CN108118362A - A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application - Google Patents
A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application Download PDFInfo
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- CN108118362A CN108118362A CN201810018879.0A CN201810018879A CN108118362A CN 108118362 A CN108118362 A CN 108118362A CN 201810018879 A CN201810018879 A CN 201810018879A CN 108118362 A CN108118362 A CN 108118362A
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title 1
- 239000002135 nanosheet Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- 239000004744 fabric Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- -1 polytetrafluoroethylene Polymers 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 25
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 229910017709 Ni Co Inorganic materials 0.000 claims description 7
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 7
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000005457 optimization Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
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Abstract
本发明涉及一种二硫化钼电催化产氢电极及其制备方法和用途，所述二硫化钼电催化产氢电极包括电极基底和负载在所述电极基底表面的二硫化钼纳米片阵列，所述二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；所述二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。本发明二硫化钼电催化产氢电极具有多级次纳米片阵列结构，具有较大的电化学活性表面积，大幅提高二硫化钼的催化活性，表现出优异的产氢性能；且采用水热法在电极基底上沉积层状双金属氢氧化物，然后以其为牺牲模板，水热反应得到具有多级次结构的二硫化钼，同时实现了元素掺杂和结构优化，便于操作。
The invention relates to a molybdenum disulfide electrocatalytic hydrogen production electrode and its preparation method and application. The molybdenum disulfide electrocatalytic hydrogen production electrode includes an electrode base and a molybdenum disulfide nanosheet array supported on the surface of the electrode base. The molybdenum disulfide nanosheet array is doped with Ni(II) and Co(II); the molybdenum disulfide nanosheet array includes a primary nanosheet perpendicular to the electrode substrate surface and a secondary nanosheets. The molybdenum disulfide electrocatalytic hydrogen production electrode of the present invention has a multi-level sub-nanometer sheet array structure, has a large electrochemically active surface area, greatly improves the catalytic activity of molybdenum disulfide, and exhibits excellent hydrogen production performance; and adopts a hydrothermal method Deposit layered double metal hydroxide on the electrode substrate, and then use it as a sacrificial template to hydrothermally react to obtain molybdenum disulfide with a multi-level structure. At the same time, element doping and structure optimization are realized, which is convenient for operation.
Description
技术领域technical field
本发明涉及纳米材料制备及应用技术领域，尤其涉及一种二硫化钼电催化产氢电极及其制备方法和用途。The invention relates to the technical field of nanomaterial preparation and application, in particular to a molybdenum disulfide electrocatalytic hydrogen production electrode and its preparation method and application.
背景技术Background technique
由于化石燃料的大量使用，导致能源危机与温室效应不断加剧，因此近年来大量研究工作致力于开发利用可再生、无污染的新能源。氢气，作为一种能量密度高，清洁无污染的可再生能源具有很好的应用前景。通常而言，氢气主要是由电解水产生，但在电解水过程中需要使用电催化剂克服过电势以提高产氢效率。二硫化钼(MoS2)是一种二维层状材料，不管在实验还是理论上均已被证实具有很高的产氢活性。但是二硫化钼的产氢活性位点位于其边沿位置处钼富集的钼边上，而其平面位置是惰性的。基于此，大量的工作合成了纳米线、纳米片、纳米盒子和双螺旋二十四面体等不同形貌的二硫化钼，以达到暴露更多边沿位置，增加材料的电化学活性表面积进而提升电催化产氢性能的目的。采用具有三维形貌的导电基底(碳布、泡沫镍等)直接负载电催化剂能够进一步提升电化学活性表面积，增强反应过程中电解液与气泡的扩散以及改善基底与催化剂间的导电性。另一方面，因为二硫化钼本身的导电性差，阻碍了其在催化产氢过程中的电荷传输，大量工作通过掺杂(O、N、F等)及相转变(2H相的二硫化钼转化为1T相二硫化钼)的方式提高材料自身导电性及反应活性。Due to the extensive use of fossil fuels, the energy crisis and the greenhouse effect have been aggravated. Therefore, in recent years, a lot of research work has been devoted to the development and utilization of renewable and non-polluting new energy sources. Hydrogen, as a high energy density, clean and pollution-free renewable energy has a good application prospect. Generally speaking, hydrogen is mainly produced by electrolysis of water, but in the process of electrolysis of water, electrocatalysts need to be used to overcome the overpotential to improve the efficiency of hydrogen production. Molybdenum disulfide (MoS 2 ) is a two-dimensional layered material, which has been proved to have high hydrogen production activity both experimentally and theoretically. But the hydrogen-generating active sites of MoS2 are located on the molybdenum-rich molybdenum edge at its edge position, while its planar position is inert. Based on this, a large number of works have synthesized molybdenum disulfide with different morphologies such as nanowires, nanosheets, nanoboxes, and double helix tetrahedrons, in order to expose more edge positions, increase the electrochemically active surface area of the material, and improve The purpose of electrocatalytic hydrogen production performance. The use of conductive substrates with three-dimensional morphology (carbon cloth, nickel foam, etc.) to directly support electrocatalysts can further increase the electrochemically active surface area, enhance the diffusion of electrolyte and bubbles during the reaction process, and improve the conductivity between the substrate and the catalyst. On the other hand, because the poor conductivity of molybdenum disulfide itself hinders its charge transport in the process of catalytic hydrogen production, a lot of work has been done by doping (O, N, F, etc.) and phase transformation (molybdenum disulfide conversion of 2H phase It is 1T phase molybdenum disulfide) to improve the conductivity and reactivity of the material itself.
因此，本领域期望通过一种简单的方法一种具有特殊纳米结构并且有异原子掺杂的二硫化钼电极，不但能增加电极的活性位点，还能提高材料本身的导电性及催化活性，从而达到提升电催化产氢性能的目的。Therefore, the field expects a molybdenum disulfide electrode with a special nanostructure and heteroatom doping through a simple method, which can not only increase the active sites of the electrode, but also improve the conductivity and catalytic activity of the material itself. So as to achieve the purpose of improving the electrocatalytic hydrogen production performance.
发明内容Contents of the invention
鉴于现有技术中存在的问题，本发明的目的之一在于提供一种具有特殊纳米结构并且有异原子掺杂的二硫化钼电极，不但能增加电极的活性位点，还能提高材料本身的导电性及催化活性，从而达到提升电催化产氢性能的目的。In view of the problems existing in the prior art, one of the objectives of the present invention is to provide a molybdenum disulfide electrode with a special nanostructure and heteroatom doping, which can not only increase the active sites of the electrode, but also improve the Conductivity and catalytic activity, so as to achieve the purpose of improving the performance of electrocatalytic hydrogen production.
为达此目的，本发明采用如下技术方案：For reaching this purpose, the present invention adopts following technical scheme:
第一方面，本发明提供一种二硫化钼电催化产氢电极，包括电极基底和负载在所述电极基底表面的二硫化钼纳米片阵列，所述二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；In a first aspect, the present invention provides a molybdenum disulfide electrocatalytic hydrogen production electrode, comprising an electrode substrate and a molybdenum disulfide nanosheet array supported on the surface of the electrode substrate, and the molybdenum disulfide nanosheet array is doped with Ni( II) and Co(II);
所述二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。The molybdenum disulfide nanosheet array includes primary nanosheets perpendicular to the surface of the electrode substrate and secondary nanosheets perpendicular to the primary nanosheets.
本发明二硫化钼电催化产氢电极具有多级次纳米片阵列结构，具有较大的电化学活性表面积，大幅提高二硫化钼的催化活性，表现出优异的产氢性能；且本发明催化产氢电极的活性材料为二硫化钼，属于非贵金属催化剂，价格低廉。The molybdenum disulfide electrocatalytic hydrogen production electrode of the present invention has a multi-level nanosheet array structure, has a large electrochemically active surface area, greatly improves the catalytic activity of molybdenum disulfide, and exhibits excellent hydrogen production performance; and the catalytic production of the present invention The active material of the hydrogen electrode is molybdenum disulfide, which belongs to non-noble metal catalyst and is cheap.
优选地，所述电极基底包括碳布和/或泡沫镍。Preferably, the electrode substrate includes carbon cloth and/or nickel foam.
优选地，所述电极基底为碳布。Preferably, the electrode substrate is carbon cloth.
优选地，所述二硫化钼电催化产氢电极中Ni(II)、Co(II)与二硫化钼的质量比为(5～10):(5～10):100，例如5:9:100、10:7:100、8:6:100、9:8:100或10:7:100等。Preferably, the mass ratio of Ni(II), Co(II) and molybdenum disulfide in the molybdenum disulfide electrocatalytic hydrogen production electrode is (5-10):(5-10):100, for example 5:9: 100, 10:7:100, 8:6:100, 9:8:100, or 10:7:100, etc.
第二方面，本发明提供一种如第一方面所述二硫化钼电催化产氢电极的制备方法，包括如下步骤：In a second aspect, the present invention provides a method for preparing a molybdenum disulfide electrocatalytic hydrogen production electrode as described in the first aspect, comprising the steps of:
(1)将钴盐、镍盐和六亚甲基四胺溶于甲醇中得到混合溶液，再将电极基底浸在所述混合溶液中，密封，150～200℃反应6～24h后冷却，取出电极基底，洗涤，干燥，得到沉积有Ni-Co层状双金属氢氧化物纳米片阵列的电极基底；(1) Dissolve cobalt salt, nickel salt and hexamethylenetetramine in methanol to obtain a mixed solution, then immerse the electrode base in the mixed solution, seal it, react at 150-200°C for 6-24 hours, cool it, and take it out The electrode substrate is washed and dried to obtain an electrode substrate deposited with a Ni-Co layered double metal hydroxide nanosheet array;
(2)将四硫代钼酸铵溶于N,N-二甲基甲酰胺中，加入还原剂，与步骤(1)处理所得的电极基底混合，密封，140～180℃下，例如140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃或180℃等，反应4～10h后冷却，例如4h、5h、6h、7h、8h、9h或10h等，取出电极基底，洗涤，干燥，得到二硫化钼电催化产氢电极。(2) Dissolve ammonium tetrathiomolybdate in N,N-dimethylformamide, add a reducing agent, mix with the electrode substrate obtained in step (1), seal it, at 140-180°C, for example 140°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C, etc., react for 4 to 10 hours and then cool, such as 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., take out The electrode substrate is washed and dried to obtain a molybdenum disulfide electrocatalytic hydrogen production electrode.
现有技术中通常将结构优化和元素掺杂视为两个工序，通过各自的技术手段分别实现。而本发明首先采用水热法在电极基底上沉积层状双金属氢氧化物，然后以其为牺牲模板，水热反应得到具有多级次结构的二硫化钼，合成方法简单，一举两得，同时实现了元素掺杂和结构优化。如图1所示，本发明Ni-Co层状双金属氢氧化物的结构作为模板，所制备的电极在保留层状双金属氢氧化物所具有的纳米片阵列结构的基础上，在大的纳米片上生长了一层垂直生长的超薄二硫化钼纳米片，如图2所示，同时实现了Ni、Co元素的掺杂。另一方面，现有技术往往为了避免掺杂元素对结构的不利影响，倾向于将掺杂元素在二硫化钼结构构建完成后进行掺杂，掺杂效果往往差强人意，不同于现有技术的是，本发明的掺杂元素是事先存在于模板中的，在二硫化钼电极的微观结构中掺杂元素分布的范围更广，对催化性能的提高更显著。实际上，本发明为二氧化钼电催化产氢电极的制备提供了一种方便且高效的新的制备方法，便于操作，具有普适性。In the prior art, structural optimization and element doping are generally regarded as two processes, which are realized through respective technical means. However, the present invention first adopts the hydrothermal method to deposit layered double metal hydroxide on the electrode substrate, and then uses it as a sacrificial template to hydrothermally react to obtain molybdenum disulfide with a multi-level structure. The synthesis method is simple and serves two purposes. element doping and structural optimization. As shown in Figure 1, the structure of the Ni-Co layered double metal hydroxide of the present invention is used as a template, and the prepared electrode is on the basis of retaining the nanosheet array structure that the layered double metal hydroxide has. A layer of vertically grown ultra-thin molybdenum disulfide nanosheets was grown on the nanosheets, as shown in Figure 2, and the doping of Ni and Co elements was realized at the same time. On the other hand, in order to avoid the adverse effect of doping elements on the structure, the existing technology tends to dope the doping elements after the molybdenum disulfide structure is constructed, and the doping effect is often unsatisfactory. The doping elements of the present invention are pre-existed in the template, and the distribution range of the doping elements in the microstructure of the molybdenum disulfide electrode is wider, and the improvement of the catalytic performance is more significant. In fact, the present invention provides a convenient and efficient new preparation method for the preparation of molybdenum dioxide electrocatalytic hydrogen production electrode, which is easy to operate and has universal applicability.
优选地，步骤(1)所述电极基底为经过前处理的电极基底；Preferably, the electrode substrate in step (1) is a pre-treated electrode substrate;
优选地，所述前处理包括：将电极基底依次用丙酮、异丙醇、乙醇、蒸馏水进行超声清洗后干燥。Preferably, the pretreatment includes: ultrasonically cleaning the electrode substrate with acetone, isopropanol, ethanol, and distilled water in sequence, and then drying.
优选地，步骤(1)所述钴盐包括六水合硝酸钴、氯化钴、硫酸钴中的任意一种或至少两种的组合。Preferably, the cobalt salt in step (1) includes any one or a combination of at least two of cobalt nitrate hexahydrate, cobalt chloride and cobalt sulfate.
优选地，步骤(1)所述镍盐包括六水合硝酸镍、氯化镍、硫酸镍中的任意一种或至少两种的组合。Preferably, the nickel salt in step (1) includes any one or a combination of at least two of nickel nitrate hexahydrate, nickel chloride, and nickel sulfate.
为优化二硫化钼中掺杂的镍钴比例，进而二硫化钼的反应活性，优选地，步骤(1)所述钴盐、镍盐的摩尔比为1:(0.5～2)，例如1:0.5、1:0.8、1:1.0、1:1.2、1:1.5、1:1.8或1:2等。In order to optimize the doped nickel-cobalt ratio in molybdenum disulfide, and then the reactivity of molybdenum disulfide, preferably, the molar ratio of cobalt salt and nickel salt described in step (1) is 1:(0.5～2), for example 1: 0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.5, 1:1.8 or 1:2 etc.
优选地，步骤(1)所述反应的温度为170～190℃，例如170℃、172℃、175℃、178℃、180℃、182℃、185℃或190℃等，时间为10～15h，例如10h、11h、12h、13h、14h或15h等。Preferably, the reaction temperature in step (1) is 170-190°C, such as 170°C, 172°C, 175°C, 178°C, 180°C, 182°C, 185°C or 190°C, etc., and the time is 10-15 hours, For example 10h, 11h, 12h, 13h, 14h or 15h etc.
优选地，步骤(1)所述反应在高压反应釜的聚四氟乙烯内衬中进行。Preferably, the reaction described in step (1) is carried out in a polytetrafluoroethylene lining of an autoclave.
优选地，步骤(2)所述还原剂包括水合肼。Preferably, the reducing agent in step (2) includes hydrazine hydrate.
优选地，步骤(2)所述四硫代钼酸铵、还原剂的摩尔比为1:(10～30)，例如1:10、1:12、1:15、1:18、1:20、1:22、1:25、1:28或1:30等。Preferably, the molar ratio of ammonium tetrathiomolybdate and reducing agent in step (2) is 1:(10-30), such as 1:10, 1:12, 1:15, 1:18, 1:20 , 1:22, 1:25, 1:28 or 1:30 etc.
优选地，步骤(2)所述反应的温度为150～160℃，时间为6～8h。Preferably, the temperature of the reaction in step (2) is 150-160° C., and the time is 6-8 hours.
优选地，步骤(2)所述反应在高压反应釜的聚四氟乙烯内衬中进行。Preferably, the reaction in step (2) is carried out in a polytetrafluoroethylene lining of an autoclave.
作为本发明优选的技术方案，所述二硫化钼电催化产氢电极的制备方法包括如下步骤：As a preferred technical solution of the present invention, the preparation method of the molybdenum disulfide electrocatalytic hydrogen production electrode comprises the following steps:
(1)将钴盐、镍盐按照摩尔比为1:(0.5～2)溶于甲醇中，加入六亚甲基四胺得到混合溶液，将电极基底依次用丙酮、异丙醇、乙醇、蒸馏水进行超声清洗后干燥，浸在所述混合溶液中，转移至聚四氟乙烯内衬中，放入高压反应釜中密封，置于鼓风干燥箱中加热至150～200℃，反应6～24h后冷却，取出电极基底，洗涤，干燥，得到沉积有Ni-Co层状双金属氢氧化物纳米片阵列的电极基底；(1) Dissolve cobalt salt and nickel salt in methanol according to the molar ratio of 1:(0.5~2), add hexamethylenetetramine to obtain a mixed solution, and use acetone, isopropanol, ethanol, and distilled water on the electrode base in sequence After ultrasonic cleaning and drying, soak in the mixed solution, transfer to the polytetrafluoroethylene lining, put it into a high-pressure reactor and seal it, place it in a blast drying oven and heat it to 150-200°C, and react for 6-24 hours After cooling, the electrode substrate is taken out, washed, and dried to obtain an electrode substrate deposited with a Ni-Co layered double metal hydroxide nanosheet array;
(2)将四硫代钼酸铵溶于N,N-二甲基甲酰胺中，加入还原剂，与步骤(1)处理所得的电极基底混合，转移至聚四氟乙烯内衬中，放入高压反应釜中密封，置于鼓风干燥箱中加热至140～180℃，反应4～10h后冷却，取出电极基底，洗涤，干燥，得到二硫化钼电催化产氢电极。(2) Dissolve ammonium tetrathiomolybdate in N,N-dimethylformamide, add a reducing agent, mix with the electrode substrate obtained in step (1), transfer to a polytetrafluoroethylene lining, and put Put it into a high-pressure reactor and seal it, place it in a blast drying oven and heat it to 140-180°C, react for 4-10 hours and then cool it down, take out the electrode base, wash it, and dry it to obtain a molybdenum disulfide electrocatalytic hydrogen production electrode.
第三方面，本发明提供如第一方面所述的二硫化钼电催化产氢电极的用途，其特征在于，所述二硫化钼电催化产氢电极用于电解水制氢。In the third aspect, the present invention provides the use of the molybdenum disulfide electrocatalytic hydrogen production electrode as described in the first aspect, characterized in that the molybdenum disulfide electrocatalytic hydrogen production electrode is used for electrolyzing water to produce hydrogen.
与现有技术相比，本发明至少具有如下有益效果：Compared with the prior art, the present invention has at least the following beneficial effects:
1.本发明二硫化钼电催化产氢电极具有多级次纳米片阵列结构，具有较大的电化学活性表面积，大幅提高二硫化钼的催化活性，表现出优异的产氢性能；且本发明催化产氢电极的活性材料为二硫化钼，属于非贵金属催化剂，价格低廉；1. The molybdenum disulfide electrocatalytic hydrogen production electrode of the present invention has a multi-level nanosheet array structure, has a large electrochemically active surface area, greatly improves the catalytic activity of molybdenum disulfide, and exhibits excellent hydrogen production performance; and the present invention The active material of the electrode for catalytic hydrogen production is molybdenum disulfide, which is a non-precious metal catalyst with low price;
2.本发明首先采用水热法在电极基底上沉积层状双金属氢氧化物，然后以其为牺牲模板，水热反应得到具有多级次结构的二硫化钼，合成方法简单，一举两得，同时实现了元素掺杂和结构优化，且便于操作，具有普适性。2. The present invention first adopts the hydrothermal method to deposit layered double metal hydroxide on the electrode substrate, then uses it as a sacrificial template, and hydrothermally reacts to obtain molybdenum disulfide with a multi-level structure. The synthesis method is simple and kills two birds with one stone. The element doping and structure optimization are realized, and it is easy to operate and has universal applicability.
附图说明Description of drawings
图1是本发明制备方法步骤(1)所得沉积有Ni-Co层状双金属氢氧化物纳米片阵列的电极基底的结构示意图；Fig. 1 is the structural representation of the electrode substrate deposited with the Ni-Co layered double metal hydroxide nanosheet array obtained in step (1) of the preparation method of the present invention;
图2是本发明二硫化钼电催化产氢电极的结构示意图。Fig. 2 is a structural schematic diagram of a molybdenum disulfide electrocatalytic hydrogen production electrode of the present invention.
图3是本发明对比例1直接在碳布上沉积二硫化钼的电极SEM平面图；Fig. 3 is the SEM plan view of the electrode of comparative example 1 of the present invention directly depositing molybdenum disulfide on carbon cloth;
图4是实施例1制备的层状双金属氢氧化物牺牲模板的SEM平面图；Fig. 4 is the SEM plan view of the layered double metal hydroxide sacrificial template prepared in embodiment 1;
图5是实施例1二硫化钼电催化产氢电极的低倍数SEM平面图；5 is a low magnification SEM plan view of the molybdenum disulfide electrocatalytic hydrogen production electrode of embodiment 1;
图6是实施例1二硫化钼电催化产氢电极的高倍数SEM平面图；Fig. 6 is the high magnification SEM plan view of embodiment 1 molybdenum disulfide electrocatalytic hydrogen production electrode;
图7是实施例1二硫化钼电催化产氢电极的SEM截面图；Fig. 7 is the SEM sectional view of molybdenum disulfide electrocatalytic hydrogen production electrode of embodiment 1;
图8是实施例1和对比例1的电极样品电流密度随电压的变化曲线。FIG. 8 is a graph showing the variation curves of the current density of the electrode samples of Example 1 and Comparative Example 1 with voltage.
图1、图2中标记示意为：1-电极基底、2-Ni-Co层状双金属氢氧化物纳米片、3-一级二硫化钼纳米片、4-二级二硫化钼纳米片。The marks in Figure 1 and Figure 2 are: 1-electrode substrate, 2-Ni-Co layered double metal hydroxide nanosheets, 3-first-order molybdenum disulfide nanosheets, 4-secondary molybdenum disulfide nanosheets.
具体实施方式Detailed ways
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。但下述的实施例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following embodiments are only simple examples of the present invention, and do not represent or limit the protection scope of the present invention, and the protection scope of the present invention shall be determined by the claims.
实施例1Example 1
一种二硫化钼电催化产氢电极，包括碳布和负载在碳布表面的二硫化钼纳米片阵列，二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。A molybdenum disulfide electrocatalytic hydrogen production electrode, including carbon cloth and a molybdenum disulfide nanosheet array supported on the surface of the carbon cloth, the molybdenum disulfide nanosheet array is doped with Ni(II) and Co(II); molybdenum disulfide The nanosheet array includes first-order nanosheets perpendicular to the surface of the electrode substrate and second-order nanosheets perpendicular to the first-order nanosheets.
其制备方法包括如下步骤：Its preparation method comprises the following steps:
1)将碳布切割成2cm*1cm尺寸大小，依次使用丙酮、异丙醇、乙醇、三次水进行超声清洗，取4片碳布用氮气吹干后，将其倾斜放置在容量为50mL的聚四氟乙烯内衬里；将145mg六水合硝酸镍、290mg六水合硝酸钴(质量比为1:2)和600mg六亚甲基四胺溶于30mL甲醇中，搅拌10min。混合溶液缓慢转移到聚四氟乙烯内衬放入高压反应釜中密封，放入鼓风干燥箱中180℃加热12h，水热反应后，将碳布取出并放在三次水中超声10秒，然后放在鼓风干燥箱中60℃烘干；得到层状双金属氢氧化物牺牲模板，如图4所示；1) Cut the carbon cloth into 2cm*1cm size, use acetone, isopropanol, ethanol, and three times of water for ultrasonic cleaning in sequence, take 4 pieces of carbon cloth and dry them with nitrogen, and place them obliquely in a polythene with a capacity of 50mL. Tetrafluoroethylene lining: Dissolve 145mg nickel nitrate hexahydrate, 290mg cobalt nitrate hexahydrate (mass ratio 1:2) and 600mg hexamethylenetetramine in 30mL methanol and stir for 10min. Slowly transfer the mixed solution to the polytetrafluoroethylene liner, put it in a high-pressure reactor and seal it, put it in a blast drying oven and heat it at 180 ° C for 12 hours. After the hydrothermal reaction, take out the carbon cloth and put it in water for 10 seconds three times, and Put it in a blast drying oven and dry it at 60°C; obtain a layered double metal hydroxide sacrificial template, as shown in Figure 4;
2)取30mg四硫代钼酸铵((NH4)2Mo2S4)溶于30mL N,N-二甲基甲酰胺中，待完全溶解后加入150μL水合肼，搅拌10min，所得混合溶液和步骤1)处理后的碳布基底转移至聚四氟乙烯内衬中，然后将聚四氟乙烯内衬放入高压反应釜中密封并将其放入鼓风干燥箱中150℃加热8h，水热反应完成后，将样品取出，用乙醇清洗干净后放入真空干燥箱中，60℃下真空干燥10h，得到的样品即为二硫化钼电催化产氢电极，如图5、图6、图7所示。2) Dissolve 30mg of ammonium tetrathiomolybdate ((NH 4 ) 2 Mo 2 S 4 ) in 30mL of N,N-dimethylformamide, add 150μL of hydrazine hydrate after complete dissolution, stir for 10min, and the resulting mixed solution and step 1) transfer the treated carbon cloth substrate to a polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a high-pressure reactor to seal it and put it in a blast drying oven at 150 ° C for 8 hours, After the hydrothermal reaction is completed, take the sample out, clean it with ethanol, put it into a vacuum drying oven, and dry it in vacuum at 60°C for 10 hours. The obtained sample is the molybdenum disulfide electrocatalytic hydrogen production electrode, as shown in Figure 5, Figure 6, Figure 7 shows.
实施例2Example 2
一种二硫化钼电催化产氢电极，包括碳布和负载在碳布表面的二硫化钼纳米片阵列，二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。A molybdenum disulfide electrocatalytic hydrogen production electrode, including carbon cloth and a molybdenum disulfide nanosheet array supported on the surface of the carbon cloth, the molybdenum disulfide nanosheet array is doped with Ni(II) and Co(II); molybdenum disulfide The nanosheet array includes first-order nanosheets perpendicular to the surface of the electrode substrate and second-order nanosheets perpendicular to the first-order nanosheets.
其制备方法包括如下步骤：Its preparation method comprises the following steps:
1)将碳布切割成2cm*1cm尺寸大小，依次使用丙酮、异丙醇、乙醇、三次水进行超声清洗，取4片碳布用氮气吹干后，将其倾斜放置在容量为50mL的聚四氟乙烯内衬里；将290mg六水合硝酸镍、145mg六水合硝酸钴(质量比为2:1)和600mg六亚甲基四胺溶于30mL甲醇中，搅拌10min；所得混合溶液缓慢转移到聚四氟乙烯内衬放入高压反应釜中密封，放入鼓风干燥箱中180℃加热12h，水热反应后，将碳布取出并放在三次水中超声10秒，然后放在鼓风干燥箱中60℃烘干；1) Cut the carbon cloth into 2cm*1cm size, use acetone, isopropanol, ethanol, and three times of water for ultrasonic cleaning in sequence, take 4 pieces of carbon cloth and dry them with nitrogen, and place them obliquely in a polythene with a capacity of 50mL. Tetrafluoroethylene lining; 290mg nickel nitrate hexahydrate, 145mg cobalt nitrate hexahydrate (mass ratio is 2:1) and 600mg hexamethylenetetramine were dissolved in 30mL methanol and stirred for 10min; the resulting mixed solution was slowly transferred to Put the polytetrafluoroethylene lining into a high-pressure reaction kettle and seal it, put it in a blast drying oven and heat it at 180°C for 12 hours. After the hydrothermal reaction, take out the carbon cloth and put it in water three times for ultrasonication for 10 seconds, and then put it in the blast drying box. Dry in oven at 60°C;
2)取30mg四硫代钼酸铵((NH4)2Mo2S4)溶于30mL N,N-二甲基甲酰胺中，待完全溶解后加入150μL水合肼，搅拌10min，所得混合溶液和步骤1)处理后的碳布基底转移至聚四氟乙烯内衬中，然后将聚四氟乙烯内衬放入高压反应釜中密封并将其放入鼓风干燥箱中150℃加热8h，水热反应完成后，将样品取出，用乙醇清洗干净后放入真空干燥箱中，60℃下真空干燥10h，得到的样品即为二硫化钼电催化产氢电极。2) Dissolve 30mg of ammonium tetrathiomolybdate ((NH 4 ) 2 Mo 2 S 4 ) in 30mL of N,N-dimethylformamide, add 150μL of hydrazine hydrate after complete dissolution, stir for 10min, and the resulting mixed solution and step 1) transfer the treated carbon cloth substrate to a polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a high-pressure reactor to seal it and put it in a blast drying oven at 150 ° C for 8 hours, After the hydrothermal reaction is completed, the sample is taken out, cleaned with ethanol, put into a vacuum drying oven, and dried in vacuum at 60°C for 10 hours. The obtained sample is the molybdenum disulfide electrocatalytic hydrogen production electrode.
实施例3Example 3
一种二硫化钼电催化产氢电极，包括碳布和负载在碳布表面的二硫化钼纳米片阵列，二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。A molybdenum disulfide electrocatalytic hydrogen production electrode, including carbon cloth and a molybdenum disulfide nanosheet array supported on the surface of the carbon cloth, the molybdenum disulfide nanosheet array is doped with Ni(II) and Co(II); molybdenum disulfide The nanosheet array includes first-order nanosheets perpendicular to the surface of the electrode substrate and second-order nanosheets perpendicular to the first-order nanosheets.
其制备方法包括如下步骤：Its preparation method comprises the following steps:
1)将碳布切割成2cm*1cm尺寸大小，依次使用丙酮、异丙醇、乙醇、三次水进行超声清洗，取4片碳布用氮气吹干后，将其倾斜放置在容量为50mL的聚四氟乙烯内衬里；将290mg六水合硝酸镍、145mg六水合硝酸钴(质量比为2:1)和600mg六亚甲基四胺溶于30mL甲醇中，搅拌10min；所得混合溶液缓慢转移到聚四氟乙烯内衬放入高压反应釜中密封，放入鼓风干燥箱中180℃加热12h，水热反应后，将碳布取出并放在三次水中超声10秒，然后放在鼓风干燥箱中60℃烘干；1) Cut the carbon cloth into 2cm*1cm size, use acetone, isopropanol, ethanol, and three times of water for ultrasonic cleaning in sequence, take 4 pieces of carbon cloth and dry them with nitrogen, and place them obliquely in a polythene with a capacity of 50mL. Tetrafluoroethylene lining; 290mg nickel nitrate hexahydrate, 145mg cobalt nitrate hexahydrate (mass ratio is 2:1) and 600mg hexamethylenetetramine were dissolved in 30mL methanol and stirred for 10min; the resulting mixed solution was slowly transferred to Put the polytetrafluoroethylene lining into a high-pressure reaction kettle and seal it, put it in a blast drying oven and heat it at 180°C for 12 hours. After the hydrothermal reaction, take out the carbon cloth and put it in water three times for ultrasonication for 10 seconds, and then put it in the blast drying box. Dry in oven at 60°C;
2)取30mg四硫代钼酸铵((NH4)2Mo2S4)溶于30mL N,N-二甲基甲酰胺中，待完全溶解后加入150μL水合肼，搅拌10min，所得混合溶液和步骤1)处理后的碳布基底转移至聚四氟乙烯内衬中，然后将聚四氟乙烯内衬放入高压反应釜中密封并将其放入鼓风干燥箱中180℃加热8h，水热反应完成后，将样品取出，用乙醇清洗干净后放入真空干燥箱中，60℃下真空干燥10h，得到的样品即为二硫化钼电催化产氢电极。2) Dissolve 30mg of ammonium tetrathiomolybdate ((NH 4 ) 2 Mo 2 S 4 ) in 30mL of N,N-dimethylformamide, add 150μL of hydrazine hydrate after complete dissolution, stir for 10min, and the resulting mixed solution and step 1) transfer the treated carbon cloth substrate to a polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a high-pressure reactor to seal it and put it in a blast drying oven at 180 ° C for 8 hours, After the hydrothermal reaction is completed, the sample is taken out, cleaned with ethanol, put into a vacuum drying oven, and dried in vacuum at 60°C for 10 hours. The obtained sample is the molybdenum disulfide electrocatalytic hydrogen production electrode.
实施例4Example 4
一种二硫化钼电催化产氢电极，包括碳布和负载在碳布表面的二硫化钼纳米片阵列，二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。A molybdenum disulfide electrocatalytic hydrogen production electrode, including carbon cloth and a molybdenum disulfide nanosheet array supported on the surface of the carbon cloth, the molybdenum disulfide nanosheet array is doped with Ni(II) and Co(II); molybdenum disulfide The nanosheet array includes first-order nanosheets perpendicular to the surface of the electrode substrate and second-order nanosheets perpendicular to the first-order nanosheets.
其制备方法包括如下步骤：Its preparation method comprises the following steps:
1)将泡沫镍切割成2cm*1cm尺寸大小，依次使用丙酮、异丙醇、乙醇、三次水进行超声清洗，取4片碳布用氮气吹干后，将其倾斜放置在容量为50mL的聚四氟乙烯内衬里；将216mg六水合硝酸镍、324mg六水合硝酸钴(质量比为1:1.5)和600mg六亚甲基四胺溶于30mL甲醇中，搅拌10min；所得混合溶液缓慢转移到聚四氟乙烯内衬放入高压反应釜中密封，放入鼓风干燥箱中150℃加热24h，水热反应后，将泡沫镍取出并放在三次水中超声10秒，然后放在鼓风干燥箱中60℃烘干；1) Cut the nickel foam into 2cm*1cm size, use acetone, isopropanol, ethanol, and three times of water for ultrasonic cleaning in sequence, take 4 pieces of carbon cloth and dry them with nitrogen, and place them obliquely in a polythene with a capacity of 50mL. Tetrafluoroethylene lining; 216mg nickel nitrate hexahydrate, 324mg cobalt nitrate hexahydrate (mass ratio is 1:1.5) and 600mg hexamethylenetetramine were dissolved in 30mL methanol and stirred for 10min; the resulting mixed solution was slowly transferred to Put the polytetrafluoroethylene lining into the high-pressure reaction kettle and seal it, put it in a blast drying oven and heat it at 150°C for 24 hours. After the hydrothermal reaction, take out the nickel foam and put it in three times of water for ultrasonication for 10 seconds, and then put it in the blast drying box. Dry in oven at 60°C;
2)取30mg四硫代钼酸铵((NH4)2Mo2S4)溶于30mL N,N-二甲基甲酰胺中，待完全溶解后加入150μL水合肼，搅拌10min，所得混合溶液和步骤1)处理后的泡沫镍基底转移至聚四氟乙烯内衬中，然后将聚四氟乙烯内衬放入高压反应釜中密封并将其放入鼓风干燥箱中140℃加热10h，水热反应完成后，将样品取出，用乙醇清洗干净后放入真空干燥箱中，60℃下真空干燥10h，得到的样品即为二硫化钼电催化产氢电极。取电极样品进行电化学性能测试，测试方法为：线性扫描伏安法。得到电流密度随电压的变化曲线，起始过电位110mV，在电流密度为10mA/cm2处的过电位为140mV。2) Dissolve 30mg of ammonium tetrathiomolybdate ((NH 4 ) 2 Mo 2 S 4 ) in 30mL of N,N-dimethylformamide, add 150μL of hydrazine hydrate after complete dissolution, stir for 10min, and the resulting mixed solution and step 1) transfer the treated foamed nickel substrate to a polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a high-pressure reactor to seal it and put it into a blast drying oven at 140 ° C for 10 hours, After the hydrothermal reaction is completed, the sample is taken out, cleaned with ethanol, put into a vacuum drying oven, and dried in vacuum at 60°C for 10 hours. The obtained sample is the molybdenum disulfide electrocatalytic hydrogen production electrode. Electrode samples were taken for electrochemical performance testing, and the testing method was linear sweep voltammetry. The variation curve of current density with voltage was obtained, the initial overpotential was 110mV, and the overpotential at the place where the current density was 10mA/ cm2 was 140mV.
实施例5Example 5
一种二硫化钼电催化产氢电极，包括碳布和负载在碳布表面的二硫化钼纳米片阵列，二硫化钼纳米片阵列掺杂有Ni(II)和Co(II)；二硫化钼纳米片阵列包括垂直于所述电极基底表面的一级纳米片和垂直于所述一级纳米片的二级纳米片。A molybdenum disulfide electrocatalytic hydrogen production electrode, including carbon cloth and a molybdenum disulfide nanosheet array supported on the surface of the carbon cloth, the molybdenum disulfide nanosheet array is doped with Ni(II) and Co(II); molybdenum disulfide The nanosheet array includes first-order nanosheets perpendicular to the surface of the electrode substrate and second-order nanosheets perpendicular to the first-order nanosheets.
其制备方法包括如下步骤：Its preparation method comprises the following steps:
1)将碳布切割成2cm*1cm尺寸大小，依次使用丙酮、异丙醇、乙醇、三次水进行超声清洗，取4片碳布用氮气吹干后，将其倾斜放置在容量为50mL的聚四氟乙烯内衬里；将324mg六水合硝酸镍、216mg六水合硝酸钴(质量比为8:6)和600mg六亚甲基四胺溶于30mL甲醇中，搅拌10min；所得混合溶液缓慢转移到聚四氟乙烯内衬放入高压反应釜中密封，放入鼓风干燥箱中200℃加热6h，水热反应后，将碳布取出并放在三次水中超声10秒，然后放在鼓风干燥箱中60℃烘干；1) Cut the carbon cloth into 2cm*1cm size, use acetone, isopropanol, ethanol, and three times of water for ultrasonic cleaning in sequence, take 4 pieces of carbon cloth and dry them with nitrogen, and place them obliquely in a polythene with a capacity of 50mL. Tetrafluoroethylene lining; 324mg nickel nitrate hexahydrate, 216mg cobalt nitrate hexahydrate (mass ratio is 8:6) and 600mg hexamethylenetetramine were dissolved in 30mL methanol and stirred for 10min; the resulting mixed solution was slowly transferred to Put the polytetrafluoroethylene lining into a high-pressure reaction kettle and seal it, put it in a blast drying oven and heat it at 200°C for 6 hours. After the hydrothermal reaction, take out the carbon cloth and put it in water three times for ultrasonication for 10 seconds, and then put it in the blast drying box. Dry in oven at 60°C;
2)取30mg四硫代钼酸铵((NH4)2Mo2S4)溶于30mL N,N-二甲基甲酰胺中，待完全溶解后加入150μL水合肼，搅拌10min，所得混合溶液和步骤1)处理后的碳布基底转移至聚四氟乙烯内衬中，然后将聚四氟乙烯内衬放入高压反应釜中密封并将其放入鼓风干燥箱中170℃加热10h，水热反应完成后，将样品取出，用乙醇清洗干净后放入真空干燥箱中，60℃下真空干燥10h，得到的样品即为二硫化钼电催化产氢电极。取电极样品进行电化学性能测试，测试方法为：线性扫描伏安法。得到电流密度随电压的变化曲线，起始过电位123mV，在电流密度为10mA/cm2处的过电位为147mV。2) Dissolve 30mg of ammonium tetrathiomolybdate ((NH 4 ) 2 Mo 2 S 4 ) in 30mL of N,N-dimethylformamide, add 150μL of hydrazine hydrate after complete dissolution, stir for 10min, and the resulting mixed solution and step 1) transfer the treated carbon cloth substrate to a polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a high-pressure reactor to seal it and put it in a blast drying oven at 170 ° C for 10 hours, After the hydrothermal reaction is completed, the sample is taken out, cleaned with ethanol, put into a vacuum drying oven, and dried in vacuum at 60°C for 10 hours. The obtained sample is the molybdenum disulfide electrocatalytic hydrogen production electrode. Electrode samples were taken for electrochemical performance testing, and the testing method was linear sweep voltammetry. The variation curve of current density with voltage was obtained, the initial overpotential was 123mV, and the overpotential at the place where the current density was 10mA/ cm2 was 147mV.
实施例6Example 6
与实施例1的区别仅在于：六水合硝酸镍、六水合硝酸钴的质量比为1:2.5，总质量不变。The difference from Example 1 is only that the mass ratio of nickel nitrate hexahydrate to cobalt nitrate hexahydrate is 1:2.5, and the total mass remains unchanged.
实施例7Example 7
与实施例1的区别仅在于：六水合硝酸镍、六水合硝酸钴的质量比为1:0.3，总质量不变。The only difference from Example 1 is that the mass ratio of nickel nitrate hexahydrate to cobalt nitrate hexahydrate is 1:0.3, and the total mass remains unchanged.
取实施例1电极样品和实施例6、实施例7的电极样品分别进行电化学性能测试，测试方法为：线性扫描伏安法。得到电流密度随电压的变化曲线，实施例1起始过电位为108mV，在电流密度为10mA/cm2处的过电位为132mV，与实施例1的电极样品相比，实施例6、实施例7电极样品分别具有较高的起始过电位113mV和131mV，在电流密度为10mA/cm2处的过电位分别为141mV和163mV，因而实施例1的电极样品表现出比实施例6、实施例7电极样品更好的催化产氢性能。说明本发明通过为优化二硫化钼中掺杂的镍钴比例，进而优化了二硫化钼的催化产氢反应活性。The electrode samples of Example 1 and the electrode samples of Example 6 and Example 7 were taken to test the electrochemical performance respectively, and the test method was linear sweep voltammetry. Obtain the variation curve of current density with voltage, the initial overpotential of embodiment 1 is 108mV, and the overpotential at current density is 10mA/cm The place is 132mV, compared with the electrode sample of embodiment 1, embodiment 6, embodiment 7. The electrode samples have higher initial overpotentials of 113mV and 131mV respectively, and the overpotentials at the current density of 10mA/ cm2 are 141mV and 163mV respectively. Therefore, the electrode samples of Example 1 show higher than that of Example 6 and Example 6. 7 Electrode samples have better catalytic hydrogen production performance. It shows that the present invention further optimizes the catalytic hydrogen production reaction activity of molybdenum disulfide by optimizing the ratio of nickel-cobalt doped in molybdenum disulfide.
对比例1Comparative example 1
直接在碳布上沉积二硫化钼的电极。与实施例1的区别在于，没有多级次阵列结构，如图3所示。制备方法如下：Molybdenum disulfide electrode deposited directly on carbon cloth. The difference from Embodiment 1 is that there is no multi-level sub-array structure, as shown in FIG. 3 . The preparation method is as follows:
1)将碳布切割成2cm*1cm尺寸大小，依次使用丙酮、异丙醇、乙醇、三次水进行超声清洗，取4片碳布用氮气吹干；1) Cut the carbon cloth into 2cm*1cm size, use acetone, isopropanol, ethanol, three times of water for ultrasonic cleaning in sequence, take 4 pieces of carbon cloth and dry them with nitrogen;
2)取30mg四硫代钼酸铵((NH4)2Mo2S4)溶于30mL N,N-二甲基甲酰胺中，待完全溶解后加入150μL水合肼，搅拌10min，所得混合溶液和步骤1)处理后的碳布基底转移至聚四氟乙烯内衬中，然后将聚四氟乙烯内衬放入高压反应釜中密封并将其放入鼓风干燥箱中150℃加热8h，水热反应完成后，将样品取出，用乙醇清洗干净后放入真空干燥箱中，60℃下真空干燥10h，得到的样品即为无多级次结构的二硫化钼电催化产氢电极。2) Dissolve 30mg of ammonium tetrathiomolybdate ((NH 4 ) 2 Mo 2 S 4 ) in 30mL of N,N-dimethylformamide, add 150μL of hydrazine hydrate after complete dissolution, stir for 10min, and the resulting mixed solution and step 1) transfer the treated carbon cloth substrate to a polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a high-pressure reactor to seal it and put it in a blast drying oven at 150 ° C for 8 hours, After the hydrothermal reaction is completed, the sample is taken out, cleaned with ethanol, put into a vacuum drying oven, and dried in vacuum at 60°C for 10 hours. The obtained sample is a molybdenum disulfide electrocatalytic hydrogen production electrode without a multi-level structure.
取实施例1电极样品和对比例1的电极样品进行电化学性能测试，测试方法为：线性扫描伏安法。得到电流密度随电压的变化曲线，如图8所示，与对比例1的电极样品相比，实施例1电极样品具有较低的起始过电位，在电流密度为10mA/cm2处的过电位也较低，因而表现出更好的催化产氢性能。实施例2和实施例3所提供的电极表现出与实施例1相似的催化产氢性能，在此不再赘述。The electrode samples of Example 1 and the electrode samples of Comparative Example 1 were taken for electrochemical performance testing, and the testing method was linear sweep voltammetry. Obtain the variation curve of current density with voltage, as shown in Figure 8, compared with the electrode sample of Comparative Example 1, the electrode sample of embodiment 1 has a lower initial overpotential, and the overpotential at the current density is 10mA/cm The potential is also lower, thus exhibiting better catalytic hydrogen production performance. The electrodes provided in Example 2 and Example 3 exhibit catalytic hydrogen production performance similar to that of Example 1, which will not be repeated here.
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow process can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.
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