CN113529124A - Electrolytic water cathode material, preparation method thereof and application of cathode material in electrocatalytic hydrogenation reduction of dye - Google Patents

Electrolytic water cathode material, preparation method thereof and application of cathode material in electrocatalytic hydrogenation reduction of dye Download PDF

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CN113529124A
CN113529124A CN202110642126.9A CN202110642126A CN113529124A CN 113529124 A CN113529124 A CN 113529124A CN 202110642126 A CN202110642126 A CN 202110642126A CN 113529124 A CN113529124 A CN 113529124A
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metal element
substrate material
nonmetal
foil
metal
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CN113529124B (en
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魏冬
刘自豪
吴晨曦
姜会钰
彭俊军
王振东
吕少仿
杨锋
刘慧宏
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Wuhan Textile University
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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
    • C25B11/073—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
    • 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
    • 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

Abstract

The invention relates to the technical field of electrochemical hydrogenation reduction, and discloses an electrolytic water cathode material, a preparation method thereof and application of the cathode material in electrocatalytic hydrogenation reduction of dyes. The method comprises the following steps: (1) pretreating a substrate material; (2) cutting the pretreated substrate material into blocks, and then carrying out nickel preplating in a nickel salt solution; (3) preparing a catalyst plating solution containing a first metal element, a second metal element and a nonmetal element, adjusting the pH of the catalyst plating solution to 8-11 by using an alkali liquor, and then placing a substrate material with a nickel coating in the catalyst plating solution by adopting a three-electrode method for electroplating to obtain a cathode material; 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 nonmetal element is at least one of P, S and N. The cathode material prepared by the method has high conversion rate of the electrocatalytic hydrogenation reduction dye.

Description

Electrolytic water cathode material, preparation method thereof and application of cathode material in electrocatalytic hydrogenation reduction of dye
Technical Field
The invention relates to the technical field of electrochemical hydrogenation reduction, in particular to an electrolytic water cathode material, a preparation method thereof and application of the cathode material in electrocatalytic hydrogenation reduction of dyes.
Background
There are three methods of electrochemically reducing dyes: direct electrochemical reduction, indirect electrochemical reduction and electrocatalytic hydrogenation reduction. The direct electrochemical reduction has the defects of low current efficiency and slow reduction rate. Indirect electrochemical reduction requires an electron mediator (Fe)2+/Fe3+) And a large amount of organic ligand is added. At present, indirect electrochemical reduction dyes are researched more, but organic ligands are high in cost and cannot be reused, and dyeing color difference of the dyes is difficult to control, so that industrial production and printing and dyeing application are difficult to realize.
The principle of the electrocatalytic hydrogenation reduction process is shown in figure 12.
In the electrolysis of water, a water reduction Hydrogen Evolution Reaction (HER) takes place in the cathode cell and a water oxidation Oxygen Evolution Reaction (OER) takes place in the anode cell, separated by a proton permeable membrane (PEM). The hydrogen atoms generated by the cathode have stronger reducing capability, can reduce the water-insoluble vat dye molecules to generate reduced dye molecules which 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 need high-pressure hydrogen and chemical reducing agents, the hydrogenation process is easy to control, the reaction condition is mild, the oxidation-reduction potential is controllable, the consumed chemicals are less, the waste water discharge is less, the industrialization is easy, and the like.
Roessler et al prepared electrodes of platinum (Pt/Fe), ruthenium (Rh/Fe), palladium (Pd/Fe), nickel (Ni/Fe), cobalt (Co/Fe) and copper (Cu/Fe) on stainless steel mesh by electrodeposition for electrocatalytic hydrogenation reduction of indigo with indigo conversions (current efficiencies) of 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%), respectively, as shown in FIG. 12. The results show that the noble metals have higher conversion rate and current use efficiency, and the non-noble metals have much poorer efficiency (Roessler A. etc. electrochemical catalytic hydrogenation of vat powers, Dyes and Pigments,2002,54, 141-146.). The electrolytic Cell is changed from The H Cell to The Flow Cell, and although The conversion rate and The current utilization efficiency of The Indigo are greatly improved, such as The conversion rate (current efficiency) of The Indigo of Ni/Fe and NiPt/Fe electrodes is 95% (13%) and 95% (19%), respectively, The current utilization efficiency is still relatively low (Roessler A. etc. Electrochemical hydrogen generation of Indigo Process Optimization and Scale-Up in a Flow Cell, Journal of The Electrochemical Society,2003,150(1) (D1-D5) (European patent EP2032740B 1).
Disclosure of Invention
The invention aims to overcome the defects that the cathode material of the electrolyzed water in the prior art is single, the price of platinum group elements (platinum, ruthenium, palladium and the like) is high, and the inactivation is easy to occur; the cathode material for the electrolyzed water contains three specific catalyst elements, the cathode material is adopted to carry out the electrocatalytic hydrogenation reduction of the dye, the overpotential of the cathode electrolyzed water is low, the current use efficiency is high, and the conversion rate of the hydrogenation reduction product can be improved.
In order to achieve the above object, a first aspect of the present invention provides a method for producing an electrolytic water cathode material, comprising the steps of:
(1) pretreating a substrate material, wherein the substrate material is at least one of stainless steel, nickel foil, copper foil or carbon foil;
(2) cutting the pretreated substrate material into blocks, and then pre-plating nickel in a nickel salt solution to obtain a substrate material with a nickel plating layer;
(3) preparing a catalyst plating solution containing a first metal element, a second metal element and a nonmetal element, adjusting the pH of the catalyst plating solution to 8-11 by using an alkali liquor, and then placing a substrate material with a nickel plating layer in the catalyst plating solution by adopting a three-electrode method for electroplating to obtain a cathode material;
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 nonmetal element is at least one of P, S and N.
Preferably, in step (1), when the base material is stainless steel, the pretreatment is specifically performed by: the substrate material is sequentially polished by using 320-mesh and 600-mesh SiC sand paper, the surface layer is removed, and then a surface oxidation layer is removed in a 0.5-2 mol/L sulfuric acid solution by using a constant potential rectifier.
Preferably, when the substrate material is a nickel foil and/or a copper foil, the pretreatment specifically comprises the following steps: soaking the substrate material in 0.5-2 mol/L hydrochloric acid solution for 10-30 minutes, and cleaning for later use.
Preferably, when the substrate material is a carbon foil, the pretreatment specifically comprises the following steps: and (3) soaking the base material in 0.5-2 mol/L nitric acid solution for more than 1 hour, and cleaning for later use.
Preferably, in the step (2), the nickel salt solution is NiCl2·6H2O solution and/or NiSO4·6H2The concentration of the O solution is 0.5-2 mol/L.
Preferably, in the step (2), nickel pre-plating is performed by electrodeposition; the conditions of the electrodeposition are as follows: the current is-50 to-200 mA cm2The time is 5-30 minutes.
Preferably, in the catalyst plating solution of step (3), the concentration of the first metal element is 0.1 to 2mol/L, the concentration of the second metal element is 0.02 to 0.5mol/L, and the concentration of the nonmetal element is 0.02 to 0.5 mol/L.
Preferably, in the step (3), the plating conditions are: the current is-50 to-200 mA cm2The time is 5-30 minutes.
Preferably, the catalyst plating solution in step (3) further contains 0.1 to 1mol/L of C6H5Na3O7·2H2And (4) O solution.
Preferably, in step (3), the alkali solution is an aqueous ammonia solution.
In a second aspect, the present invention provides an electrolyzed water cathode material prepared by the method described above, the cathode material comprising a base material and a catalyst, the base material being at least one of stainless steel, a nickel foil, a copper foil, or a carbon foil, the catalyst containing a first metal element, a second metal element, and a non-metal element, 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.
Preferably, the cathode material has a composition of: the substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N.
In a third aspect the present invention provides the use of an electrolyzed water cathode material as hereinbefore described in an electrocatalytic hydrogenation of a vat dye.
Preferably, the vat dye is at least one of indigo, sulphur black BR, vat yellow G, vat blue BC, vat green FFB, vat red R, vat brown R, vat gold orange 3G and vat violet RR.
The inventor of the invention finds that when the ternary composite electrocatalyst containing two specific metal elements and one specific non-metal element is used as the cathode material of the electrolyzed water, the two metals are compounded when the dye is subjected to electrocatalytic hydrogenation, and the composite electrocatalyst plays an important role in stabilizing the hydrogen atoms in the adsorption state; (2) bimetallic active sites are heterogenized, and the synergistic effect of the bimetallic active sites can promote the kinetics of electrocatalytic reduction of hydrogen; (3) the introduction of non-metal atoms is beneficial to the redistribution of electrons, and the electronic structure of the catalyst is optimized; (4) the non-metal atoms can enhance the capability of adsorbing organic molecules and increase the contact probability and reaction time of the vat dye molecules and atomic hydrogen. Therefore, the electrolytic water cathode material containing the three-way composite electrocatalyst is adopted to carry out electrocatalytic hydrogenation reduction on the dye, so that the overpotential of the reduced hydrogen can be reduced, and the conversion rate of the hydrogenation reduction product can be improved.
Drawings
FIGS. 1 and 2 are a scanning electron micrograph and an energy spectrum of the Ni-Mo-P/stainless steel cathode material prepared in example 1, respectively.
FIGS. 3 and 4 are a scanning electron micrograph and an energy spectrum of the Ni-Mo-P/nickel foil cathode material prepared in example 2, respectively.
Fig. 5 to 8 are uv-vis absorption spectra of indigo solutions before and after cathodic reduction using the cathode materials prepared in examples 1 to 4, respectively.
FIGS. 9-10 are linear voltammograms of the Ni-Mo-P cathode materials prepared in examples 1-4.
FIG. 11 is a graph showing the effect of Ni-Mo-P/carbon foiling on dyeing cotton after reducing indigo.
FIG. 12 is a schematic diagram of the principle of the electrocatalytic hydrogenation reduction process.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for preparing an electrolytic water cathode material, comprising the steps of:
(1) pretreating a substrate material, wherein the substrate material is at least one of stainless steel, nickel foil, copper foil or carbon foil;
(2) cutting the pretreated substrate material into blocks, and then pre-plating nickel in a nickel salt solution to obtain a substrate material with a nickel plating layer;
(3) preparing a catalyst plating solution containing a first metal element, a second metal element and a nonmetal element, adjusting the pH of the catalyst plating solution to 8-11 by using an alkali liquor, and then placing a substrate material with a nickel plating layer in the catalyst plating solution by adopting a three-electrode method for electroplating to obtain a cathode material;
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 nonmetal element is at least one of P, S and N.
In the method for preparing the electrolytic water cathode material, a base material is pretreated, cut to a certain size (for example, 1 × 2cm), and then preplated with nickel, and then a first metal element, a second metal element and a nonmetal element are plated on the base material at a specific pH. In the invention, the pre-nickel plating can increase the binding force between the three-element catalyst and the electrode after the pre-nickel plating, so that the catalyst plating layer is not easy to fall off.
In particular embodiments, different base materials require different pretreatment methods. For example: in the step (1), when the substrate material is stainless steel, the pretreatment specifically comprises the following steps: the substrate material is sequentially polished by using 320-mesh and 600-mesh SiC sand paper, the surface layer is removed, and then a potentiostat is used for removing a surface oxidation layer in a 0.5-2 mol/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 (the electrolyte is a sulfuric acid solution, and the surface oxidation layer can be quickly removed only under the condition that the potentiostat is used for electrifying). When the substrate material is nickel foil and/or copper foil, the pretreatment comprises the following specific operations: the base material is soaked in a hydrochloric acid solution of 0.5-2 mol/L (specifically, 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, 1.75mol/L or 2mol/L) for 10-30 minutes (for example, 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes), and then cleaned for standby. When the substrate material is carbon foil, the pretreatment specifically comprises the following operations: the substrate material is soaked in nitric acid solution of 0.5-2 mol/L (specifically, 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, 1.75mol/L or 2mol/L) for more than 1 hour, and then cleaned for later use.
In step (2), the nickel salt solution may be a conventional choice in the art, and may be, for example, NiCl2·6H2O solution and/or NiSO4·6H2And (4) O solution. In specific embodiments, the NiCl2·6H2The concentration of the O solution may be 0.5 to 2mol/L, for example, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2 mol/L.
In a particular embodiment, inIn the step (2), the nickel pre-plating can be performed in an electrodeposition mode. The electric current of the electrodeposition can be between-50 and-200 mA cm2For example, -50mA · cm2、 -100mA·cm2、-150mA·cm2Or-200 mA · cm2. In specific embodiments, in step (2), the electrodeposition time may be 5 to 30 minutes, for example, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes.
In the method of the present invention, the catalyst plating solution used needs to contain appropriate amounts of the first metal element, the second metal element, and the nonmetal element.
In a specific embodiment, in the catalyst plating solution of step (3), the concentration of the first metallic element may be 0.1 to 2mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, or 2 mol/L; the concentration of the second metal element may be 0.02 to 0.5mol/L, such as 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5 mol/L; the concentration of the non-metallic element may be 0.02 to 0.5mol/L, such as 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5 mol/L.
In a specific embodiment, the first metal element, the second metal element, and the non-metal element are provided by compounds conventionally used in the art. For example: when the first metal element is Ni, Ni in the catalyst plating solution can be NiSO4·6H2Providing O; when the first metal element is Co, the Co in the catalyst plating solution can be formed by CoSO4·7H2Providing O; when the first metal element is Fe, the Fe in the catalyst plating solution can be FeSO4·7H2And O. When the second metal element is Mo, the Mo in the catalyst plating solution may be Na2MoO4·2H2Providing O; when the second metal element is W, W in the catalyst plating solution may be Na2WO4·2H2And O. When the non-metallic element is P, the P in the catalyst plating solution can be NaH2PO4·2H2Providing O; when the non-metal element is S, the S in the catalyst plating solution can be provided by thiourea; the non-metal elementWhen the element is N, N in the catalyst plating solution may be provided by sodium nitrate.
In a specific embodiment, in the step (3), the current of the electroplating may be-50 to-200 mA-cm2For example, -50mA · cm2、-100mA·cm2、-150mA·cm2Or-200 mA · cm2. In a specific embodiment, in the step (3), the electrodeposition time may be 5 to 30 minutes, for example, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes.
In the method of the present invention, in order to facilitate the plating of the first metal element, the second metal element and the nonmetal element on the substrate, the catalyst plating solution of the step (3) further contains 0.1 to 1mol/L (for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.8mol/L or 1mol/L) of C6H5Na3O7·2H2And (4) O solution.
In a preferred embodiment, in step (3), the alkali solution is an ammonia solution, and ammonium ions in the ammonia solution can coordinate with the first metal element and the second metal element to facilitate electroplating.
In a second aspect, the present invention provides an electrolyzed water cathode material prepared by the method described above, the cathode material comprising a base material and a catalyst, the base material being at least one of stainless steel, a nickel foil, a copper foil, or a carbon foil, the catalyst containing a first metal element, a second metal element, and a non-metal element, 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.
In particular embodiments, the cathode material may have a composition of:
the substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P (Ni-Mo-P/stainless steel); or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P (Co-Mo-P/stainless steel); or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P (Fe-Mo-P/stainless steel); or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is P (Ni-W-P/stainless steel); or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is P (Co-W-P/stainless steel); or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is P (Fe-W-P/stainless steel); or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S (Ni-Mo-S/stainless steel); or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S (Co-Mo-S/stainless steel); or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S (Fe-Mo-S/stainless steel); or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is S (Ni-W-S/stainless steel); or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is S (Co-W-S/stainless steel); or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is S (Fe-W-S/stainless steel); or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N (Ni-Mo-N/stainless steel); or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N (Co-Mo-N/stainless steel); or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N (Fe-Mo-N/stainless steel); or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is N (Ni-W-N/stainless steel); or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is N (Co-W-N/stainless steel); or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is N (Fe-W-N/stainless steel); or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P (Ni-Mo-P/nickel foil); or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P (Co-Mo-P/nickel foil); or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P (Fe-Mo-P/nickel foil); or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P (Ni-W-P/nickel foil); or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P (Co-W-P/nickel foil); or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P (Fe-W-P/nickel foil); or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S (Ni-Mo-S/nickel foil); or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S (Co-Mo-S/nickel foil); or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S (Fe-Mo-S/nickel foil); or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S (Ni-W-S/nickel foil); or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S (Co-W-S/nickel foil); or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S (Fe-W-S/nickel foil); or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N (Ni-Mo-N/nickel foil); or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N (Co-Mo-N/nickel foil); or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N (Fe-Mo-N/nickel foil); or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N (Ni-W-N/nickel foil); or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N (Co-W-N/nickel foil); or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N (Fe-W-N/nickel foil); or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P (Ni-Mo-P/copper foil); or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P (Co-Mo-P/copper foil); or
The substrate material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P (Fe-Mo-P/copper foil); or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P (Ni-W-P/copper foil); or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P (Co-W-P/copper foil); or
The substrate material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P (Fe-W-P/copper foil); or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S (Ni-Mo-S/copper foil); or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S (Co-Mo-S/copper foil); or
The substrate material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S (Fe-Mo-S/copper foil); or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S (Ni-W-S/copper foil); or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S (Co-W-S/copper foil); or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S (Fe-W-S/copper foil); or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N (Ni-Mo-N/copper foil); or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N (Co-Mo-N/copper foil); or
The substrate material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N (Fe-Mo-N/copper foil); or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N (Ni-W-N/copper foil); or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N (Co-W-N/copper foil); or
The substrate material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N (Fe-W-N/copper foil); or
The substrate material is a carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P (Ni-Mo-P/carbon foil); or
The substrate material is a carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P (Co-Mo-P/carbon foil); or
The substrate material is a carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P (Fe-Mo-P/carbon foil); or
The substrate material is a carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P (Ni-W-P/carbon foil); or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P (Co-W-P/carbon foil); or
The substrate material is a carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P (Fe-W-P/carbon foil); or
The substrate material is a carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S (Ni-Mo-S/carbon foil); or
The substrate material is a carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S (Co-Mo-S/carbon foil); or
The substrate material is a carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S (Fe-Mo-S/carbon foil); or
The substrate material is a carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S (Ni-W-S/carbon foil); or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S (Co-W-S/carbon foil); or
The substrate material is a carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S (Fe-W-S/carbon foil); or
The substrate material is a carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N (Ni-Mo-N/carbon foil); or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N (Co-Mo-N/carbon foil); or
The substrate material is a carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N (Fe-Mo-N/carbon foil); or
The substrate material is a carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N (Ni-W-N/carbon foil); or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N (Co-W-N/carbon foil); or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N (Fe-W-N/carbon foil).
In a preferred embodiment, the composition of the cathode material may be: the base material is a nickel foil, the first metal element is Ni, the second metal element is Mo, the nonmetal element is P (N i-Mo-P/nickel foil) or the base material is a copper foil, the first metal element is Ni, the second metal element is Mo, the nonmetal element is P (Ni-Mo-P/copper foil) or the base material is a carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P (Ni-Mo-P/carbon foil). When the cathode material is composed in the modes, the current efficiency and the conversion rate of the cathode material electrocatalytic hydrogenation reduction dye are high.
In a third aspect the present invention provides the use of an electrolyzed water cathode material as hereinbefore described in an electrocatalytic hydrogenation of a vat dye. The electrolytic water cathode material is used for electrocatalytic hydrogenation reduction of dye, can reduce overpotential of reduced hydrogen and improve conversion rate of hydrogenation reduction products.
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 gold orange 3G, and vat violet RR, preferably indigo, sulfur black, vat yellow, and vat violet.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The following examples are provided to illustrate the preparation of the electrolytic water cathode material.
Example 1
(1) Pretreating a base material: sequentially polishing stainless steel by using 320-mesh and 600-mesh SiC sand paper, removing a surface layer, and then removing a surface oxide layer in 1mol/L sulfuric acid solution by using a potentiostat;
(2) pre-nickel plating: cutting the pretreated stainless steel into1X 2cm blocks, then NiCl at 1mol/L2·6H2In O solution at-160 mA cm2Performing electrodeposition for 20 minutes to obtain stainless steel with a nickel coating;
(3) preparing a Ni-Mo-P/stainless steel cathode material: preparing a catalyst plating solution containing Ni, Mo and P, wherein the composition of the catalyst plating solution is shown in Table 1, adjusting the pH of the catalyst plating solution to 9, and then placing the stainless steel with the nickel coating in the catalyst plating solution at-100 mA/cm by adopting a three-electrode method2Electroplating for 5 minutes to obtain the Ni-Mo-P/stainless steel cathode material.
Example 2
(1) Pretreating a base material: soaking the nickel foil in 1mol/L hydrochloric acid solution for 20 minutes;
(2) pre-nickel plating: cutting the pretreated nickel foil into blocks of 1X 2cm, and adding 1.5mol/L NiCl2·6H2In O solution at-160 mA cm2Performing electrodeposition for 15 minutes to obtain a nickel foil with a nickel coating;
(3) preparing a Ni-Mo-P/nickel foil cathode material: preparing a catalyst plating solution containing Ni, Mo and P, wherein the composition of the catalyst plating solution is shown in Table 1, adjusting the pH of the catalyst plating solution to 10, and then placing a nickel foil with a nickel plating layer in the catalyst plating solution at-100 mA cm by using a three-electrode method2Electroplating for 5 minutes to obtain the Ni-Mo-P/nickel foil cathode material.
Example 3
(1) Pretreating a base material: soaking the copper foil in 1.5mol/L hydrochloric acid solution for 15 minutes;
(2) pre-nickel plating: cutting the pretreated copper foil into blocks of 1 × 2cm, and adding NiSO of 0.5mol/L4·6H2In O solution at-160 mA cm2Carrying out electrodeposition for 25 minutes to obtain a copper foil with a nickel plating layer;
(3) preparing a Ni-Mo-P/copper foil cathode material: preparing a catalyst plating solution containing Ni, Mo and P, wherein the composition of the catalyst plating solution is shown in Table 1, adjusting the pH of the catalyst plating solution to 9.5, and then placing the copper foil with the nickel plating layer in the catalyst plating solution at-100 mA cm by using a three-electrode method2Bottom electroplatingAnd obtaining the Ni-Mo-P/copper foil cathode material after 15 minutes.
Example 4
(1) Pretreating a base material: soaking the carbon foil in 2mol/L nitric acid solution for 2 hours;
(2) pre-nickel plating: cutting the pretreated carbon foil into blocks of 1 × 2cm, and adding 1mol/L NiCl2·6H2In O solution at-160 mA cm2Performing electrodeposition for 20 minutes to obtain a carbon foil with a nickel coating;
(3) preparing a Ni-Mo-P/carbon foil cathode material: preparing a catalyst plating solution containing Ni, Mo and P, wherein the composition of the catalyst plating solution is shown in Table 1, adjusting the pH of the catalyst plating solution to 8.5, and then placing the carbon foil with the nickel coating in the catalyst plating solution at-100 mA/cm by adopting a three-electrode method2Electroplating for 5 minutes to obtain the Ni-Mo-P/carbon foil cathode material.
TABLE 1 composition of catalyst plating solution
Figure BDA0003108344970000221
Example 5
Was conducted in accordance with the procedure of example 1 except that CH was added to the catalyst plating solution4N2S replaces NaH2PO4·2H2And O to obtain the Ni-Mo-S/stainless steel cathode material.
Example 6
Was conducted in accordance with the procedure of example 1 except that CoSO was added to the catalyst plating solution4·7H2O instead of NiSO4·6H2And O, obtaining the Co-Mo-P/stainless steel cathode material.
Comparative example 1
Was carried out in accordance with the procedure of example 1, except that no NiSO was added to the catalyst plating solution4·6H2And O, obtaining the Mo-P/stainless steel cathode material.
Comparative example 2
Was carried out in the same manner as in example 1, except that Na was not added to the catalyst plating solution2MoO4·2H2And O, obtaining the Ni-P/stainless steel cathode material.
Comparative example 3
Was carried out in accordance with the procedure of example 1, except that NaH was not added to the catalyst plating solution2PO4·2H2And O to obtain the Ni-Mo/stainless steel cathode material.
Test example 1
5g of indigo is dissolved in 1L of a 1mol/L KOH solution, and the solution is sonicated for 5 minutes to completely disperse the indigo particles in the solution. Then, the cathode materials prepared in examples 1 to 6 and comparative examples 1 to 3 were used as a cathode and a platinum electrode was used as an anode, and they were connected by a potentiostat to carry out electrocatalytic hydrogenation reduction of indigo. Before the indigo is reduced, nitrogen is introduced for 30 minutes to fully discharge oxygen in the reaction tank, and then the nitrogen is added at 10 mA-cm2Reducing indigo at the current density of (1) for 12 hours. The current efficiency was calculated by measuring the decrease in the absorbance of indigo after the reaction using a spectrophotometer and determining the amount of reduction, and the results are shown in table 2.
Test example 2
The indigo solutions before and after the reduction using the cathode materials prepared in examples 1 to 6 and comparative examples 1 to 3 as cathodes were scanned at a scanning speed of 5nm/s within the interval of 200-800nm to determine the maximum absorption wavelength. From the uv-vis absorption spectrum, the maximum absorption wavelength of the indigo solution is 690nm, so the reduction efficiency of indigo can be obtained by comparing the absorption intensity of the indigo solution reduced for 12 hours with the original solution before reduction, and the results are shown in table 2. Wherein the cathode materials prepared in examples 1 to 4 had UV-VIS absorption spectra as shown in FIGS. 5 to 8
TABLE 2
Examples Electrode for electrochemical cell Area of electrode (cm)2) Conversion (%) Current efficiency (%)
Example 1 Ni-Mo-P/stainless steel 2 13.33 3.41
Example 2 Ni-Mo-P/nickel foil 2 27.21 4.19
Example 3 Ni-Mo-P/copper foil 2 16.37 6.96
Example 4 Ni-Mo-P/carbon foil 2 32.43 8.29
Example 5 Ni-Mo-S/stainless steel 2 14.22 3.63
Example 6 Co-Mo-P/stainless steel 2 12.52 3.20
Comparative example 1 Mo-P/stainless steel 2 9.23 2.36
Comparative example 2 Ni-P/stainless steel 2 11.61 2.97
Comparative example 3 Ni-Mo/stainless steel 2 10.53 2.69
As can be seen from the results in Table 2, the cathode material prepared by the method of the present invention has high current efficiency and conversion rate in the electrocatalytic hydrogenation reduction of indigo.
Test example 3
The kinetics process of electrochemical hydrogenation is similar to that of electrocatalytic hydrogen evolution, and all the processes are that hydrogen atoms with reducing capacity and adsorption states are generated on the surface of an electrode, and then the hydrogen atoms and water or organic molecules are utilized to carry out reaction. Therefore, this experiment also used the electrocatalytic hydrogen evolution test method to analyze the kinetics of the Ni-Mo-P cathode materials prepared in examples 1-4.
From the linear voltammetry scanning results, as shown in fig. 9 and fig. 10, the Ni-Mo-P/stainless steel has the best kinetics, and the overpotential is higher; the Ni-Mo-P/carbon foil has the lowest overpotential but the dynamic process is poor; the overpotential and Tafel slope of Ni-Mo-P/Ni foil and Ni-Mo-P/copper foil are similar, and the two may have similar kinetic processes. But due to the difference of the material substrate properties, Ni-Mo-P shows different reducing power to indigo on different electrode substrates. The Ni-Mo-P/stainless steel net has low contact frequency with indigo molecules due to small surface area, so that the effect of reducing the indigo is poor. While the nickel foil has a large surface area and a pore structure, Ni is a catalyst commonly used in electrocatalytic hydrogen evolution, and the effect of reducing indigo blue due to severe hydrogen evolution reaction on the surface is not high. The copper foil has a large surface area and a pore structure as the nickel foil, but copper is a catalyst capable of inhibiting hydrogen evolution in electrocatalysis, and thus exhibits a higher reduction effect than Ni — Mo — P/nickel foil. The carbon foil is used as the only non-metal substrate in several substrates, the main component of the carbon foil is graphite, the carbon foil has certain water absorption and certain affinity with indigo molecules, and therefore even though the dynamic process of the carbon foil is the worst, the Ni-Mo-P/carbon foil has the best effect of reducing indigo due to the good performance of the substrate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method for producing an electrolytic water cathode material, characterized in that the method comprises the steps of:
(1) pretreating a substrate material, wherein the substrate material is at least one of stainless steel, nickel foil, copper foil or carbon foil;
(2) cutting the pretreated substrate material into blocks, and then carrying out nickel preplating in a nickel salt solution to obtain a substrate material with a nickel plating layer;
(3) preparing a catalyst plating solution containing a first metal element, a second metal element and a nonmetal element, adjusting the pH of the catalyst plating solution to 8-11 by using an alkali liquor, and then placing a substrate material with a nickel coating in the catalyst plating solution by adopting a three-electrode method for electroplating to obtain a cathode material;
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 nonmetal element is at least one of P, S and N.
2. The method according to claim 1, wherein, in the step (1), when the substrate material is stainless steel, the pretreatment is carried out by: sequentially polishing the substrate material by using 320-mesh and 600-mesh SiC sand paper, removing a surface layer, and then removing a surface oxide layer in a 0.5-2 mol/L sulfuric acid solution by using a constant potential rectifier;
preferably, when the substrate material is a nickel foil and/or a copper foil, the pretreatment specifically comprises the following steps: soaking the substrate material in 0.5-2 mol/L hydrochloric acid solution for 10-30 minutes, and cleaning for later use;
preferably, when the substrate material is a carbon foil, the pretreatment specifically comprises the following steps: and (3) soaking the substrate material in a nitric acid solution of 0.5-2 mol/L for more than 1 hour, and cleaning for later use.
3. The method of claim 1, wherein in step (2), the nickel salt solution is NiCl2·6H2O and/or NiSO4·6H2O solution with the concentration of 0.5-2 mol/L;
preferably, in the step (2), nickel pre-plating is performed by electrodeposition; the conditions of the electrodeposition are as follows: the current is-50 to-200 mA cm2The time is 5-30 minutes.
4. The method according to claim 1, wherein in the catalyst plating solution of step (3), the concentration of the first metal element is 0.1 to 2mol/L, the concentration of the second metal element is 0.02 to 0.5mol/L, and the concentration of the nonmetal element is 0.02 to 0.5 mol/L;
the electroplating conditions are as follows: the current is-50 to-200 mA cm2The time is 5-30 minutes.
5. The method according to claim 4, wherein the catalyst plating solution of step (3) further contains 0.1 to 1mol/L of C6H5Na3O7·2H2And (4) O solution.
6. The method according to claim 1, wherein in the step (3), the alkali solution is an aqueous ammonia solution.
7. The electrolytic water cathode material produced by the method according to any one of claims 1 to 6, characterized in that the cathode material comprises a base material and a catalyst, the base material is at least one of stainless steel, nickel foil, copper foil or carbon foil, and the catalyst contains a first metal element, a second metal element and a non-metal element, 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.
8. The cathode material of claim 7, wherein the cathode material has a composition of:
the substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The substrate material is stainless steel, the first metal element is Fe, the second metal element is W, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The substrate material is nickel foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The base material is copper foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is copper foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The base material is copper foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is P; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is S; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is Mo, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Ni, the second metal element is W, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Co, the second metal element is W, and the nonmetal element is N; or
The substrate material is carbon foil, the first metal element is Fe, the second metal element is W, and the nonmetal element is N.
9. Use of the electrolytic water cathode material of claim 7 or 8 for electrocatalytic hydrogenation of vat dyes.
10. The use according to claim 9, wherein 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 gold orange 3G and vat violet RR.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19962155A1 (en) * 1999-12-22 2001-06-28 Basf Ag Electrochemical reduction of vat dye using cathode with electroconductive, cathodically-polarized layer formed in situ by sedimentation on electroconductive substrate, is carried out in presence of base
CN102787329A (en) * 2012-08-31 2012-11-21 重庆大学 Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode
US20150065339A1 (en) * 2013-07-03 2015-03-05 Yale University Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof
CN105483751A (en) * 2015-12-08 2016-04-13 天津市大陆制氢设备有限公司 Efficient Ni-S-Mo hydrogen evolution electrode and preparation method thereof
CN107081163A (en) * 2017-05-10 2017-08-22 北京工业大学 A kind of NiWP electrocatalyst materials of three-dimensional structure are prepared and applied
CN110158126A (en) * 2019-05-31 2019-08-23 上海交通大学 A kind of method that metal surface prepares ternary metal hydrogen-precipitating electrode
CN112279344A (en) * 2020-09-10 2021-01-29 燕山大学 Method for fully recycling dye waste liquid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19962155A1 (en) * 1999-12-22 2001-06-28 Basf Ag Electrochemical reduction of vat dye using cathode with electroconductive, cathodically-polarized layer formed in situ by sedimentation on electroconductive substrate, is carried out in presence of base
CN102787329A (en) * 2012-08-31 2012-11-21 重庆大学 Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode
US20150065339A1 (en) * 2013-07-03 2015-03-05 Yale University Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof
CN105483751A (en) * 2015-12-08 2016-04-13 天津市大陆制氢设备有限公司 Efficient Ni-S-Mo hydrogen evolution electrode and preparation method thereof
CN107081163A (en) * 2017-05-10 2017-08-22 北京工业大学 A kind of NiWP electrocatalyst materials of three-dimensional structure are prepared and applied
CN110158126A (en) * 2019-05-31 2019-08-23 上海交通大学 A kind of method that metal surface prepares ternary metal hydrogen-precipitating electrode
CN112279344A (en) * 2020-09-10 2021-01-29 燕山大学 Method for fully recycling dye waste liquid

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