CN115608389A - MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material and preparation method and application thereof - Google Patents
MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material and preparation method and application thereof Download PDFInfo
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- CN115608389A CN115608389A CN202211167832.3A CN202211167832A CN115608389A CN 115608389 A CN115608389 A CN 115608389A CN 202211167832 A CN202211167832 A CN 202211167832A CN 115608389 A CN115608389 A CN 115608389A
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- zinc sulfide
- hydrogen production
- indium zinc
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 73
- 239000010439 graphite Substances 0.000 title claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 7
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 239000007770 graphite material Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000002904 solvent Substances 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- NPUQCECELINJML-UHFFFAOYSA-N 2-ethylimidazole Chemical compound CCC1=NC=C[N]1 NPUQCECELINJML-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910039444 MoC Inorganic materials 0.000 description 52
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 15
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 239000012919 MOF-derived carbon material Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- CNEOGBIICRAWOH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo] CNEOGBIICRAWOH-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material and a preparation method and application thereof. The method comprises the following steps: calcining ZIF-8 impregnated with ammonium molybdate tetrahydrate at high temperature in a nitrogen atmosphere to obtain MoC 3D graphite carbon, adding the MoC 3D graphite carbon material into a solution containing zinc chloride, indium chloride tetrahydrate and thioacetamide, and synthesizing the photocatalytic material by a hydrothermal method. The hydrogen production material has larger specific surface area, ensures the full contact between the catalyst and reactants, and increases the exposure of catalytic active sites. In addition, the addition of MoC 3D graphite carbon promotes the separation of photoproduction electrons and holes, reduces the recombination of the photoproduction electrons and the holes, and realizes the high-efficiency photocatalytic decomposition of water to produce hydrogen. The hydrogen production efficiency of the material prepared by the method is improved by 10.1 times compared with that of single-phase indium zinc sulfide, and the material has good stability and shows good anti-light corrosion capability.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material and a preparation method thereof.
Background
Energy crisis and environmental pollution are important threats faced by human society due to excessive dependence on fossil fuels. Hydrogen is one of the most potential fuels to replace the traditional fossil energy as a novel environment-friendly, clean and pollution-free energy. To achieve sustainable development, solar-driven semiconductor photocatalyst water splitting systems are considered as a promising measure to address energy shortages and environmental issues. One of the key challenges in this area is the development of visible light active photocatalysts. In recent years, znIn 2 S 4 As an important component of the ternary chalcogenide, due to the appropriate forbidden band width and energy band position, the ternary chalcogenide has remarkable solar energy acquisition capacity and high stability and can be used for producing H under photocatalysis 2 The field is receiving wide attention. However, the relatively high hydrogen evolution overpotential and the fast electron-hole recombination rate limit the ZnIn 2 S 4 The hydrogen production efficiency under visible light can not meet the requirements of practical application.
The introduction of the cocatalyst is an effective method for inhibiting the recombination of electron hole pairs and improving the hydrogen production efficiency. Molybdenum carbide (MoC), a transition metal carbide, has the advantages of low cost, good conductivity, good chemical stability, etc., and has been widely used in many conventional reaction systems. In addition, the catalyst is a good promoter for the photocatalytic or electrocatalytic hydrogen evolution reaction due to the fact that the d-charge electron state density of the catalyst is very similar to that of noble metals and the conductivity is high. According to previous studies, moC synthesis processes typically experience high temperatures (typically >800 ℃). However, the high temperature treatment process causes the MoC to have a large particle size and serious agglomeration, which limits the hydrogen evolution activity and application in photocatalysis. Metal Organic Frameworks (MOFs) have the advantages of adjustable pore structures, larger specific surface areas, functionalized framework structures and the like. The MOF derivative has high stability and high conductivity, and reserves the rich pore channel structure and large specific surface area of the MOF. In order to break through the limitation, molybdenum carbide is uniformly embedded in the MOF derived carbon material to prevent agglomeration and expose more active sites, and the MoC @3D graphite carbon @ indium zinc sulfide sample is prepared by compounding indium zinc sulfide and the indium zinc sulfide, so that the reaction efficiency in the hydrogen production process is improved.
Disclosure of Invention
The invention provides a preparation method and application of a MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material. The photocatalyst prepared by the method inherits the rich pore structure of the MOF, and is beneficial to material exchange in the hydrogen production process; but also overcomes the defect that MoC is easy to agglomerate in the preparation process, and fully exposes the active site. The rapid recombination of electron hole pairs on the indium zinc sulfide is inhibited, so that the hydrogen production efficiency is improved.
The purpose of the invention is realized by the following technical scheme:
the preparation method and application of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material are characterized in that the MoC @3D graphite carbon is obtained by calcining ZIF-8 impregnated with ammonium molybdate tetrahydrate at high temperature in a nitrogen atmosphere, then the MoC @3D graphite carbon material is added into a solution containing zinc chloride, indium chloride tetrahydrate and thioacetamide, and the MoC @3D graphite carbon @ indium zinc sulfide composite photocatalytic material is synthesized by a hydrothermal method.
A preparation method of MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material comprises the following steps:
(1) Preparation of ZIF-8: 1.1-1.2 g zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ) And 1.3-1.4 g of 2-methylimidazole are respectively dissolved in 40-60 mL of methanol solution. The two solutions were then mixed and stirred at room temperature for 20-24 h. Then washing with methanol, centrifuging for three times, and drying in a vacuum oven at the drying temperature of 80-100 ℃. Grinding to obtain white powder, namely ZIF-8.
(2) Preparation of MoC 3D graphite carbon: vacuum drying ZIF-8, and dispersing in ethanol water solution. Ammonium molybdate tetrahydrate (Mo) is added 7 O 24 .6NH 4 ·4H 2 O) solution, stirring at room temperature, performing ultrasonic treatment, and drying in a vacuum drying oven; grinding, placing the mixture into a crucible, placing the crucible into a tube furnace, and calcining the mixture in a nitrogen atmosphere. And naturally cooling to room temperature to obtain a sample, namely MoC @3D graphite carbon.
(3) Preparation of MoC @3D graphite carbon @ indium zinc sulfide: adding MoC @3D graphite carbon into the aqueous solution, and performing ultrasonic dispersion uniformly at room temperature to obtain a mixed dispersion liquid A. Adding zinc chloride, indium chloride tetrahydrate and thioacetamide into water, and stirring at room temperature until the zinc chloride, the indium chloride tetrahydrate and the thioacetamide are completely dissolved to obtain a mixed solution B. And adding the A into the mixed solution B, and mixing and stirring to obtain a mixed solution C. And transferring the mixed solution C into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction, naturally cooling, centrifuging and washing the precipitate, drying in vacuum, and grinding to finally obtain bright yellow powder, namely MoC @3D graphite carbon @ indium zinc sulfide.
In the method, in the step (1), the addition amount of the zinc nitrate is 1.1-1.2 g; the addition amount of the 2-methylimidazole is 1.3-1.4 g; the addition amount of the methanol is 80-120 mL. The stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the time is as follows: 20-24 h; the solvent used for washing is methanol, the washing centrifugal speed is 5000-8000 r/min, and the vacuum drying temperature is 80-100 ℃.
In the method, in the step (2), the dosage of the ZIF-8 is 0.2-0.4 g; the dosage of the ammonium molybdate is 0.2 to 0.4g; the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the time is as follows: 3 to 5 hours. The calcining temperature of the tubular furnace is 700-900 ℃, the time is 2-4 h, and the heating rate is 2-5 ℃/min.
In the method, in the step (3), the amount of MoC @3D graphite carbon is 0.01-0.03 g; the temperature of the ultrasound at room temperature is 25-35 ℃, and the time is as follows: 0.5-1 h. The addition amount of the zinc chloride is 0.25-0.30 g; the addition amount of the indium chloride tetrahydrate is 1.15-1.20 g; the addition amount of thioacetamide is 0.55-0.65 g; the addition amount of the pure water is 40-60 mL; the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the time is as follows: 1-2 h.
In the method, in the step (3), the hydrothermal temperature is 180-200 ℃, the hydrothermal reaction pressure is 0.15-0.4 MPa, and the hydrothermal reaction time is 12-24 h; the solvent used for washing is ethanol, the washing centrifugal speed is 2500-3500 r/min, and the vacuum drying temperature is 80-100 ℃.
The utility model provides a MoC @3D graphite carbon @ indium zinc sulfide photocatalysis hydrogen production material, including the compound MoC of ZIF-8 derivative and compound the numerous and diverse form spheroid of crossing constitution of nanometer piece inserted sheet on MoC @3D graphite carbon in the photocatalysis hydrogen production material. The hydrogen production material has larger specific surface area, ensures the full contact between the catalyst and reactants, and increases the exposure of catalytic active sites. In addition, the addition of MoC @3D graphite carbon promotes the separation of photoproduction electrons and holes, reduces the recombination of the photoproduction electrons and the holes, and realizes the high-efficiency hydrogen production by photocatalytic water decomposition. The hydrogen production efficiency of the material prepared by the method is improved by 10.1 times compared with that of single-phase indium zinc sulfide, and the material has good stability and shows good light corrosion resistance.
Three-layer MoC @3D graphite carbon @ indium zinc sulfide composite catalyst with visible light response function, wherein the catalyst is used in the presence of 150mW/cm 2 The photocatalytic hydrogen production efficiency is 1012 mu mol h under the simulated sunlight irradiation -1 g -1 . Compared with pure indium zinc sulfide, the MoC @3D graphite carbon @ indium zinc sulfide composite catalyst has more excellent photocatalytic performance, and the load of the MoC @3D graphite carbon remarkably promotes the effective separation of photoproduction electrons and holes, so that the photocatalytic efficiency is improved.
Compared with the prior art, the invention has the advantages that:
the hydrogen production material takes MoC as a cocatalyst, and takes 3D graphite carbon formed by ZIF-8 derivatives as a carrier of the MoC. MoC has very low hydrogen evolution overpotential and high conductivity, but is prone to agglomeration during the manufacturing process. The ZIF-8 derivative is a three-dimensional structure material with good electrical conductivity, has rich pore structure and larger specific surface area, can prevent the agglomeration of MoC so as to expose sufficient hydrogen evolution active sites and promote the contact and catalytic action between the catalyst and reactants. MoC @3D graphite carbon is compounded with the semiconductor indium zinc sulfide responding to visible light, so that the photocatalytic hydrogen production performance of the indium zinc sulfide is greatly improved. The invention solves the defect of easy agglomeration in the preparation method of the cocatalyst MoC on one hand, and prepares the three-layer composite material with high photocatalytic hydrogen production activity, and the hydrogen production efficiency reaches 1012 mu mol h -1 g -1 Compared with pure indium zinc sulfide, the zinc sulfide is improved by 10.1 times, and good stability is shown.
Drawings
FIG. 1 is an SEM image of 3D graphitic carbon, moC @3D graphitic carbon @ indium zinc sulfide;
FIG. 2 is an XRD plot of 3D graphite carbon, moC @3D graphite carbon @ indium zinc sulfide;
FIG. 3 is a UV-vis diagram of 3D graphite carbon, moC @3D graphite carbon @ indium zinc sulfide;
FIG. 4 is a diagram of photocatalytic hydrogen production activity of 3D graphite carbon, moC @3D graphite carbon @ indium zinc sulfide over time;
FIG. 5 is a diagram of MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production cycle stability.
FIG. 6 is a diagram of photocatalytic hydrogen production activity of different MoC @3D graphite carbon loading samples.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and the process parameters not specifically mentioned may be performed with reference to conventional techniques.
Example 1
Preparing indium zinc sulfide:
0.26g of zinc chloride, 1.16g of indium chloride tetrahydrate and 0.60g of thioacetamide are added into 50mL of water, and the mixture is stirred at room temperature for 1h until the components are completely dissolved, so that a precursor solution is obtained. And transferring the precursor solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12h, naturally cooling, and centrifuging at 300 r/min. And finally, centrifugally washing the precipitate, drying in vacuum, and grinding to finally obtain bright yellow powder, namely indium zinc sulfide.
Example 2
Preparing ZIF-8:
1.19g of zinc nitrate hexahydrate and 1.36g of 2-methylimidazole were dissolved in 50mL of a methanol solution, respectively. The two solutions were then mixed and stirred at room temperature for 24h. Then washed with methanol and centrifuged three times, and dried in a vacuum oven at 80 ℃. Grinding to obtain white powder, namely ZIF-8.
Preparation of MoC @3D graphite carbon:
0.4g ZIF-8 is dried in vacuum at 120 ℃, dispersed evenly in 30mL of ethanol water solution, and then 0.2g of ammonium molybdate tetrahydrate (Mo) is added 7 O 24 .6NH 4 ·4H 2 O), stirring at room temperature, performing ultrasonic treatment for 30min, and drying in a vacuum drying oven at 80 ℃. Grinding, placing the mixture into a crucible, placing the crucible into a tube furnace, and calcining the mixture in a nitrogen atmosphere. The calcination temperature is 800 ℃, the time is 2h, and the heating rate is 3 ℃/min. And naturally cooling to room temperature to obtain a sample, namely MoC 3D graphite carbon.
Example 3
Preparing MoC @3D graphite carbon @ indium zinc sulfide:
0.01g of MoC @3D graphite carbon is added into 50mL of water, and ultrasonic treatment is carried out for 30min at room temperature to obtain a black uniform dispersion liquid. 0.26g of zinc chloride, 1.16g of indium chloride tetrahydrate and 0.60g of thioacetamide were added to the dispersion and stirred at room temperature for 1 hour until complete dissolution. And transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12h, naturally cooling, and centrifuging at 300 r/min. And finally, centrifugally washing the precipitate with ethanol, drying in vacuum, and grinding to obtain yellow green powder, namely MoC @3D graphite carbon @ indium zinc sulfide.
Example 4
And (3) material characterization and analysis: FIG. 1 is an SEM image of MoC @3D graphite carbon @ indium zinc sulfide, which is a flower-shaped sphere formed by nanosheet inserts in a crossed manner, and is consistent with a conventional zinc sulfide material. No direct observation was made because a trace of moc @3d graphite carbon was scattered under the indium zinc sulfide layer sheet. FIG. 2 is an XRD pattern for indium zinc sulfide, moC @3D graphite carbon @ indium zinc sulfide. The position of a diffraction peak of the indium zinc sulfide series sample corresponds to the hexagonal ZnIn 2 S 4 Characteristic peak of (2). Compared with the indium zinc sulfide sample, the MoC @3D graphite carbon @ indium zinc sulfide sample retains the characteristic peak of the indium zinc sulfide. However, no significant MoC diffraction peak was observed, probably due to the low content and small size of the MoC nanoparticles. FIG. 3 is a UV-vis plot of indium sulfide and MoC @3D graphite carbon @ indium zinc sulfide. As can be seen from the figure, the absorption band edge of the indium zinc sulfide sample is about 538nm, while the absorption band of the MoC @3D graphite carbon @ indium zinc sulfide sample is red-shifted and shifted to 565nm, which enhances the absorption of visible light. And are combinedAnd the light absorption intensity in the range of 250-800nm is obviously improved.
Example 5
Testing the photocatalytic hydrogen production performance of indium zinc sulfide, moC 3D graphite carbon @ indium zinc sulfide samples, wherein the specific operation steps are as follows:
(1) 100mg of sample and 200mL of an aqueous solution containing 10vol.% triethanolamine were added to a 400mL top-irradiated quartz vessel.
(2) A300W xenon lamp was used as a visible light source, and a filter (. Lamda. Gtoreq.420 nm) was used.
(3) The reaction quartz vessel was bubbled with nitrogen gas under sealed conditions for 30min to remove dissolved oxygen. Stirring by a magnetic stirrer. The reaction temperature was kept around 25 ℃ with circulating cooling water. Gas chromatography was performed using a TCD detector (GC 9790II, nitrogen carrier,
molecular sieve column) was used to detect the production of hydrogen.
FIG. 4 shows the results of the hydrogen production performance tests of different samples. As can be seen from the figure, the hydrogen production efficiency of the MoC @3D graphite carbon @ indium zinc sulfide sample is 1012 mu mol h -1 g -1 Which is 10.1 times that of the indium zinc sulfide sample. FIG. 5 is the cyclic hydrogen production test result of MoC @3D graphite carbon @ indium zinc sulfide sample. It can be seen from the figure that the sample still maintains excellent hydrogen production performance after 5 cycles of 12h, and shows that the material has excellent stability.
Example 6
The photocatalytic hydrogen production performance of MoC @3D graphite carbon @ indium zinc sulfide samples with different loading amounts is tested, and the specific operation steps are as follows.
Preparing MoC @3D graphite carbon @ indium zinc sulfide:
0.001,0.0025,0.005,0.0075,0.01,0.03g of MoC @3D graphite carbon was added to 50mL of water, and ultrasonic treatment was performed at room temperature for 30min to obtain a black uniform dispersion. 0.26g of zinc chloride, 1.16g of indium chloride tetrahydrate and 0.60g of thioacetamide are added to the dispersion and stirred at room temperature for 1h until complete dissolution. And transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12h, naturally cooling, and centrifuging at 300 r/min. And finally, centrifugally washing the precipitate with ethanol, drying in vacuum, and grinding to finally obtain bright yellow powder, namely MoC 3D graphite carbon @ indium zinc sulfide.
The prepared sample was subjected to the photocatalytic hydrogen production rate test of example 6, and the result is shown in fig. 6. The result shows that the hydrogen production rate is increased and then reduced along with the increase of the addition amount of MoC 3D graphite carbon. When the addition amount of MoC @3D graphite carbon is 0.75%, the photocatalytic hydrogen production rate of the sample reaches the maximum.
The above examples are merely illustrative of the technical solutions of the present invention and not restrictive, and it will be understood by those of ordinary skill in the art that various changes in the details or forms thereof may be made without departing from the spirit and scope of the present invention as defined by the claims.
Claims (10)
1. A preparation method of MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material is characterized in that ZIF-8 impregnated with ammonium molybdate tetrahydrate is calcined at high temperature in a nitrogen atmosphere to obtain MoC @3D graphite carbon, then the MoC @3D graphite carbon material is added into a solution containing zinc chloride, indium chloride tetrahydrate and thioacetamide, and the MoC @3D graphite carbon @ indium zinc sulfide composite photocatalytic material is synthesized by a hydrothermal method;
the method specifically comprises the following steps:
(1) Preparation of ZIF-8: zinc nitrate hexahydrate Zn (NO) 3 ) 2 And 2-methylimidazole are respectively dissolved in the methanol solution; mixing and stirring the two solutions, then centrifugally washing, drying in a vacuum oven, and grinding to finally obtain white powder, namely ZIF-8;
(2) Preparation of MoC 3D graphite carbon: vacuum drying ZIF-8, dispersing ZIF-8 in water solution, and adding ammonium molybdate tetrahydrate Mo 7 O 24 .6NH 4 ·4H 2 Stirring the O solution at room temperature, performing ultrasonic treatment, drying in a vacuum drying oven, grinding, putting into a crucible, putting into a tubular furnace, calcining in a nitrogen atmosphere, and naturally cooling to room temperature to obtain a sample, namely MoC @3D graphite carbon;
(3) Preparation of MoC @3D graphite carbon @ indium zinc sulfide: adding MoC @3D graphite carbon into water, and performing ultrasonic dispersion uniformly at room temperature to obtain a mixed dispersion liquid A; adding zinc chloride, indium chloride tetrahydrate and thioacetamide into pure water, and stirring at room temperature until the zinc chloride, the indium chloride tetrahydrate and the thioacetamide are completely dissolved to obtain a mixed solution B; adding the A into the mixed solution B, and mixing and stirring to obtain a mixed solution C; then transferring the mixed solution C into a polytetrafluoroethylene reaction kettle for hydrothermal reaction; after natural cooling, the precipitate is centrifugally washed, dried in vacuum and ground to finally obtain yellow green powder, namely MoC 3D graphite carbon @ indium zinc sulfide.
2. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material according to claim 1, wherein in the step (1), the addition amount of zinc nitrate is 1.1-1.2 g; the addition amount of the 2-methylimidazole is 1.3-1.4 g; the addition amount of the methanol is 80-120 mL.
3. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material according to claim 1, wherein in the step (1), the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the time is as follows: 20-24 h; the solvent used for washing is methanol, the washing centrifugal speed is 5000-8000 r/min, and the vacuum drying temperature is 80-100 ℃.
4. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material as claimed in claim 1, wherein in the step (2), the amount of the ZIF-8 is 0.2-0.4 g; the dosage of the ammonium molybdate tetrahydrate is 0.2 to 0.4g; the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the stirring time is as follows: 3 to 5 hours.
5. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material as claimed in claim 1, wherein in the step (2), the calcination temperature of the tubular furnace is 700-900 ℃, the calcination time is 2-4 h, and the heating rate is 2-5 ℃/min.
6. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material as claimed in claim 1, wherein in the step (3), the amount of the MoC @3D graphite carbon is 0.01-0.03 g; the temperature of the ultrasound at room temperature is 25-35 ℃, and the time is as follows: 0.5 to 1 hour.
7. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material as claimed in claim 1, wherein in the step (3), the addition amount of zinc chloride is 0.25-0.30 g; the addition amount of the indium chloride tetrahydrate is 1.15-1.20 g; the addition amount of the thioacetamide is 0.55-0.65 g; the addition amount of the pure water is 40-60 mL; the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the stirring time is as follows: 1-2 h.
8. The preparation method of the MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material according to claim 1, wherein in the step (3), the hydrothermal temperature is 180-200 ℃, the hydrothermal reaction pressure is 0.15-0.4 MPa, and the hydrothermal reaction time is 12-24 h; the solvent used in washing is ethanol, the washing centrifugal speed is 2500-3500 r/min, and the vacuum drying temperature is 80-100 ℃.
9. The MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material prepared by the preparation method of any one of claims 1 to 8 is characterized by comprising a complex MoC of a ZIF-8 derivative and a flower-shaped sphere formed by crossing nanosheet inserts compounded on MoC @3D graphite carbon.
10. The MoC @3D graphite carbon @ indium zinc sulfide photocatalytic hydrogen production material as claimed in claim 9, applied to the field of photocatalytic hydrogen production, and characterized in that the concentration of the triethanolamine is 150mW/cm in an aqueous solution with 10vol.% of triethanolamine as a sacrificial agent 2 The hydrogen production rate is 1012 mu mol g –1 h –1 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108043436A (en) * | 2017-12-21 | 2018-05-18 | 福州大学 | The preparation method and applications of molybdenum carbide/sulfur-indium-zinc composite photo-catalyst |
| CN110354878A (en) * | 2019-06-12 | 2019-10-22 | 河南大学 | A kind of molybdenum carbide catalyst and preparation method thereof |
| CN110918109A (en) * | 2019-12-19 | 2020-03-27 | 吉林大学 | Carbon/molybdenum carbide coated titanium dioxide composite photocatalytic water decomposition hydrogen production catalyst and preparation method thereof |
| CN110975918A (en) * | 2019-12-18 | 2020-04-10 | 武汉理工大学 | Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof |
| CN112551571A (en) * | 2020-11-18 | 2021-03-26 | 汕头大学 | Preparation and application of ultrathin nanosheet microcell hollow indium zinc sulfide nanocage |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043436A (en) * | 2017-12-21 | 2018-05-18 | 福州大学 | The preparation method and applications of molybdenum carbide/sulfur-indium-zinc composite photo-catalyst |
| CN110354878A (en) * | 2019-06-12 | 2019-10-22 | 河南大学 | A kind of molybdenum carbide catalyst and preparation method thereof |
| CN110975918A (en) * | 2019-12-18 | 2020-04-10 | 武汉理工大学 | Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof |
| CN110918109A (en) * | 2019-12-19 | 2020-03-27 | 吉林大学 | Carbon/molybdenum carbide coated titanium dioxide composite photocatalytic water decomposition hydrogen production catalyst and preparation method thereof |
| CN112551571A (en) * | 2020-11-18 | 2021-03-26 | 汕头大学 | Preparation and application of ultrathin nanosheet microcell hollow indium zinc sulfide nanocage |
Non-Patent Citations (6)
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