CN115608389B - 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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- CN115608389B CN115608389B CN202211167832.3A CN202211167832A CN115608389B CN 115608389 B CN115608389 B CN 115608389B CN 202211167832 A CN202211167832 A CN 202211167832A CN 115608389 B CN115608389 B CN 115608389B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 49
- 239000010439 graphite Substances 0.000 title claims abstract description 49
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 47
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 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 22
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 11
- 239000011592 zinc chloride Substances 0.000 claims abstract description 11
- 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 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 6
- 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 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 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 22
- 239000000243 solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002131 composite material Substances 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
- 238000001035 drying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 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
- -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
- 238000002156 mixing Methods 0.000 claims description 4
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 230000035484 reaction time Effects 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
- 239000012298 atmosphere Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 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 18
- 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
- 229910039444 MoC Inorganic materials 0.000 description 53
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 13
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 230000006872 improvement Effects 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 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
- 239000002064 nanoplatelet Substances 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
- 239000010453 quartz Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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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: and calcining ZIF-8 impregnated with ammonium molybdate tetrahydrate at a high temperature in a nitrogen atmosphere to obtain MoC@3D graphite carbon, and then adding the MoC@3D graphite carbon material into a solution containing zinc chloride, indium chloride tetrahydrate and thioacetamide to synthesize the photocatalytic material by a hydrothermal method. The hydrogen-generating material has larger specific surface area, ensures sufficient contact between the catalyst and reactants, and increases exposure of catalytic active sites. In addition, the addition of MoC@3D graphite carbon promotes the separation of photo-generated electrons and holes, reduces the recombination of the photo-generated electrons and 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 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 facing the human society due to excessive reliance on fossil fuels. Hydrogen is one of the most potential fuels to replace traditional fossil energy as a novel energy source that is environmentally friendly, clean and pollution-free. In order to achieve sustainable development, solar-driven semiconductor photocatalyst water splitting systems are considered as one promising approach to solve energy shortage and environmental problems. 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 ternary chalcogenide, due to the proper forbidden band width and energy band position, the ternary chalcogenide has remarkable solar energy collection capability and high stability and can produce H in photocatalysis 2 The field is widely concerned. However, the relatively high hydrogen evolution overpotential and the fast electron-hole recombination rate limit ZnIn 2 S 4 The hydrogen production efficiency under the visible light can not meet the requirements of practical application.
The introduction of the cocatalyst is an effective method for inhibiting electron hole pair recombination and improving hydrogen production efficiency. Molybdenum carbide (MoC), a transition metal carbide, has advantages of low cost, good conductivity, good chemical stability, etc., and has been widely used in many conventional reaction systems. In addition, the d-type electron density is very similar to that of noble metal, and the electric conductivity is high, so that the catalyst is a good promoter for photocatalytic or electrocatalytic hydrogen evolution reaction. According to previous studies, the synthesis of MoC is typically subjected to high temperatures (typically >800 ℃). However, the high temperature treatment process can cause the MoC to have larger particle size and serious agglomeration, so that the hydrogen evolution activity and the application in photocatalysis are limited. The Metal Organic Frameworks (MOFs) have the advantages of adjustable pore structures, large specific surface area, functionalized frame structures and the like. The MOF derivative has high stability and high conductivity, and maintains the rich pore structure and large specific surface area of the MOF. In order to break through the limitation, the molybdenum carbide is uniformly embedded in the carbon material derived from the MOF to prevent agglomeration and expose more active sites, and the indium zinc sulfide is compounded with the molybdenum carbide to prepare the MoC@3D graphite carbon@indium zinc sulfide sample, so that the reaction efficiency of 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 channel structure of MOF, and is beneficial to the material exchange in the hydrogen production process; and overcomes the defect of easy agglomeration of MoC 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 aim of the invention is achieved by the following technical scheme:
a preparation method and application of a 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 tetrahydrated ammonium molybdate at a high temperature in a nitrogen atmosphere, then the MoC@3D graphite carbon material is added into a solution containing zinc chloride, tetrahydrated indium chloride and thioacetamide, and the MoC@3D graphite carbon@indium zinc sulfide composite photocatalytic material is synthesized by a hydrothermal method.
A preparation method of a MoC@3D graphite carbon@indium zinc sulfide photocatalytic hydrogen production material comprises the following steps:
(1) Preparation of ZIF-8: 1.1 to 1.2g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ) And 1.3 to 1.4g of 2-methylimidazole are dissolved in 40 to 60mL of methanol solution, respectively. The two solutions were then mixed and stirred at room temperature for 20-24 h. And then washing with methanol, centrifuging for three times, and drying in a vacuum oven at the drying temperature of 80-100 ℃. After milling, a white powder, ZIF-8, was finally obtained.
(2) Preparation of MoC@3D graphitic carbon: ZIF-8 was dried in vacuo and then dispersed uniformly in an aqueous ethanol solution. Ammonium molybdate tetrahydrate (Mo) 7 O 24 .6NH 4 ·4H 2 O) stirring the solution at room temperature, performing ultrasonic treatment, and drying in a vacuum drying oven; grinding, placing into a crucible, placing into a tube furnace, and calcining under nitrogen atmosphere. Naturally cooling to room temperature to obtain a sample which is MoC@3D stoneAnd (3) ink carbon.
(3) Preparation of MoC@3D graphite carbon@indium zinc sulfide: and adding MoC@3D graphite carbon into the aqueous solution, and uniformly dispersing the mixture by ultrasonic at room temperature to obtain a mixed dispersion liquid A. Zinc chloride, indium chloride tetrahydrate and thioacetamide are added into water and stirred at room temperature until the mixture is completely dissolved, so as 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. Transferring the mixed solution C into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction, naturally cooling, centrifugally washing the precipitate, carrying out vacuum drying, 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 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 ZIF-8 is used in an amount of 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: 3-5 h. The calcining temperature of the tube 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 dosage of the MoC@3D graphite carbon is 0.01-0.03 g; the temperature of the ultrasonic wave at room temperature is 25-35 ℃, and the time is as follows: 0.5 to 1 hour. The addition amount of the zinc chloride is 0.25-0.30 g; the addition amount of the tetrahydrate indium chloride is 1.15-1.20 g; the addition amount of thioacetamide is 0.55 to 0.65g; the adding 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: and 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 ℃.
A photocatalytic hydrogen-generating material of MoC@3D graphite carbon@indium zinc sulfide comprises a ZIF-8 derivative composite MoC and a flower-shaped sphere formed by intersecting nano-sheet inserting sheets which are composited on the MoC@3D graphite carbon. The hydrogen-generating material has larger specific surface area, ensures sufficient contact between the catalyst and reactants, and increases exposure of catalytic active sites. In addition, the addition of MoC@3D graphite carbon promotes the separation of photo-generated electrons and holes, reduces the recombination of the photo-generated electrons and 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 good anti-light corrosion capability.
Visible light response three-layer MoC@3D graphite carbon@indium zinc sulfide composite catalyst, wherein the catalyst is 150mW/cm in the catalyst 2 Under the simulated sunlight irradiation, the photocatalytic hydrogen production efficiency is 1012 mu mol h -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 photo-generated electrons and holes, so that the photocatalytic efficiency is improved.
Compared with the prior art, the invention has the advantages that:
the hydrogen-generating material of the invention takes MoC as a cocatalyst and takes 3D graphite carbon formed by ZIF-8 derivatives as a carrier of 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 conductivity, has rich pore canal structures and larger specific surface area, and can prevent MoC agglomeration so as to expose sufficient hydrogen evolution active sites and promote the contact and catalytic action between the catalyst and reactants. The 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, and prepares the three-layer composite material with high photocatalytic hydrogen production activity, and the hydrogen production efficiency reaches 1012μmol h -1 g -1 Compared with pure indium zinc sulfide, the zinc sulfide has the advantages of improvement by 10.1 times, and good stability.
Drawings
FIG. 1 is an SEM image of 3D graphitic carbon, moC@3D graphitic carbon@indium zinc sulfide;
FIG. 2 is an XRD pattern for 3D graphitic carbon, moC@3D graphitic carbon@indium zinc sulfide;
FIG. 3 is a UV-vis diagram of 3D graphitic carbon, moC@3D graphitic carbon@indium zinc sulfide;
FIG. 4 is a graph of photocatalytic hydrogen production activity over time for 3D graphitic carbon, moC@3D graphitic carbon@indium zinc sulfide;
FIG. 5 is a graph of the stability of a MoC@3D graphitic carbon@indium zinc sulfide photocatalytic hydrogen production cycle.
FIG. 6 is a graph of photocatalytic hydrogen production activity for samples of different MoC@3D graphitic carbon loadings.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters that are not specifically noted.
Example 1
Preparing indium zinc sulfide:
0.26g of zinc chloride, 1.16g of indium chloride tetrahydrate and 0.60g of thioacetamide were added to 50mL of water, and stirred at room temperature for 1 hour until complete dissolution, to obtain a precursor solution. Transferring the precursor solution into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 12 hours at 200 ℃, naturally cooling, and centrifuging at 300 r/min. And finally, centrifugally washing the precipitate, drying in vacuum, and grinding to obtain bright yellow powder, namely indium zinc sulfide.
Example 2
Preparation of ZIF-8:
1.19g of zinc nitrate hexahydrate and 1.36g of 2-methylimidazole were each dissolved in 50mL of methanol solution. 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 ℃. After milling, a white powder, ZIF-8, was finally obtained.
Preparing MoC@3D graphite carbon:
after 0.4g ZIF-8 was dried under vacuum at 120℃and dispersed uniformly in 30mL of ethanol in water, 0.2g ammonium molybdate tetrahydrate (Mo 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 into a crucible, placing into a tube furnace, and calcining under nitrogen atmosphere. The calcination temperature is 800 ℃, the time is 2 hours, and the temperature rising rate is 3 ℃/min. And naturally cooling to room temperature to obtain a sample which is MoC@3D graphite carbon.
Example 3
Preparing MoC@3D graphite carbon@indium zinc sulfide:
0.01g of MoC@3D graphitic carbon was added to 50mL of water and sonicated at room temperature for 30min to give a black uniform dispersion. To this dispersion was added 0.26g of zinc chloride, 1.16g of indium chloride tetrahydrate and 0.60g of thioacetamide, and stirred at room temperature for 1 hour to complete dissolution. Transferring the solution into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 12 hours at 200 ℃, naturally cooling, and centrifuging at 300 r/min. And finally, centrifugally washing the precipitate with ethanol, vacuum drying, and grinding to obtain yellow-green powder, namely MoC@3D graphite carbon@indium zinc sulfide.
Example 4
Material characterization analysis: fig. 1 is an SEM image of moc@3d graphitic carbon@indium zinc sulfide, and the material is a complex flower-like sphere formed by intersecting nanoplatelet inserting sheets, consistent with a conventional zinc sulfide material. The trace amount of moc@3d graphitic carbon was not directly observed as it was scattered under the indium zinc sulfide flakes. Fig. 2 is an XRD pattern of indium zinc sulfide, moc@3d graphitic carbon, moc@3d graphitic carbon@indium zinc sulfide. Diffraction peak positions of indium zinc sulfide series samples correspond to hexagonal phase ZnIn 2 S 4 Is a characteristic peak of (2). The moc@3d graphitic carbon@indium zinc sulfide samples retained the characteristic peaks of indium zinc sulfide compared to the indium zinc sulfide samples. However, no significant MoC diffraction peak was found, which may be due to the low MoC nanoparticle content and small size. FIG. 3 is a UV-vis graph of indium sulfide and MoC@3D graphitic carbon@indium zinc sulfide. As can be seen, the absorption band edge of the sample of indium zinc sulfide is 538nm, and the absorption band of the MoC@3D graphite carbon@indium zinc sulfide sample is subjected to red shift to 565nm, so that the absorption of visible light is enhanced. And the light absorption intensity in the range of 250-800nm is obviously improved.
Example 5
The photocatalytic hydrogen production performance of indium zinc sulfide, moC@3D graphite carbon and MoC@3D graphite carbon@indium zinc sulfide samples is tested, and 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 (lambda. Gtoreq.420 nm) was used.
(3) The reaction vessel was bubbled with nitrogen under sealed conditions for 30min to remove dissolved oxygen. The magnetic stirrer is used for stirring. The reaction temperature was kept at about 25℃by circulating cooling water. Gas chromatography was performed using a TCD detector (GC 9790II, nitrogen carrier,molecular sieve columns) are used to detect the hydrogen production.
FIG. 4 shows the results of testing the hydrogen generating performance of different samples. From the graph, the hydrogen production efficiency of the MoC@3D graphite carbon@indium zinc sulfide sample is 1012 mu mol h -1 g -1 Is 10.1 times of the indium zinc sulfide sample. FIG. 5 is a graph showing the results of a cyclic hydrogen production test of a MoC@3D graphitic carbon@indium zinc sulfide sample. From the figure, it can be seen that the sample still maintains excellent hydrogen production performance after 5 cycles of 12 hours, showing that the material has excellent stability.
Example 6
The photocatalytic hydrogen production performance of the MoC@3D graphite carbon@indium zinc sulfide samples with different loadings 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 graphitic carbon was added to 50mL of water, respectively, and sonicated at room temperature for 30min to give a black uniform dispersion. To this dispersion was added 0.26g of zinc chloride, 1.16g of indium chloride tetrahydrate and 0.60g of thioacetamide, and stirred at room temperature for 1 hour to complete dissolution. Transferring the solution into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 12 hours at 200 ℃, naturally cooling, and centrifuging at 300 r/min. And finally, centrifugally washing the precipitate with ethanol, vacuum drying, and grinding to obtain bright yellow powder, namely MoC@3D graphite carbon@indium zinc sulfide.
The prepared samples were subjected to the photocatalytic hydrogen production rate test of example 6, and the results are shown in fig. 6. The result shows that the hydrogen production rate is increased and then decreased with the increase of the carbon addition amount of the MoC@3D graphite. When the addition amount of the MoC@3D graphite carbon is 0.75%, the photocatalytic hydrogen production rate of the sample is maximum.
The foregoing examples are merely illustrative of the principles of the present invention and are not strictly conditional, it being understood by those skilled in the art that various changes in detail or form may be made therein without departing from the spirit and scope of the invention as defined by the claims.
Claims (10)
1. The preparation method of the MoC@3D graphite carbon@indium zinc sulfide photocatalytic hydrogen production material is characterized by comprising the steps of calcining ZIF-8 impregnated with ammonium molybdate tetrahydrate at a 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 MoC@3D graphite carbon@indium zinc sulfide composite photocatalytic material 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 methanol solution; then mixing and stirring the two solutions, centrifugally washing, drying in a vacuum oven, and grinding to finally obtain white powder, namely ZIF-8;
(2) Preparation of MoC@3D graphitic 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 O solution at room temperature, performing ultrasonic treatment, drying in a vacuum drying oven, grinding, placing into a crucible, placing into a tube furnace, and adding nitrogen gasCalcining in atmosphere, naturally cooling to room temperature, and obtaining a sample which is MoC@3D graphite carbon;
(3) Preparation of MoC@3D graphite carbon@indium zinc sulfide: adding MoC@3D graphite carbon into water, and uniformly dispersing by ultrasonic 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, mixing and stirring to obtain a mixed solution C; transferring the mixed solution C into a polytetrafluoroethylene reaction kettle for hydrothermal reaction; and naturally cooling, centrifugally washing the precipitate, vacuum drying, and grinding to obtain yellow-green powder, namely MoC@3D graphite carbon@indium zinc sulfide.
2. The preparation method of the MoC@3D graphitic carbon@indium zinc sulfide photocatalytic hydrogen generating material according to claim 1, wherein in the step (1), the adding 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 graphitic carbon@indium zinc sulfide photocatalytic hydrogen generating material according to claim 1, wherein in the step (1), the temperature of mixing and stirring is 25-35 ℃, and the stirring rate 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 graphitic carbon@indium zinc sulfide photocatalytic hydrogen generating material according to claim 1, wherein in the step (2), the use amount of 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: 3-5 h.
5. The preparation method of the MoC@3D graphite carbon@indium zinc sulfide photocatalytic hydrogen generating material according to claim 1, wherein in the step (2), the calcining temperature of the tube furnace is 700-900 ℃, the calcining time is 2-4 h, and the heating rate is 2-5 ℃/min.
6. The preparation method of the MoC@3D graphitic carbon@indium zinc sulfide photocatalytic hydrogen generating material according to claim 1, wherein in the step (3), the dosage of the MoC@3D graphitic carbon is 0.01-0.03 g; the temperature of the ultrasonic wave 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 graphitic carbon@indium zinc sulfide photocatalytic hydrogen generating material according to claim 1, wherein in the step (3), the adding amount of zinc chloride is 0.25-0.30 g; the addition amount of the tetrahydrate indium chloride is 1.15-1.20 g; the addition amount of the thioacetamide is 0.55-0.65 g; the adding 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: and 1-2 h.
8. The preparation method of the MoC@3D graphite carbon@indium zinc sulfide photocatalytic hydrogen generating 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 hours; the solvent used for washing is ethanol, the washing centrifugal speed is 2500-3500 r/min, and the vacuum drying temperature is 80-100 ℃.
9. The preparation method of the invention according to any one of claims 1 to 8 is used for preparing the MoC@3D graphite carbon@indium zinc sulfide photocatalytic hydrogen production material, which is characterized by comprising a complex flower-shaped sphere formed by intersecting ZIF-8 derivative composite MoC and nano sheet inserting sheets composite on the MoC@3D graphite carbon.
10. The application of the MoC@3D graphite carbon@indium zinc sulfide photocatalytic hydrogen production material as claimed in claim 9 in the field of photocatalytic hydrogen production, wherein in an aqueous solution taking 10vol.% triethanolamine as a sacrificial agent, the water solution is prepared at a concentration of 150mW/cm 2 At a hydrogen production rate of 1012. Mu. Mol g -1 h -1 。
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