CN113529124B - Cathode material for electrolyzing water, preparation method thereof and application of cathode material in electrocatalytic hydrogenation of vat dye - Google Patents
Cathode material for electrolyzing water, preparation method thereof and application of cathode material in electrocatalytic hydrogenation of vat dye Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000000984 vat dye Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 376
- 239000002184 metal Substances 0.000 claims abstract description 367
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 214
- 239000000463 material Substances 0.000 claims abstract description 208
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 174
- 239000000243 solution Substances 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000007747 plating Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 239000000975 dye Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 238000009713 electroplating Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 86
- 239000010935 stainless steel Substances 0.000 claims description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 81
- 229910052799 carbon Inorganic materials 0.000 claims description 80
- 239000011888 foil Substances 0.000 claims description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 79
- 239000011889 copper foil Substances 0.000 claims description 77
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 27
- 229940097275 indigo Drugs 0.000 claims description 27
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 241000080590 Niso Species 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 5
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002659 electrodeposit Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004048 vat dyeing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- C25B11/073—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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
Description
技术领域technical field
本发明涉及电化学氢化还原技术领域，具体涉及一种电解水阴极材料及 其制备方法以及该阴极材料在电催化氢化还原染料中的应用。The present invention relates to the technical field of electrochemical hydrogenation reduction, in particular to a cathode material for electrolysis of water, a preparation method thereof and the application of the cathode material in electrocatalytic hydrogenation reduction of dyes.
背景技术Background technique
电化学还原染料的方法有三种：直接电化学还原、间接电化学还原和电 催化氢化还原。直接电化学还原存在电流效率低、还原速率慢的缺陷。间接 电化学还原需要电子媒介体(Fe2+/Fe3+)，而且要加入大量的有机配体。目 前间接电化学还原染料的研究较多，但有机配体成本高，且不能重复使用， 而且染料染色色差不好控制，难以实现工业生产和印染应用。There are three methods for electrochemical reduction of dyes: direct electrochemical reduction, indirect electrochemical reduction and electrocatalytic hydrogenation reduction. Direct electrochemical reduction has the disadvantages of low current efficiency and slow reduction rate. Indirect electrochemical reduction requires electron mediators (Fe 2+ /Fe 3+ ), and a large amount of organic ligands must be added. At present, there are many studies on indirect electrochemical reduction of dyes, but the cost of organic ligands is high, and they cannot be reused, and the dyeing color difference is not easy to control, making it difficult to realize industrial production and printing and dyeing applications.
电催化氢化还原方法的原理如图12所示。The principle of the electrocatalytic hydrogenation reduction method is shown in Figure 12.
电解水时，在阴极槽中发生水还原析氢反应(HER)，在阳极槽中发生 水氧化析氧反应(OER)，中间用质子渗透膜(PEM)分隔。阴极产生的氢 原子具有较强的还原能力，能将不溶于水的还原染料分子还原，生成能溶于 碱性溶液的还原态染料分子，阳极产生的氧气。与传统的液相催化氢化方法 相比，电催化氢化还原不需要高压氢气和化学还原剂，氢化过程易于控制、 反应条件温和、氧化还原电位可控、消耗化学品少、废水排放少，容易工业 化等优点，是一种绿色的还原过程，成为还原染料染色方法中最具有吸引力 的新方法。When electrolyzing water, the water reduction hydrogen evolution reaction (HER) occurs in the cathode cell, and the water oxidation oxygen evolution reaction (OER) occurs in the anode cell, separated by a proton permeable membrane (PEM). The hydrogen atoms generated by the cathode have strong reducing ability, and can reduce the water-insoluble vat dye molecules to generate reduced dye molecules that can be dissolved in alkaline solution, and the oxygen generated by the anode. Compared with the traditional liquid-phase catalytic hydrogenation method, the electrocatalytic hydrogenation reduction does not require high-pressure hydrogen and chemical reducing agents, the hydrogenation process is easy to control, the reaction conditions are mild, the oxidation-reduction potential is controllable, the consumption of chemicals is less, and the waste water discharge is less, and it is easy to industrialize It is a green reduction process and has become the most attractive new method in vat dyeing methods.
Roessler等采用电沉积方法，在不锈钢网上分别制备了铂(Pt/Fe),钌 (Rh/Fe),钯(Pd/Fe),镍(Ni/Fe),钴(Co/Fe)和铜(Cu/Fe)等电极，用于电催化氢化还 原靛蓝，其靛蓝的转化率(电流效率)分别为81.9％(65.5％)，61.1％(48.9％)，54.5％(43.6％)，4.4％(3.5％)，2.9％(2.3％)和1.4％(1.1％)，原理如 图12所示。结果表明，贵金属内具有较高的转化率和电流使用效率，非贵 金属的效率要差许多(RoesslerA.etc.Electrocatalytic hydrogenation of vat dyes,Dyes and Pigments,2002,54,141–146.)。而电解池由H池改变为流动 池，虽大大提高了靛蓝的转化率和电流使用效率，如Ni/Fe和NiPt/Fe电极 的靛蓝的转化率(电流效率)分别为95％(13％)和95％(19％)，但电流 的使用效率仍比较低(Roessler A.etc.Electrocatalytic Hydrogenation ofIndigo Process Optimization and Scale-Up in a Flow Cell,Journal of TheElectrochemical Society,2003,150(1)D1-D5)(欧洲专利EP2032740B1)。Roessler et al prepared platinum (Pt/Fe), ruthenium (Rh/Fe), palladium (Pd/Fe), nickel (Ni/Fe), cobalt (Co/Fe) and copper ( Cu/Fe) and other electrodes are used for electrocatalytic hydrogenation reduction of indigo, and the conversion rate (current efficiency) of its indigo is 81.9% (65.5%), 61.1% (48.9%), 54.5% (43.6%), 4.4% ( 3.5%), 2.9% (2.3%) and 1.4% (1.1%), the principle is shown in Figure 12. The results show that there are higher conversion rates and current usage efficiencies in noble metals, and the efficiency of non-noble metals is much worse (RoesslerA. etc. Electrocatalytic hydrogenation of vat dyes, Dyes and Pigments, 2002, 54, 141–146.). And electrolytic cell is changed into flow cell by H pool, though greatly improved the conversion rate and the current use efficiency of indigo, as the conversion rate (current efficiency) of the indigo of Ni/Fe and NiPt/Fe electrode is respectively 95% (13%) and 95% (19%), but the efficiency of current use is still relatively low (Roessler A.etc.Electrocatalytic Hydrogenation of Indigo Process Optimization and Scale-Up in a Flow Cell, Journal of The Electrochemical Society, 2003, 150(1) D1-D5 ) (European patent EP2032740B1).
发明内容Contents of the invention
本发明的目的是为了克服现有技术存在的电解水阴极材料单一，铂族元 素(铂、钌、钯等)价格高，且易于失活；过渡金属元素(铁、钴、镍、钼、 钨等)电解水过电位高，电流的使用效率不高的问题，提供了一种电解水阴 极材料及其制备方法以及该阴极材料在电催化氢化还原染料中的应用，该电 解水阴极材料含有三种特定的催化剂元素，采用该阴极材料进行电催化氢化 还原染料，阴极电解水过电位低，电流使用效率高，能够提高氢化还原产物 的转化率。The purpose of the present invention is in order to overcome the electrolysis water cathode material that prior art exists is single, and platinum group element (platinum, ruthenium, palladium etc.) price is high, and is easy to deactivate; Transition metal element (iron, cobalt, nickel, molybdenum, tungsten) etc.) electrolyzed water with high overpotential and low current use efficiency, provide a cathode material for electrolyzed water and its preparation method as well as the application of the cathode material in electrocatalytic hydrogenation reduction of dyes, the cathode material for electrolyzed water contains three A specific catalyst element, using the cathode material for electrocatalytic hydrogenation and reduction of dyes, has low overpotential for cathodic electrolysis of water, high current use efficiency, and can improve the conversion rate of hydrogenation reduction products.
为了实现上述目的，本发明第一方面提供了一种制备电解水阴极材料的 方法，该方法包括以下步骤：In order to achieve the above object, a first aspect of the present invention provides a method for preparing cathode material for electrolysis of water, the method comprising the following steps:
(1)对基底材料进行预处理，其中，所述基底材料为不锈钢、镍箔、 铜箔或碳箔中的至少一种；(1) Pretreating the base material, wherein the base material is at least one of stainless steel, nickel foil, copper foil or carbon foil;
(2)将预处理后的基底材料裁剪为块状，然后在镍盐溶液中进行预镀 镍，得到具有镍镀层的基底材料；(2) the base material after pretreatment is cut into bulk, then carries out pre-nickel plating in nickel salt solution, obtains the base material with nickel coating;
(3)配制含有第一金属元素、第二金属元素和非金属元素的催化剂镀 液，并用碱液将催化剂镀液调节至pH为8～11，然后采用三电极法将具有镍 镀层的基底材料置于催化剂镀液中进行电镀，得到阴极材料；(3) Prepare the catalyst plating solution containing the first metal element, the second metal element and non-metallic elements, and adjust the catalyst plating solution to
其中，所述第一金属元素为Ni、Co和Fe中的至少一种，所述第二金属 元素为Mo和/或W，所述非金属元素为P、S和N中的至少一种。Wherein, the first metal element is at least one of Ni, Co and Fe, the second metal element is Mo and/or W, and the non-metal element is at least one of P, S and N.
优选地，在步骤(1)中，所述基底材料为不锈钢时，所述预处理的具 体操作为：采用320目和600目的SiC砂纸依次对基底材料进行打磨，去除 表层，然后采用恒电位仪在0.5～2mol/L的硫酸溶液中去除表面氧化层。Preferably, in step (1), when the base material is stainless steel, the specific operation of the pretreatment is: use 320-mesh and 600-mesh SiC sandpaper to sequentially polish the base material, remove the surface layer, and then use a potentiostat Remove the surface oxide layer in 0.5-2mol/L sulfuric acid solution.
优选地，所述基底材料为镍箔和/或铜箔时，所述预处理的具体操作为： 将基底材料在0.5～2mol/L的盐酸溶液中浸泡10～30分钟，清洗后备用。Preferably, when the base material is nickel foil and/or copper foil, the specific operation of the pretreatment is as follows: soak the base material in 0.5-2 mol/L hydrochloric acid solution for 10-30 minutes, wash and set aside.
优选地，所述基底材料为碳箔时，所述预处理的具体操作为：将基底材 料置于0.5～2mol/L的硝酸溶液中浸泡1小时以上，清洗后备用。Preferably, when the base material is carbon foil, the specific operation of the pretreatment is: immerse the base material in 0.5-2 mol/L nitric acid solution for more than 1 hour, wash and set aside.
优选地，在步骤(2)中，所述镍盐溶液为NiCl2·6H2O溶液和/或 NiSO4·6H2O溶液，浓度为0.5～2mol/L。Preferably, in step (2), the nickel salt solution is NiCl 2 ·6H 2 O solution and/or NiSO 4 ·6H 2 O solution, the concentration of which is 0.5-2 mol/L.
优选地，在步骤(2)中，采用电沉积进行预镀镍；所述电沉积的条件 为：电流为-50～-200mA·cm2，时间为5-30分钟。Preferably, in step (2), nickel pre-plating is performed by electro-deposition; the conditions of the electro-deposition are: a current of -50˜-200 mA·cm 2 and a time of 5-30 minutes.
优选地，在步骤(3)所述催化剂镀液中，第一金属元素的浓度为 0.1-2mol/L，第二金属元素的浓度为0.02-0.5mol/L，非金属元素的浓度为 0.02-0.5mol/L。Preferably, in the catalyst plating solution described in step (3), the concentration of the first metal element is 0.1-2mol/L, the concentration of the second metal element is 0.02-0.5mol/L, and the concentration of the non-metal element is 0.02- 0.5mol/L.
优选地，在步骤(3)中，所述电镀的条件为：电流为-50～-200mA·cm2， 时间为5～30分钟。Preferably, in step (3), the conditions of the electroplating are: the current is -50 to -200 mA·cm 2 , and the time is 5 to 30 minutes.
优选地，在步骤(3)所述催化剂镀液中，还含有0.1-1mol/L的 C6H5Na3O7·2H2O溶液。Preferably, the catalyst plating solution in step (3) also contains 0.1-1 mol/L C 6 H 5 Na 3 O 7 ·2H 2 O solution.
优选地，在步骤(3)中，所述碱液为氨水溶液。Preferably, in step (3), the lye is ammonia solution.
本发明第二方面提供了一种由前文所述的方法制备的电解水阴极材料， 所述阴极材料包括基底材料和催化剂，所述基底材料为不锈钢、镍箔、铜箔 或碳箔中的至少一种，所述催化剂含有第一金属元素、第二金属元素和非金 属元素，其中，所述第一金属元素为Ni、Co和Fe中的至少一种，所述第二 金属元素为Mo和/或W，所述非金属元素为P、S和N中的至少一种。The second aspect of the present invention provides a cathode material for electrolysis of water prepared by the method described above, the cathode material includes a base material and a catalyst, and the base material is at least one of stainless steel, nickel foil, copper foil or carbon foil One, the catalyst contains a first metal element, a second metal element and a metalloid element, wherein the first metal element is at least one of Ni, Co and Fe, and the second metal element is Mo and /or W, the non-metal element is at least one of P, S and N.
优选地，所述阴极材料的组成为：所述基底材料为不锈钢，所述第一金 属元素为Ni，所述第二金属元素为Mo，所述非金属元素为P；或Preferably, the composition of the cathode material is: the base material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为Mo，所述非金属元素为P；或The base material is stainless steel, the first metal element is Co, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为W，所述非金属元素为P；或The base material is stainless steel, the first metal element is Ni, the second metal element is W, and the non-metal element is P; or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为W，所述非金属元素为P；或The base material is stainless steel, the first metal element is Co, the second metal element is W, and the non-metal element is P; or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P；或The base material is stainless steel, the first metal element is Fe, the second metal element is W, and the non-metal element is P; or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为Mo，所述非金属元素为S；或The base material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为Mo，所述非金属元素为S；或The base material is stainless steel, the first metal element is Co, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为W，所述非金属元素为S；或The base material is stainless steel, the first metal element is Ni, the second metal element is W, and the non-metal element is S; or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为W，所述非金属元素为S；或The base material is stainless steel, the first metal element is Co, the second metal element is W, and the non-metal element is S; or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S；或The base material is stainless steel, the first metal element is Fe, the second metal element is W, and the non-metal element is S; or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为Mo，所述非金属元素为N；或The base material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为Mo，所述非金属元素为N；或The base material is stainless steel, the first metal element is Co, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为W，所述非金属元素为N；或The base material is stainless steel, the first metal element is Ni, the second metal element is W, and the non-metal element is N; or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为W，所述非金属元素为N；或The base material is stainless steel, the first metal element is Co, the second metal element is W, and the non-metal element is N; or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N；或The base material is stainless steel, the first metal element is Fe, the second metal element is W, and the non-metal element is N; or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is nickel foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为Mo，所述非金属元素为P；或The base material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为P；或The base material is nickel foil, the first metal element is Ni, the second metal element is W, and the non-metal element is P; or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为P；或The base material is nickel foil, the first metal element is Co, the second metal element is W, and the non-metal element is P; or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P；或The base material is nickel foil, the first metal element is Fe, the second metal element is W, and the non-metal element is P; or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is nickel foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为S；或The base material is nickel foil, the first metal element is Ni, the second metal element is W, and the non-metal element is S; or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为S；或The base material is nickel foil, the first metal element is Co, the second metal element is W, and the non-metal element is S; or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S；或The base material is nickel foil, the first metal element is Fe, the second metal element is W, and the non-metal element is S; or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is nickel foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为N；或The base material is nickel foil, the first metal element is Ni, the second metal element is W, and the non-metal element is N; or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为N；或The base material is nickel foil, the first metal element is Co, the second metal element is W, and the non-metal element is N; or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N；或The base material is nickel foil, the first metal element is Fe, the second metal element is W, and the non-metal element is N; or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is copper foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为P；或The base material is copper foil, the first metal element is Ni, the second metal element is W, and the non-metal element is P; or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为P；或The base material is copper foil, the first metal element is Co, the second metal element is W, and the non-metal element is P; or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P；或The base material is copper foil, the first metal element is Fe, the second metal element is W, and the non-metal element is P; or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is copper foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为W，所述非金属元素为S；或The base material is copper foil, the first metal element is Ni, the second metal element is W, and the non-metal element is S; or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为S；或The base material is copper foil, the first metal element is Co, the second metal element is W, and the non-metal element is S; or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S；或The base material is copper foil, the first metal element is Fe, the second metal element is W, and the non-metal element is S; or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is copper foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为N；或The base material is copper foil, the first metal element is Ni, the second metal element is W, and the non-metal element is N; or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为N；或The base material is copper foil, the first metal element is Co, the second metal element is W, and the non-metal element is N; or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N；或The base material is copper foil, the first metal element is Fe, the second metal element is W, and the non-metal element is N; or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is carbon foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P；或The base material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P; or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为P；或The base material is carbon foil, the first metal element is Ni, the second metal element is W, and the non-metal element is P; or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为P；或The base material is carbon foil, the first metal element is Co, the second metal element is W, and the non-metal element is P; or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P；或The base material is carbon foil, the first metal element is Fe, the second metal element is W, and the non-metal element is P; or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is carbon foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S；或The base material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S; or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为S；或The base material is carbon foil, the first metal element is Ni, the second metal element is W, and the non-metal element is S; or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为S；或The base material is carbon foil, the first metal element is Co, the second metal element is W, and the non-metal element is S; or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S；或The base material is carbon foil, the first metal element is Fe, the second metal element is W, and the non-metal element is S; or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is carbon foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N；或The base material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N; or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为N；或The base material is carbon foil, the first metal element is Ni, the second metal element is W, and the non-metal element is N; or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为W，所述非金属元素为N；或The base material is carbon foil, the first metal element is Co, the second metal element is W, and the non-metal element is N; or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N。The base material is carbon foil, the first metal element is Fe, the second metal element is W, and the non-metal element is N.
本发明第三方面提供了一种前文所述的电解水阴极材料在电催化氢化 还原染料中的应用。The third aspect of the present invention provides an application of the above-mentioned electrolyzed water cathode material in the electrocatalytic hydrogenation reduction of dyes.
优选地，所述还原染料为靛蓝、硫化黑BR、还原黄G、还原蓝BC、还 原绿FFB、还原红R、还原棕R、还原金橙3G和还原紫RR中的至少一种。Preferably, the vat dye is at least one of indigo, sulfur black BR, vat yellow G, vat blue BC, vat green FFB, vat red R, vat brown R, vat golden orange 3G and vat violet RR.
本发明发明人发现，采用含有两种特定金属元素和一种特定非金属元素 作为电解水阴极材料的三元复合电催化剂，在电催化氢化还原染料时，(1) 两种金属发生复合，对于稳定吸附态氢原子起着重要作用；(2)双金属活性 位点异质化，其协同作用可以促进电催化还原氢的动力学；(3)非金属原子 的引入，利于电子的重新分布，优化催化剂的电子结构；(4)非金属原子可 以增强吸附有机分子的能力，增加还原染料分子与原子氢的接触几率和反应 时间。因此，采用含有三元复合电催化剂的电解水阴极材料进行电催化氢化 还原染料，既可降低还原氢的过电位，同时可以提高氢化还原产物的转化率。The inventors of the present invention have found that by using a ternary composite electrocatalyst containing two specific metal elements and a specific non-metallic element as the cathode material for electrolysis of water, when the electrocatalyzed hydrogenation reduces the dye, (1) the two metals are recombined, for The stable adsorbed hydrogen atoms play an important role; (2) the heterogeneity of the bimetallic active sites, and its synergistic effect can promote the kinetics of electrocatalytic reduction of hydrogen; (3) the introduction of non-metallic atoms facilitates the redistribution of electrons, Optimize the electronic structure of the catalyst; (4) non-metallic atoms can enhance the ability to adsorb organic molecules, and increase the contact probability and reaction time between vat dye molecules and atomic hydrogen. Therefore, the electrocatalytic hydrogenation reduction of dyes by using electrolytic water cathode materials containing ternary composite electrocatalysts can not only reduce the overpotential of hydrogen reduction, but also increase the conversion rate of hydrogenation reduction products.
附图说明Description of drawings
图1和图2分别是实施例1制备的Ni-Mo-P/不锈钢阴极材料的扫描电镜 图和能谱图。Fig. 1 and Fig. 2 are the scanning electron micrograph and the energy spectrum of the Ni-Mo-P/stainless steel cathode material prepared in
图3和图4分别是实施例2制备的Ni-Mo-P/镍箔阴极材料的扫描电镜图 和能谱图。Fig. 3 and Fig. 4 are the scanning electron micrograph and the energy spectrum of the Ni-Mo-P/nickel foil cathode material that
图5-图8分别是采用实施例1-4中制备的阴极材料作为阴极还原前和还 原后靛蓝溶液的紫外可见吸收光谱。Fig. 5-Fig. 8 is to adopt the cathode material prepared in embodiment 1-4 respectively as the ultraviolet-visible absorption spectrum of indigo solution before and after reduction of cathode reduction.
图9-图10是实施例1-4制备的Ni-Mo-P阴极材料的线性伏安扫描图。9-10 are the linear voltammetry scan diagrams of the Ni-Mo-P cathode materials prepared in Examples 1-4.
图11是Ni-Mo-P/碳箔化还原靛蓝后对棉布染色的效果图。Fig. 11 is an effect diagram of dyeing cotton cloth after reducing indigo by Ni-Mo-P/carbon foil.
图12是电催化氢化还原方法的原理示意图。Fig. 12 is a schematic diagram of the principle of the electrocatalytic hydrogenation reduction method.
具体实施方式Detailed ways
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是， 此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这 些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各 个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点 值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视 为在本文中具体公开。Neither the endpoints of the ranges nor any values disclosed herein are to be limited to such precise ranges or values, which are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明一方面提供了一种制备电解水阴极材料的方法，该方法包括以下 步骤：One aspect of the present invention provides a method for preparing cathode material for electrolysis of water, the method comprising the following steps:
(1)对基底材料进行预处理，其中，所述基底材料为不锈钢、镍箔、 铜箔或碳箔中的至少一种；(1) Pretreating the base material, wherein the base material is at least one of stainless steel, nickel foil, copper foil or carbon foil;
(2)将预处理后的基底材料裁剪为块状，然后在镍盐溶液中进行预镀 镍，得到具有镍镀层的基底材料；(2) the base material after pretreatment is cut into bulk, then carries out pre-nickel plating in nickel salt solution, obtains the base material with nickel coating;
(3)配制含有第一金属元素、第二金属元素和非金属元素的催化剂镀 液，并用碱液将催化剂镀液调节至pH为8～11，然后采用三电极法将具有镍 镀层的基底材料置于催化剂镀液中进行电镀，得到阴极材料；(3) Prepare the catalyst plating solution containing the first metal element, the second metal element and non-metallic elements, and adjust the catalyst plating solution to
其中，所述第一金属元素为Ni、Co和Fe中的至少一种，所述第二金属 元素为Mo和/或W，所述非金属元素为P、S和N中的至少一种。Wherein, the first metal element is at least one of Ni, Co and Fe, the second metal element is Mo and/or W, and the non-metal element is at least one of P, S and N.
在制备电解水阴极材料的方法中，对基体材料进行预处理、裁剪为一定 的尺寸(例如1×2cm)后，进行预镀镍，然后在特定的pH值下将第一金属 元素、第二金属元素和非金属元素电镀在基底材料上。在本发明中，预镀镍 可以增加三元素催化剂和预镀镍后电极之间的结合力，使催化剂镀层不易脱 落。In the method for preparing the electrolyzed water cathode material, the base material is pretreated, cut into a certain size (for example, 1×2cm), and then pre-plated with nickel, and then the first metal element, the second Metal elements and non-metal elements are electroplated on the base material. In the present invention, pre-nickel plating can increase the binding force between the three-element catalyst and the electrode after pre-nickel plating, so that the catalyst coating is not easy to fall off.
在具体实施方式中，不同的基体材料需要采用不同的预处理方法。例如： 在步骤(1)中，所述基底材料为不锈钢时，所述预处理的具体操作为：采 用320目和600目的SiC砂纸依次对基底材料进行打磨，去除表层，然后采 用恒电位仪在0.5～2mol/L(具体可以为0.5mol/L、0.75mol/L、1mol/L、 1.25mol/L、1.5mol/L、1.75mol/L或2mol/L)的硫酸溶液中去除表面氧化层 (电解质为硫酸溶液，需要在使用恒电位仪通电的情况下，才能快速去除表 面氧化层)。所述基底材料为镍箔和/或铜箔时，所述预处理的具体操作为： 将基底材料在0.5～2mol/L(具体可以为0.5mol/L、0.75mol/L、1mol/L、 1.25mol/L、1.5mol/L、1.75mol/L或2mol/L)的盐酸溶液中浸泡10～30分钟 (例如可以为10分钟、15分钟、20分钟、25分钟或30分钟)，清洗后备用。 所述基底材料为碳箔时，所述预处理的具体操作为：将基底材料置于 0.5～2mol/L(具体可以为0.5mol/L、0.75mol/L、1mol/L、1.25mol/L、1.5mol/L、 1.75mol/L或2mol/L)的硝酸溶液中浸泡1小时以上，清洗后备用。In specific embodiments, different base materials require different pretreatment methods. For example: In step (1), when the base material is stainless steel, the specific operation of the pretreatment is: use 320 mesh and 600 mesh SiC sandpaper to polish the base material in turn, remove the surface layer, and then use a potentiostat to 0.5～2mol/L (specifically 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, 1.75mol/L or 2mol/L) sulfuric acid solution to remove the surface oxide layer (The electrolyte is a sulfuric acid solution, which needs to be energized with a potentiostat to quickly remove the surface oxide layer). When the base material is nickel foil and/or copper foil, the specific operation of the pretreatment is as follows: the base material is treated at 0.5-2mol/L (specifically, it can be 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, 1.75mol/L or 2mol/L) hydrochloric acid solution for 10 to 30 minutes (for example, 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes), wash and reserve use. When the base material is carbon foil, the specific operation of the pretreatment is: place the base material at 0.5 to 2 mol/L (specifically 0.5 mol/L, 0.75 mol/L, 1 mol/L, 1.25 mol/L , 1.5mol/L, 1.75mol/L or 2mol/L) in nitric acid solution for more than 1 hour, wash and set aside.
在步骤(2)中，所述镍盐溶液可以为本领域的常规选择，例如可以为 NiCl2·6H2O溶液和/或NiSO4·6H2O溶液。在具体实施方式中，所述NiCl2·6H2O 溶液的浓度可以为0.5～2mol/L，例如0.5mol/L、1.0mol/L、1.5mol/L、2mol/L。In step (2), the nickel salt solution can be a conventional choice in the art, for example, it can be a NiCl 2 ·6H 2 O solution and/or a NiSO 4 ·6H 2 O solution. In a specific embodiment, the concentration of the NiCl 2 ·6H 2 O solution may be 0.5˜2 mol/L, such as 0.5 mol/L, 1.0 mol/L, 1.5 mol/L, 2 mol/L.
在具体实施方式中，在步骤(2)中，预镀镍可以采用电沉积的方式进 行。所述电沉积的电流可以为-50～-200mA·cm2，例如-50mA·cm2、 -100mA·cm2、-150mA·cm2或-200mA·cm2。在具体实施方式中，在步骤(2) 中，所述电沉积的时间可以为5-30分钟，例如5分钟、10分钟、15分钟、 20分钟、25分钟、或30分钟。In a specific embodiment, in step (2), nickel pre-plating can be performed by means of electrodeposition. The electrodeposition current may be -50˜-200mA·cm 2 , for example -50mA·cm 2 , -100mA·cm 2 , -150mA·cm 2 or -200mA·cm 2 . In a specific embodiment, in step (2), the electrodeposition time may be 5-30 minutes, such as 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes.
在本发明所述的方法中，采用的催化剂镀液中需要含有适量的第一金属 元素、第二金属元素和非金属元素。In the method of the present invention, need to contain appropriate amount of first metal element, second metal element and metalloid element in the catalyst bath that adopts.
在具体实施实施方式中，在步骤(3)所述催化剂镀液中，第一金属元 素的浓度可以为0.1-2mol/L，例如0.1mol/L、0.5mol/L、1mol/L、1.5mol/L 或2mol/L；第二金属元素的浓度可以为0.02-0.5mol/L，例如0.02mol/L、 0.05mol/L、0.1mol/L、0.2mol/L、0.3mol/L、0.4mol/L或0.5mol/L；非金属元 素的浓度可以为0.02-0.5mol/L，例如0.02mol/L、0.05mol/L、0.1mol/L、 0.2mol/L、0.3mol/L、0.4mol/L或0.5mol/L。In a specific embodiment, in the catalyst plating solution described in step (3), the concentration of the first metal element can be 0.1-2mol/L, such as 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol /L or 2mol/L; the concentration of the second metal element can be 0.02-0.5mol/L, such as 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol /L or 0.5mol/L; the concentration of non-metal elements can be 0.02-0.5mol/L, such as 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol /L or 0.5mol/L.
在具体实施方式中，所述第一金属元素、所述第二金属元素和所述非金 属元素由本领域常规使用的化合物提供。例如：所述第一金属元素为Ni时， 催化剂镀液中的Ni可以由NiSO4·6H2O提供；所述第一金属元素为Co时， 催化剂镀液中的Co可以由CoSO4·7H2O提供；所述第一金属元素为Fe时， 催化剂镀液中的Fe可以由FeSO4·7H2O提供。所述第二金属元素为Mo时， 催化剂镀液中的Mo可以由Na2MoO4·2H2O提供；所述第二金属元素为W时， 催化剂镀液中的W可以由Na2WO4·2H2O提供。所述非金属元素为P时，催 化剂镀液中的P可以由NaH2PO4·2H2O提供；所述非金属元素为S时，催化 剂镀液中的S可以由硫脲提供；所述非金属元素为N时，催化剂镀液中的N 可以由硝酸钠提供。In a specific embodiment, the first metal element, the second metal element and the non-metal element are provided by compounds commonly used in the art. For example: when the first metal element is Ni, the Ni in the catalyst plating solution can be provided by NiSO 4 6H 2 O; when the first metal element is Co, the Co in the catalyst plating solution can be provided by CoSO 4 7H 2 O; when the first metal element is Fe, the Fe in the catalyst plating solution may be provided by FeSO 4 ·7H 2 O. When the second metal element is Mo, Mo in the catalyst plating solution can be provided by Na 2 MoO 4 ·2H 2 O; when the second metal element is W, W in the catalyst plating solution can be provided by Na 2 WO 4 · 2H 2 O provided. When the non-metallic element is P, the P in the catalyst plating solution can be provided by NaH 2 PO 4 ·2H 2 O; when the non-metallic element is S, the S in the catalyst plating solution can be provided by thiourea; When the non-metallic element is N, N in the catalyst bath can be provided by sodium nitrate.
在具体实施实施方式中，在步骤(3)中，所述电镀的电流可以为-50～ -200mA·cm2，例如-50mA·cm2、-100mA·cm2、-150mA·cm2或-200mA·cm2。 在具体实施实施方式中，在步骤(3)中，所述电沉积的时间可以为5～30分 钟，例如5分钟、10分钟、15分钟、20分钟、25分钟或30分钟。In a specific embodiment, in step (3), the electroplating current may be -50 to -200mA·cm 2 , for example -50mA·cm 2 , -100mA·cm 2 , -150mA·cm 2 or - 200 mA·cm 2 . In a specific embodiment, in step (3), the electrodeposition time may be 5-30 minutes, such as 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.
在本发明所述方法中，为了便于第一金属元素、第二金属元素和非金属 元素电镀在基体材料上，在步骤(3)所述催化剂镀液中，还含有0.1-1mol/L (例如可以为0.1mol/L、0.2mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.8mol/L 或1mol/L)的C6H5Na3O7·2H2O溶液。In the method of the present invention, in order to facilitate the electroplating of the first metal element, the second metal element and the non-metal element on the base material, in the catalyst plating solution described in step (3), also contain 0.1-1mol/L (such as Can be 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.8mol/L or 1mol/L) C 6 H 5 Na 3 O 7 2H 2 O solution .
在优选实施方式中，在步骤(3)中，所述碱液为氨水溶液，氨水溶液 中的铵离子可以与第一金属元素和第二金属元素进行配位，便于电镀。In a preferred embodiment, in step (3), the lye is an ammonia solution, and the ammonium ions in the ammonia solution can coordinate with the first metal element and the second metal element to facilitate electroplating.
本发明第二方面提供了一种由前文所述的方法制备的电解水阴极材料， 所述阴极材料包括基底材料和催化剂，所述基底材料为不锈钢、镍箔、铜箔 或碳箔中的至少一种，所述催化剂含有第一金属元素、第二金属元素和非金 属元素，其中，所述第一金属元素为Ni、Co和Fe中的至少一种，所述第二 金属元素为Mo和/或W，所述非金属元素为P、S和N中的至少一种。The second aspect of the present invention provides a cathode material for electrolysis of water prepared by the method described above, the cathode material includes a base material and a catalyst, and the base material is at least one of stainless steel, nickel foil, copper foil or carbon foil One, the catalyst contains a first metal element, a second metal element and a metalloid element, wherein the first metal element is at least one of Ni, Co and Fe, and the second metal element is Mo and /or W, the non-metal element is at least one of P, S and N.
在具体实施方式中，所述阴极材料的组成可以为：In a specific embodiment, the composition of the cathode material can be:
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为Mo，所述非金属元素为P(Ni-Mo-P/不锈钢)；或The base material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P (Ni-Mo-P/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为Mo，所述非金属元素为P(Co-Mo-P/不锈钢)；或The base material is stainless steel, the first metal element is Co, the second metal element is Mo, and the non-metal element is P (Co-Mo-P/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P(Fe-Mo-P/不锈钢)；或The base material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P (Fe-Mo-P/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为W，所述非金属元素为P(Ni-W-P/不锈钢)；或The base material is stainless steel, the first metal element is Ni, the second metal element is W, and the non-metal element is P (Ni-W-P/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为W，所述非金属元素为P(Co-W-P/不锈钢)；或The base material is stainless steel, the first metal element is Co, the second metal element is W, and the non-metal element is P (Co-W-P/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P(Fe-W-P/不锈钢)；或The base material is stainless steel, the first metal element is Fe, the second metal element is W, and the non-metal element is P (Fe-W-P/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为Mo，所述非金属元素为S(Ni-Mo-S/不锈钢)；或The base material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S (Ni-Mo-S/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为Mo，所述非金属元素为S(Co-Mo-S/不锈钢)；或The base material is stainless steel, the first metal element is Co, the second metal element is Mo, and the non-metal element is S (Co-Mo-S/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S(Fe-Mo-S/不锈钢)；或The base material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S (Fe-Mo-S/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为W，所述非金属元素为S(Ni-W-S/不锈钢)；或The base material is stainless steel, the first metal element is Ni, the second metal element is W, and the non-metal element is S (Ni-W-S/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为W，所述非金属元素为S(Co-W-S/不锈钢)；或The base material is stainless steel, the first metal element is Co, the second metal element is W, and the non-metal element is S (Co-W-S/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S(Fe-W-S/不锈钢)；或The base material is stainless steel, the first metal element is Fe, the second metal element is W, and the non-metal element is S (Fe-W-S/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为Mo，所述非金属元素为N(Ni-Mo-N/不锈钢)；或The base material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N (Ni-Mo-N/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为Mo，所述非金属元素为N(Co-Mo-N/不锈钢)；或The base material is stainless steel, the first metal element is Co, the second metal element is Mo, and the non-metal element is N (Co-Mo-N/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N(Fe-Mo-N/不锈钢)；或The base material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N (Fe-Mo-N/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Ni，所述第二金属元素 为W，所述非金属元素为N(Ni-W-N/不锈钢)；或The base material is stainless steel, the first metal element is Ni, the second metal element is W, and the non-metal element is N (Ni-W-N/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Co，所述第二金属元素 为W，所述非金属元素为N(Co-W-N/不锈钢)；或The base material is stainless steel, the first metal element is Co, the second metal element is W, and the non-metal element is N (Co-W-N/stainless steel); or
所述基底材料为不锈钢，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N(Fe-W-N/不锈钢)；或The base material is stainless steel, the first metal element is Fe, the second metal element is W, and the non-metal element is N (Fe-W-N/stainless steel); or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为P(Ni-Mo-P/镍箔)；或The base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P (Ni-Mo-P/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为P(Co-Mo-P/镍箔)；或The base material is nickel foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is P (Co-Mo-P/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P(Fe-Mo-P/镍箔)；或The base material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P (Fe-Mo-P/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为P(Ni-W-P/镍箔)；或The base material is nickel foil, the first metal element is Ni, the second metal element is W, and the non-metal element is P (Ni-W-P/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为W，所述非金属元素为P(Co-W-P/镍箔)；或The base material is nickel foil, the first metal element is Co, the second metal element is W, and the non-metal element is P (Co-W-P/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P(Fe-W-P/镍箔)；或The base material is nickel foil, the first metal element is Fe, the second metal element is W, and the non-metal element is P (Fe-W-P/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为S(Ni-Mo-S/镍箔)；或The base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S (Ni-Mo-S/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为S(Co-Mo-S/镍箔)；或The base material is nickel foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is S (Co-Mo-S/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S(Fe-Mo-S/镍箔)；或The base material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S (Fe-Mo-S/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为S(Ni-W-S/镍箔)；或The base material is nickel foil, the first metal element is Ni, the second metal element is W, and the non-metal element is S (Ni-W-S/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为S(Co-W-S/镍箔)；或The base material is nickel foil, the first metal element is Co, the second metal element is W, and the non-metal element is S (Co-W-S/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S(Fe-W-S/镍箔)；或The base material is nickel foil, the first metal element is Fe, the second metal element is W, and the non-metal element is S (Fe-W-S/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为N(Ni-Mo-N/镍箔)；或The base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N (Ni-Mo-N/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为N(Co-Mo-N/镍箔)；或The base material is nickel foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is N (Co-Mo-N/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N(Fe-Mo-N/镍箔)；或The base material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N (Fe-Mo-N/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为N(Ni-W-N/镍箔)；或The base material is nickel foil, the first metal element is Ni, the second metal element is W, and the non-metal element is N (Ni-W-N/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为N(Co-W-N/镍箔)；或The base material is nickel foil, the first metal element is Co, the second metal element is W, and the non-metal element is N (Co-W-N/nickel foil); or
所述基底材料为镍箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N(Fe-W-N/镍箔)；或The base material is nickel foil, the first metal element is Fe, the second metal element is W, and the non-metal element is N (Fe-W-N/nickel foil); or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为P(Ni-Mo-P/铜箔)；或The base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P (Ni-Mo-P/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为P(Co-Mo-P/铜箔)；或The base material is copper foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is P (Co-Mo-P/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P(Fe-Mo-P/铜箔)；或The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P (Fe-Mo-P/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为P(Ni-W-P/铜箔)；或The base material is copper foil, the first metal element is Ni, the second metal element is W, and the non-metal element is P (Ni-W-P/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为P(Co-W-P/铜箔)；或The base material is copper foil, the first metal element is Co, the second metal element is W, and the non-metal element is P (Co-W-P/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P(Fe-W-P/铜箔)；或The base material is copper foil, the first metal element is Fe, the second metal element is W, and the non-metal element is P (Fe-W-P/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为S(Ni-Mo-S/铜箔)；或The base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S (Ni-Mo-S/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为S(Co-Mo-S/铜箔)；或The base material is copper foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is S (Co-Mo-S/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S(Fe-Mo-S/铜箔)；或The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S (Fe-Mo-S/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为S(Ni-W-S/铜箔)；或The base material is copper foil, the first metal element is Ni, the second metal element is W, and the non-metal element is S (Ni-W-S/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为S(Co-W-S/铜箔)；或The base material is copper foil, the first metal element is Co, the second metal element is W, and the non-metal element is S (Co-W-S/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为W，所述非金属元素为S(Fe-W-S/铜箔)；或The base material is copper foil, the first metal element is Fe, the second metal element is W, and the non-metal element is S (Fe-W-S/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为N(Ni-Mo-N/铜箔)；或The base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N (Ni-Mo-N/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为N(Co-Mo-N/铜箔)；或The base material is copper foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is N (Co-Mo-N/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N(Fe-Mo-N/铜箔)；或The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N (Fe-Mo-N/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为N(Ni-W-N/铜箔)；或The base material is copper foil, the first metal element is Ni, the second metal element is W, and the non-metal element is N (Ni-W-N/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为N(Co-W-N/铜箔)；或The base material is copper foil, the first metal element is Co, the second metal element is W, and the non-metal element is N (Co-W-N/copper foil); or
所述基底材料为铜箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N(Fe-W-N/铜箔)；或The base material is copper foil, the first metal element is Fe, the second metal element is W, and the non-metal element is N (Fe-W-N/copper foil); or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为P(Ni-Mo-P/碳箔)；或The base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P (Ni-Mo-P/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为P(Co-Mo-P/碳箔)；或The base material is carbon foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is P (Co-Mo-P/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为P(Fe-Mo-P/碳箔)；或The base material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is P (Fe-Mo-P/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为P(Ni-W-P/碳箔)；或The base material is carbon foil, the first metal element is Ni, the second metal element is W, and the non-metal element is P (Ni-W-P/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为P(Co-W-P/碳箔)；或The base material is carbon foil, the first metal element is Co, the second metal element is W, and the non-metal element is P (Co-W-P/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为P(Fe-W-P/碳箔)；或The base material is carbon foil, the first metal element is Fe, the second metal element is W, and the non-metal element is P (Fe-W-P/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为S(Ni-Mo-S/碳箔)；或The base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is S (Ni-Mo-S/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为S(Co-Mo-S/碳箔)；或The base material is carbon foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is S (Co-Mo-S/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为S(Fe-Mo-S/碳箔)；或The base material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is S (Fe-Mo-S/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为S(Ni-W-S/碳箔)；或The base material is carbon foil, the first metal element is Ni, the second metal element is W, and the non-metal element is S (Ni-W-S/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为S(Co-W-S/碳箔)；或The base material is carbon foil, the first metal element is Co, the second metal element is W, and the non-metal element is S (Co-W-S/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为S(Fe-W-S/碳箔)；或The base material is carbon foil, the first metal element is Fe, the second metal element is W, and the non-metal element is S (Fe-W-S/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 Mo，所述非金属元素为N(Ni-Mo-N/碳箔)；或The base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is N (Ni-Mo-N/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 Mo，所述非金属元素为N(Co-Mo-N/碳箔)；或The base material is carbon foil, the first metal element is Co, the second metal element is Mo, and the non-metal element is N (Co-Mo-N/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 Mo，所述非金属元素为N(Fe-Mo-N/碳箔)；或The base material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the non-metal element is N (Fe-Mo-N/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Ni，所述第二金属元素为 W，所述非金属元素为N(Ni-W-N/碳箔)；或The base material is carbon foil, the first metal element is Ni, the second metal element is W, and the non-metal element is N (Ni-W-N/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Co，所述第二金属元素为 W，所述非金属元素为N(Co-W-N/碳箔)；或The base material is carbon foil, the first metal element is Co, the second metal element is W, and the non-metal element is N (Co-W-N/carbon foil); or
所述基底材料为碳箔，所述第一金属元素为Fe，所述第二金属元素为 W，所述非金属元素为N(Fe-W-N/碳箔)。The base material is carbon foil, the first metal element is Fe, the second metal element is W, and the non-metal element is N (Fe-W-N/carbon foil).
在优选实施方式中，所述阴极材料的组成可以为：所述基底材料为镍箔， 所述第一金属元素为Ni，所述第二金属元素为Mo，所述非金属元素为P(N i-Mo-P/镍箔)或者所述基底材料为铜箔，所述第一金属元素为Ni，所述第 二金属元素为Mo，所述非金属元素为P(Ni-Mo-P/铜箔)或者所述基底材 料为碳箔，所述第一金属元素为Ni，所述第二金属元素为Mo，所述非金属 元素为P(Ni-Mo-P/碳箔)。当所述阴极材料的组成为这几种方式时，阴极材料电催化氢化还原染料的电流效率和转化率较高。In a preferred embodiment, the composition of the cathode material can be: the base material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P(N i-Mo-P/nickel foil) or the base material is copper foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P (Ni-Mo-P/ copper foil) or the base material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the non-metal element is P (Ni-Mo-P/carbon foil). When the composition of the cathode material is in these modes, the current efficiency and conversion rate of the electrocatalytic hydrogenation of the cathode material to reduce the dye are relatively high.
本发明第三方面提供了一种前文所述的电解水阴极材料在电催化氢化 还原染料中的应用。所述电解水阴极材料用于电催化氢化还原染料，可以降 低还原氢的过电位，提高氢化还原产物的转化率。The third aspect of the present invention provides an application of the above-mentioned electrolyzed water cathode material in the electrocatalytic hydrogenation reduction of dyes. The electrolyzed water cathode material is used for electrocatalytic hydrogenation reduction of dyes, which can reduce the overpotential of hydrogen reduction and increase the conversion rate of hydrogenation reduction products.
在具体实施方式中，所述还原染料为靛蓝、硫化黑BR、还原黄G、还 原蓝BC、还原绿FFB、还原红R、还原棕R、还原金橙3G和还原紫RR中 的至少一种，优选为靛蓝、硫化黑、还原黄和还原紫。In a specific embodiment, the vat dye is at least one of indigo, sulfur black BR, vat yellow G, vat blue BC, vat green FFB, vat red R, vat brown R, vat golden orange 3G and vat violet RR , preferably indigo, sulfur black, vat yellow and vat violet.
以下将通过实施例对本发明进行详细描述，但本发明的保护范围并不仅 限于此。The present invention will be described in detail below by embodiment, but protection scope of the present invention is not limited thereto.
以下实施例用于说明电解水阴极材料的制备过程。The following examples are used to illustrate the preparation process of cathode materials for electrolysis of water.
实施例1Example 1
(1)对基体材料进行预处理：采用320目和600目的SiC砂纸依次对 不锈钢进行打磨，去除表层，然后采用恒电位仪在1mol/L的硫酸溶液中去 除表面氧化层；(1) Carry out pretreatment to matrix material: adopt 320 order and 600 order SiC sandpaper to polish stainless steel successively, remove surface layer, then adopt potentiostat to remove surface oxide layer in the sulfuric acid solution of 1mol/L;
(2)预镀镍：将预处理后的不锈钢裁剪为1×2cm的块状，然后在1mol/L 的NiCl2·6H2O溶液中于-160mA·cm2下电沉积20分钟，得到具有镍镀层的不 锈钢；(2) Pre-nickel plating: Cut the pre-treated stainless steel into 1×2cm blocks, and then electrodeposit it in 1mol/L NiCl 2 6H 2 O solution at -160mA·cm 2 for 20 minutes to obtain Nickel-plated stainless steel;
(3)Ni-Mo-P/不锈钢阴极材料的制备：配制含有Ni、Mo、P的催化剂 镀液，催化剂镀液的组成如表1所示，然后将催化剂镀液的pH调节至9， 然后采用三电极法将具有镍镀层的不锈钢置于催化剂镀液中于-100mA·cm2下电镀5分钟，得到Ni-Mo-P/不锈钢阴极材料。(3) Preparation of Ni-Mo-P/stainless steel cathode material: preparation contains the catalyst bath of Ni, Mo, P, the composition of catalyst bath is as shown in table 1, then the pH of catalyst bath is adjusted to 9, then Using the three-electrode method, the stainless steel with nickel coating was placed in the catalyst plating solution and electroplated at -100mA·cm 2 for 5 minutes to obtain the Ni-Mo-P/stainless steel cathode material.
实施例2Example 2
(1)对基体材料进行预处理：将镍箔在1mol/L的盐酸溶液中浸泡20 分钟；(1) Carry out pretreatment to matrix material: soak nickel foil in the hydrochloric acid solution of 1mol/L for 20 minutes;
(2)预镀镍：将预处理后的镍箔裁剪为1×2cm的块状，然后在1.5mol/L 的NiCl2·6H2O溶液中于-160mA·cm2下电沉积15分钟，得到具有镍镀层的镍 箔；(2) Pre-plating nickel: cut the pre-treated nickel foil into a block of 1×2 cm, and then electrodeposit it in a 1.5mol/L NiCl 2 6H 2 O solution at -160mA cm 2 for 15 minutes. obtaining a nickel foil with a nickel coating;
(3)Ni-Mo-P/镍箔阴极材料的制备：配制含有Ni、Mo、P的催化剂镀 液，催化剂镀液的组成如表1所示，然后将催化剂镀液的pH调节至10，然 后采用三电极法将具有镍镀层的镍箔置于催化剂镀液中于-100mA·cm2下电 镀5分钟，得到Ni-Mo-P/镍箔阴极材料。(3) Preparation of Ni-Mo-P/nickel foil cathode material: prepare a catalyst plating solution containing Ni, Mo, P, the composition of the catalyst plating solution is as shown in Table 1, then adjust the pH of the catalyst plating solution to 10, Then use the three-electrode method to place the nickel foil with nickel coating in the catalyst plating solution and electroplate it at -100mA· cm2 for 5 minutes to obtain the Ni-Mo-P/nickel foil cathode material.
实施例3Example 3
(1)对基体材料进行预处理：将铜箔在1.5mol/L的盐酸溶液中浸泡15 分钟；(1) Pretreatment of the base material: soak the copper foil in 1.5mol/L hydrochloric acid solution for 15 minutes;
(2)预镀镍：将预处理后的铜箔裁剪为1×2cm的块状，然后在0.5mol/L 的NiSO4·6H2O溶液中于-160mA·cm2下电沉积25分钟，得到具有镍镀层的 铜箔；(2) Pre-plating nickel: cut the pre-treated copper foil into a block of 1×2 cm, and then electrodeposit it in a 0.5mol/L NiSO 4 6H 2 O solution at -160mA cm 2 for 25 minutes. A copper foil with nickel plating is obtained;
(3)Ni-Mo-P/铜箔阴极材料的制备：配制含有Ni、Mo、P的催化剂镀 液，催化剂镀液的组成如表1所示，然后将催化剂镀液的pH调节至9.5，然 后采用三电极法将具有镍镀层的铜箔置于催化剂镀液中于-100mA·cm2下电 镀15分钟，得到Ni-Mo-P/铜箔阴极材料。(3) Preparation of Ni-Mo-P/copper foil cathode material: prepare a catalyst plating solution containing Ni, Mo, P, the composition of the catalyst plating solution is as shown in Table 1, then adjust the pH of the catalyst plating solution to 9.5, Then use the three-electrode method to place the copper foil with nickel coating in the catalyst plating solution and electroplate it for 15 minutes at -100mA·cm 2 to obtain the Ni-Mo-P/copper foil cathode material.
实施例4Example 4
(1)对基体材料进行预处理：将碳箔置于2mol/L的硝酸溶液中浸泡2 小时；(1) Pretreatment of the base material: soak the carbon foil in 2mol/L nitric acid solution for 2 hours;
(2)预镀镍：将预处理后的碳箔裁剪为1×2cm的块状，然后在1mol/L 的NiCl2·6H2O溶液中于-160mA·cm2下电沉积20分钟，得到具有镍镀层的碳 箔；(2) Pre-plating nickel: Cut the pretreated carbon foil into a block of 1×2 cm, and then electrodeposit it in a 1mol/L NiCl 2 6H 2 O solution at -160mA cm 2 for 20 minutes to obtain Carbon foil with nickel plating;
(3)Ni-Mo-P/碳箔阴极材料的制备：配制含有Ni、Mo、P的催化剂镀 液，催化剂镀液的组成如表1所示，然后将催化剂镀液的pH调节至8.5，然 后采用三电极法将具有镍镀层的碳箔置于催化剂镀液中于-100mA·cm2下电 镀5分钟，得到Ni-Mo-P/碳箔阴极材料。(3) Preparation of Ni-Mo-P/carbon foil cathode material: prepare a catalyst plating solution containing Ni, Mo, P, the composition of the catalyst plating solution is as shown in Table 1, then adjust the pH of the catalyst plating solution to 8.5, Then, the carbon foil with nickel coating was placed in the catalyst plating solution and electroplated at -100mA· cm2 for 5 minutes by the three-electrode method to obtain the Ni-Mo-P/carbon foil cathode material.
表1催化剂镀液的组成The composition of table 1 catalyst bath
实施例5Example 5
按照实施例1的方法实施，不同的是，所述催化剂镀液中加入CH4N2S 代替NaH2PO4·2H2O，得到Ni-Mo-S/不锈钢阴极材料。The implementation was carried out according to the method of Example 1, except that CH 4 N 2 S was added to the catalyst plating solution instead of NaH 2 PO 4 ·2H 2 O to obtain a Ni-Mo-S/stainless steel cathode material.
实施例6Example 6
按照实施例1的方法实施，不同的是，所述催化剂镀液中加入 CoSO4·7H2O代替NiSO4·6H2O，得到Co-Mo-P/不锈钢阴极材料。Implement according to the method of Example 1, except that CoSO 4 .7H 2 O is added to the catalyst plating solution instead of NiSO 4 .6H 2 O to obtain a Co-Mo-P/stainless steel cathode material.
对比例1Comparative example 1
按照实施例1的方法实施，不同的是，所述催化剂镀液中不加入 NiSO4·6H2O，得到Mo-P/不锈钢阴极材料。Implement according to the method of Example 1, the difference is that NiSO 4 ·6H 2 O is not added to the catalyst plating solution to obtain the Mo-P/stainless steel cathode material.
对比例2Comparative example 2
按照实施例1的方法实施，不同的是，所述催化剂镀液中不加入 Na2MoO4·2H2O，得到Ni-P/不锈钢阴极材料。Implement according to the method of Example 1, the difference is that Na 2 MoO 4 ·2H 2 O is not added to the catalyst plating solution to obtain a Ni-P/stainless steel cathode material.
对比例3Comparative example 3
按照实施例1的方法实施，不同的是，所述催化剂镀液中不加入 NaH2PO4·2H2O，得到Ni-Mo/不锈钢阴极材料。Implement according to the method of Example 1, the difference is that NaH 2 PO 4 ·2H 2 O is not added to the catalyst plating solution to obtain a Ni-Mo/stainless steel cathode material.
测试例1
将5g靛蓝溶于1L的1mol/L的KOH溶液中，超声5分钟使靛蓝颗粒完 全分散在溶液中。然后将实施例1-6和对比例1-3中制备的阴极材料作为阴 极，铂电极作为阳极，用恒电位仪连接，进行电催化氢化还原靛蓝。开始还 原靛蓝前，需通入30分钟氮气充分排出反应池内的氧气，然后在10mA·cm2的电流密度下还原靛蓝12小时。使用分光光度计测量反应后靛蓝吸光度的 下降值并确定还原量，从而计算电流效率，结果如表2所示。Dissolve 5 g of indigo in 1 L of 1 mol/L KOH solution, and ultrasonicate for 5 minutes to completely disperse the indigo particles in the solution. Then, the cathode materials prepared in Examples 1-6 and Comparative Examples 1-3 were used as the cathode, and the platinum electrode was used as the anode, connected with a potentiostat to perform electrocatalytic hydrogenation reduction of indigo. Before starting to reduce indigo, it is necessary to pass through nitrogen for 30 minutes to fully discharge the oxygen in the reaction cell, and then reduce indigo at a current density of 10mA·cm 2 for 12 hours. Use a spectrophotometer to measure the decrease in the absorbance of indigo after the reaction and determine the amount of reduction to calculate the current efficiency. The results are shown in Table 2.
测试例2
将采用实施例1-6和对比例1-3中制备的阴极材料作为阴极还原前和还 原后的靛蓝溶液在200-800nm区间内扫描，扫描速度为5nm/s，确定其最大 吸收波长。由紫外可见吸收光谱可以看出，靛蓝溶液的最大吸收波长在 690nm处，所以根据其还原12h的吸收强度和还原前的原溶液进行对比，可 以得到靛蓝的还原效率，结果如表2所示。其中，实施例1-4中制备的阴极 材料的紫外可见吸收光谱如图5-图8所示Will adopt the cathode material prepared in embodiment 1-6 and comparative example 1-3 to scan in the interval of 200-800nm as the indigo solution before and after the reduction of the cathode, and the scan speed is 5nm/s to determine its maximum absorption wavelength. As can be seen from the ultraviolet-visible absorption spectrum, the maximum absorption wavelength of the indigo solution is at 690nm, so the reduction efficiency of indigo can be obtained according to the absorption intensity of its reduction 12h and the original solution before reduction, and the results are shown in Table 2. Wherein, the ultraviolet-visible absorption spectrum of the cathode material prepared in embodiment 1-4 is as shown in Fig. 5-Fig. 8
表2Table 2
通过表2的结果可以看出，采用本发明所述方法制备的阴极材料电催化 氢化还原靛蓝的电流效率和转化率较高。Can find out by the result of table 2, adopt the cathode material electrocatalytic hydrogenation reduction indigo electric current efficiency and conversion ratio prepared by the method of the present invention to be higher.
测试例3Test case 3
电化学氢化的动力学过程与电催化析氢是相近的，都是在电极表面生成 了具有还原能力的吸附态的氢原子，然后利用氢原子和水或有机分子进行反 应。故本实验也采用电催化析氢的测试方法，分析实施例1-4制备的Ni-Mo-P 阴极材料的动力学过程。The kinetic process of electrochemical hydrogenation is similar to that of electrocatalytic hydrogen evolution, both of which generate adsorbed hydrogen atoms with reducing ability on the electrode surface, and then use hydrogen atoms to react with water or organic molecules. Therefore, this experiment also adopts the test method of electrocatalytic hydrogen evolution to analyze the kinetic process of the Ni-Mo-P cathode material prepared in Examples 1-4.
根据线性伏安扫描结果图9和图10可知，Ni-Mo-P/不锈钢具有最佳的 动力学过程，其过电位较高；Ni-Mo-P/碳箔具有最低的过电位但是其动力学 过程较差；而Ni-Mo-P/镍箔和Ni-Mo-P/铜箔的过电位相近且Tafel斜率也相 近，两者可能动力学过程相似。但是由于材料基底性质的差异，Ni-Mo-P在 不同的电极基底上表现出了对靛蓝不同的还原能力。Ni-Mo-P/不锈钢网由于 其表面积小导致与靛蓝分子接触频次较低导致了还原靛蓝效果不佳。而镍箔 虽然具有较大的表面积而且具有孔隙结构，但Ni本身就是在电催化析氢中常用的催化剂，导致了其表面有严重的析氢反应从而还原靛蓝的效果不高。 铜箔和镍箔一样具有较大表面积和孔隙结构，但是铜为电催化中能够抑制析 氢的催化剂，因此表现出了比Ni-Mo-P/镍箔高的还原效果。而碳箔作为几种 基底中唯一的非金属基底其主要成分为石墨，具有一定的吸水性并且与对靛 蓝分子有一定的亲和力，所以即使碳箔的动力学过程最差但是由于基底的良 好的性能导致了Ni-Mo-P/碳箔还原靛蓝具有最佳的效果。According to the results of linear voltammetry scans in Figure 9 and Figure 10, it can be seen that Ni-Mo-P/stainless steel has the best kinetic process, and its overpotential is higher; Ni-Mo-P/carbon foil has the lowest overpotential but its kinetics The overpotential and Tafel slope of Ni-Mo-P/nickel foil and Ni-Mo-P/copper foil are similar, and the kinetic process of the two may be similar. However, due to the difference in the properties of the material substrates, Ni-Mo-P exhibited different reduction abilities to indigo on different electrode substrates. The Ni-Mo-P/stainless steel mesh has a poor effect on reducing indigo due to its small surface area resulting in low frequency of contact with indigo molecules. Although nickel foil has a large surface area and a pore structure, Ni itself is a commonly used catalyst in electrocatalytic hydrogen evolution, which leads to a serious hydrogen evolution reaction on its surface and the effect of reducing indigo is not high. Copper foil has the same large surface area and pore structure as nickel foil, but copper is a catalyst that can inhibit hydrogen evolution in electrocatalysis, so it shows a higher reduction effect than Ni-Mo-P/nickel foil. Carbon foil is the only non-metallic substrate among several substrates, and its main component is graphite, which has a certain degree of water absorption and has a certain affinity with indigo molecules, so even though the kinetic process of carbon foil is the worst, due to the good substrate properties lead to Ni-Mo-P/carbon foil with the best effect on reducing indigo.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在 本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包 括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样 应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
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