acid for etching for 24 hours to obtain Ti3C2Mxene, in which the etching temperature is 40 ℃ and the rotation speed is 300 rpm. Then, the reaction mixture was centrifuged, washed with ultrapure water to pH 6, and vacuum-dried at 60 ℃.
S2, mixing 400mg of Ti3C2Mxene dispersed in a solution containing 1M HCl and 1M NaBF4The aqueous solution is subjected to hydrothermal treatment at 180 ℃ for 24 hours, then washed by ultrapure water and absolute ethyl alcohol, and dried to obtain Ti3C2 MXene@TiO2A composite material;
s3, mixing 14.06mg InCl3·4H2O and 24.18mg CuCl2·2H2O was dispersed in 50ml of ethylenediamine, and then 5.29mg of sulfur powder and 100mg of Ti were added3C2MXene@TiO2The composite material is subjected to heat treatment for 15h at 180 ℃, and diluted 1mol/L HNO is sequentially used after being cooled to room temperature3Washed with ultrapure water and then dried to obtain Ti3C2MXene@TiO2/CuInS2A catalytic material.
Comparative example 1:
the only difference from example 1 isComparative example 1 CuInS without performing step S32The final product is Ti in the preparation process of the material3C2 MXene@TiO2A material.
Comparative example 2:
the only difference from example 1 is that comparative example 2 has only CuInS2The preparation process of the material comprises the following specific steps: adding InCl3·4H2O and CuCl2·2H2Fully dispersing O in ethylenediamine, adding sulfur powder, transferring the mixed solution into a hydrothermal reactor, reacting at 180 ℃ for 15 hours, taking out, centrifuging, drying to obtain CuInS2A material.
Application example 1:
0.01g of Ti prepared in example 1 was weighed3C2 MXene@TiO2/CuInS2The catalytic material is dispersed in a solution consisting of 80ml of deionized water and 20ml of methanol, and placed in a photocatalytic hydrogen production vacuum system after ultrasonic dispersion for 10 min. A300W xenon lamp is used as a simulated solar light source for catalyzing and producing hydrogen.
Application comparative example 1:
0.01g of Ti prepared in comparative example 1 was weighed3C2 MXene@TiO2The material is dispersed in a solution consisting of 80ml of deionized water and 20ml of methanol, and placed in a photocatalytic hydrogen production vacuum system after ultrasonic dispersion for 10 min. A300W xenon lamp is used as a simulated solar light source for catalyzing and producing hydrogen.
Application comparative example 2:
0.01g of CuInS prepared in comparative example 2 was weighed2The material is dispersed in a solution consisting of 80ml of deionized water and 20ml of methanol, and placed in a photocatalytic hydrogen production vacuum system after ultrasonic dispersion for 10 min. A300W xenon lamp is used as a simulated solar light source for catalyzing and producing hydrogen.
FIG. 1 shows Ti being produced3C2Scanning electron microscope images of MXene materials. Demonstrating a typical accordion-like structure.
FIG. 2 shows Ti being produced3C2XRD diffraction pattern of MXene material. The material prepared was proved to be Ti3C2。
FIG. 3 shows Ti thus prepared3C2 MXene@TiO2Macroscopic scanning electron microscopy of catalytic materials. The uniform growth of the titanium oxide flakes thereon was demonstrated.
FIG. 4 shows Ti thus prepared3C2 MXene@TiO2High power scanning electron microscopy of catalytic materials. Uniform growth of titanium oxide nanoplates thereon was demonstrated.
FIG. 5 shows Ti thus prepared3C2 MXene@TiO2X-ray diffraction pattern of catalytic material. Proving Ti3C2Successful partial oxidation of MXene to TiO2。
FIG. 6 shows Ti thus prepared3C2 MXene@TiO2/CuInS2High power scanning electron microscopy of catalytic materials. Demonstration of CuInS2Nanoparticles in Ti3C2 MXene@TiO2The successful growth of the above.
FIG. 7 shows Ti thus prepared3C2 MXene@TiO2/CuInS2The X-ray diffraction pattern of the catalytic material proves that the prepared material is Ti3C2 MXene、TiO2And CuInS2The composite material of (1).
FIG. 8 shows Ti thus prepared3C2 MXene@TiO2/CuInS2Low power transmission electron micrographs of the catalytic material. Flake TiO 22Successful growth thereon.
FIG. 9 shows Ti thus prepared3C2 MXene@TiO2/CuInS2High power transmission electron micrographs of the catalytic material. Flake TiO 22And CuInS2Successful growth on MXene.
FIG. 10 shows Ti thus prepared3C2 MXene@TiO2/CuInS2The selected electron diffraction pattern of the catalytic material. The prepared material is Ti3C2 MXene、TiO2And CuInS2The composite material of (1).
FIG. 11 is the Ti thus prepared3C2 MXene@TiO2/CuInS2High resolution transmission electron microscopy spectra of catalytic materials. Part of Ti was confirmed again3C2Ti obtained by in-situ oxidation of MXene3C2MXene@TiO2A composite material.
FIG. 12 is the Ti thus prepared3C2 MXene@TiO2/CuInS2High resolution transmission electron microscopy spectra of catalytic materials. It was confirmed again that the prepared MXene was partially oxidized to obtain TiO2And CuInS2And (4) compounding.
FIG. 13 is the Ti thus prepared3C2 MXene@TiO2/CuInS2High resolution transmission electron microscopy spectra of catalytic materials. Reconfirmation of the Ti produced3C2MXene and CuInS2And (4) compounding.
FIG. 14 is the Ti thus prepared3C2 MXene@TiO2/CuInS2Surface scanning energy spectrum of catalytic material. The material is detected to mainly contain C, Ti, O, Cu, In and S elements, and the prepared material is proved to be Ti3C2 MXene@TiO2And CuInS2And C, Ti, O, Cu, In and S In the prepared Ti3C2 MXene@TiO2/CuInS2The heterojunction composite material is uniformly distributed in the heterojunction composite material.
FIG. 15 shows Ti thus prepared3C2 MXene@TiO2/CuInS2The X-ray photoelectron spectrum of the catalytic material. The material is detected to mainly contain C, Ti, O, Cu, In and S elements, and the prepared material is further proved to be Ti3C2 MXene@TiO2And CuInS2The composite material of (1).
FIG. 16 is Ti3AlC2Scanning Electron Microscopy (SEM) of the precursor. It was confirmed to have a typical laminated block structure.
FIG. 17 is the Ti thus prepared3C2 MXene@TiO2Low power transmission electron microscopy of the catalytic material. It was confirmed that the material produced was Ti3C2MXene is partially oxidized to produce flake TiO2。
FIG. 18 is Ti thus prepared3C2 MXene@TiO2High power transmission electron microscopy of catalytic materials. It was confirmed that TiO was produced2Is adhered to Ti3C2MXene surface.
FIG. 19 is the Ti thus prepared3C2 MXene@TiO2The selected electron diffraction pattern of the catalytic material. It was confirmed that the material produced was Ti3C2 MXene@TiO2A composite material.
FIG. 20 is the Ti thus prepared3C2 MXene@TiO2High resolution transmission electron microscopy spectra of catalytic materials. Confirmation of Ti3C2MXene@TiO2And TiO successfully prepared, and2the crystallinity of (2) is good.
FIG. 21 is the Ti thus prepared3C2 MXene@TiO2The X-ray photoelectron spectrum of the catalytic material. The material is detected to mainly contain C, Ti and O elements, and the prepared material is further proved to be Ti3C2 MXene@TiO2A material.
FIG. 22 is CuInS2Scanning electron micrograph (c). It was confirmed to have a block structure.
FIG. 23 is CuInS2X-ray diffraction pattern of (a). The prepared material is proved to be CuInS2。
FIG. 24 is the CuInS prepared2The X-ray photoelectron spectrum of the catalytic material. The material is detected to mainly contain Cu, In and S elements, and the prepared material is further proved to be CuInS2A material.
FIG. 25 is a graph showing the comparison of photocatalytic hydrogen production performance of the catalytic materials prepared in application example 1 and comparative application examples 1 and 2 under different illumination times3C2 MXene@TiO2/CuInS2Material used as photocatalyst is compared with Ti3C2 MXene@TiO2With pure CuInS2The material has obviously improved photocatalytic hydrogen production performance, and the hydrogen production amount can reach 7481.76 mu mol g after 21 hours of illumination-1And Ti3C2 MXene@TiO2Only 107.91. mu. mol. g-1，CuInS2It is almost zero.
FIG. 26 shows a catalyst material according to the present invention in application example 1, comparative application example 1, and comparative application example 2The photocatalytic hydrogen production rate of the material is compared, and the result shows that the Ti prepared by the method is3C2 MXene@TiO2/CuInS2Material used as photocatalyst is compared with Ti3C2MXene@TiO2With pure CuInS2The material can obviously improve the photocatalytic hydrogen production rate which can reach 356.27 mu mol g-1·h-1And Ti3C2 MXene@TiO2Only 5.13. mu. mol. g-1Pure CuInS2There is little photocatalytic activity.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. Ti3C2 MXene@TiO2/CuInS2Catalytic material, characterized in that the catalytic material consists of Ti3C2 MXene、TiO2And CuInS2Composed of an accordion/nanosheet/nanoparticle heterostructure in which CuInS2The loading of the nano particles is 4-18%.
2. The Ti of claim 13C2 MXene@TiO2/CuInS2A method for preparing a catalytic material, comprising the steps of:
s1, mixing Ti3AlC2MAX is slowly added into hydrofluoric acid for etching to obtain Ti3C2Mxene, then centrifugally washing with ultrapure water, and then carrying out vacuum drying;
s2, mixing Ti3C2Mxene dispersed in HCl and NaBF4Is subjected to hydrothermal treatment in the aqueous solution of (1), and is dried to obtain Ti3C2MXene@TiO2A composite material;
s3, adding InCl3·4H2O and CuCl2·2H2Dispersing O in ethylenediamine, and adding sulfur powder and Ti3C2 MXene@TiO2The composite material is subjected to heat treatment, cooled and cleaned and dried to obtain Ti3C2 MXene@TiO2/CuInS2Schottky/S type integrated heterojunction photocatalytic material.
3. A Ti according to claim 23C2 MXene@TiO2/CuInS2The preparation method of the catalytic material is characterized in that the etching temperature of the step S1 is 35-45 ℃, the rotating speed is 250-360rpm, and the time is 20-30 h.
4. A Ti according to claim 23C2 MXene@TiO2/CuInS2The preparation method of the catalytic material is characterized in that step S2 is implemented by dilute hydrochloric acid and NaBF in aqueous solution4The concentrations of (A) and (B) are all 0.8-1.2M.
5. A Ti according to claim 23C2 MXene@TiO2/CuInS2The preparation method of the catalytic material is characterized in that the hydrothermal treatment temperature of the step S2 is 150-200 ℃, and the time is 20-30 h.
6. A Ti according to claim 23C2 MXene@TiO2/CuInS2The preparation method of the catalytic material is characterized in that InCl is added in the step S33·4H2O and CuCl2·2H2The mass ratio of O is 1 (1.5-2).
7. A Ti according to claim 23C2 MXene@TiO2/CuInS2The preparation method of the catalytic material is characterized in that the sulfur powder and Ti in the step S33C2 MXene@TiO2The mass ratio of the composite material is (0.05-0.1): 1.
8. a Ti according to claim 23C2 MXene@TiO2/CuInS2The preparation method of the catalytic material is characterized in that the heat treatment temperature of the step S3 is 160-200 ℃, and the time is 2-18 h.
9. The Ti of claim 13C2 MXene@TiO2/CuInS2The application of the catalytic material in the catalytic hydrogen production.
10. A Ti according to claim 93C2 MXene@TiO2/CuInS2The application of the catalytic material in the catalytic hydrogen production is characterized in that Ti is used3C2MXene@TiO2/CuInS2The Schottky/S type integrated heterojunction photocatalytic material is ultrasonically dispersed in deionized water, and then a sacrificial agent is added to catalyze and produce hydrogen under the irradiation of a visible light source.
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