CN110629249B - Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate - Google Patents

Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate Download PDF

Info

Publication number
CN110629249B
CN110629249B CN201910936965.4A CN201910936965A CN110629249B CN 110629249 B CN110629249 B CN 110629249B CN 201910936965 A CN201910936965 A CN 201910936965A CN 110629249 B CN110629249 B CN 110629249B
Authority
CN
China
Prior art keywords
steel plate
pore
preparing
hydrogen evolution
forming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910936965.4A
Other languages
Chinese (zh)
Other versions
CN110629249A (en
Inventor
田栋
夏方诠
周长利
刘建辉
刘汉彪
衣姜乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201910936965.4A priority Critical patent/CN110629249B/en
Publication of CN110629249A publication Critical patent/CN110629249A/en
Application granted granted Critical
Publication of CN110629249B publication Critical patent/CN110629249B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • 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
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • 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 discloses a method for preparing a high-activity hydrogen evolution electrode by surface chemical plating-pore forming of a flocked steel plate, and relates to a method for preparing a high-electrolysis hydrogen evolution active electrode. The invention aims to solve the problem that the prior non-noble metal hydrogen evolution catalyst for electrolysis has poor performance. The method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate comprises the following steps: (1) preparing an activating solution; (2) preparing a plating solution; (3) preparing a pore-forming vulcanizing liquid; (4) chemically spraying an alloy coating; (5) and (3) performing pore-forming vulcanization treatment, and preparing a catalyst layer with excellent hydrogen evolution reaction activity on the surface of the flocked steel plate, so that the reduction of the energy consumption for hydrogen evolution by alkaline solution electrolysis is facilitated.

Description

Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate
Technical Field
The invention belongs to the field of hydrogen evolution electrode preparation, and relates to a method for preparing a high-activity hydrogen evolution electrode on the surface of a flocked steel plate by adopting chemical plating-pore forming, so that the activity of the hydrogen evolution electrode is improved.
Background
The year-by-year increase of the usage amount of fossil fuel in the life process of human in recent years not only causes the sharp consumption of fossil energy, but also causes the environment to suffer from huge pollution. Carbon dioxide and nitrogen oxides generated in the combustion process of fossil fuels greatly increase harmful components in the air, and easily cause greenhouse effect and acid rain. Furthermore, hydrocarbons and solid particles generated by insufficient combustion of fossil fuels are one of the main causes of serious degradation of air quality in recent years. Therefore, substitutes of traditional fossil fuels are greatly sought, the urgent need of energy exhaustion can be solved, and the method has important significance for environmental management and protection.
Hydrogen is a new clean energy, and if it is burned, it generates a large amount of heat energy and only clean water in its combustion process, while if it is used as a negative active material of a fuel cell, it emits a large amount of electric energy and its discharge product is only clean water. Therefore, hydrogen will play an increasing role in the future energy world and is also an important factor for the evolution of human society. However, hydrogen in nature is very rare, and how to prepare pure hydrogen by proper means is a significant issue facing the energy field at present. Among the various hydrogen production methods, the hydrogen production by electrolyzing water has unique advantages, such as high hydrogen production purity, simple and easy process, strong production capacity and the like. The hydrogen production by water electrolysis is an important way for solving the future energy crisis by converting the electrical energy which cannot be stored into chemical energy in hydrogen which can be stored by an electrolysis method so as to store the electrical energy generated by renewable energy sources such as solar energy, wind energy and the like. At present, the hydrogen production by water electrolysis has important industrial basis, namely the chlor-alkali industry, and the principle is that water is electrolyzed in an alkaline aqueous solution and high-purity hydrogen is generated at a cathode.
However, the current industrial hydrogen production by water electrolysis faces an important technical bottleneck, that is, non-noble metal electrodes with low activity, such as steel plates, nickel plates and other metal electrodes, are adopted in the electrolysis process to reduce the hardware input cost. The non-noble metal electrode has serious electrochemical polarization in the electrolytic process, namely the efficiency of converting electric energy into chemical energy is too low, and a large amount of electric energy is consumed. Therefore, in order to improve the catalytic capability of the non-noble metal electrode in the hydrogen production process by electrolysis, the non-noble metal electrode needs to be effectively modified to reduce the hydrogen evolution overpotential. The hydrogen evolution activity of the non-noble metal electrode is improved by preparing the catalytic material which has huge specific surface area and excellent catalytic activity from two aspects of geometric factors and energy factors of the electrode, so that the catalytic material can really have practical application value. The flocked steel plate fixes the fluff with huge specific surface area on the surface of the steel plate in an electrostatic flocking mode, the fluff with huge specific surface area is used as a template to effectively improve the specific surface area of an electrode, and a film layer with excellent catalytic activity is obtained on the surface of the flocked steel plate in a chemical plating mode, so that the catalytic capability can be exerted to the maximum extent, and if the flocked steel plate is used as a basis to prepare the hydrogen evolution electrode with excellent performance, the flocked steel plate has important significance for the development of renewable energy sources and the sustainable development of society.
Disclosure of Invention
The invention provides a method for preparing a high-activity hydrogen evolution electrode on the surface of a flocked steel plate by chemical plating-pore forming, aiming at solving the problem that the prior non-noble metal electrolytic hydrogen evolution catalyst has poorer performance.
The method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate comprises the following steps:
(1) preparing an activating solution: a. sequentially dissolving anionic polyacrylamide with the concentration of 0.3-1.6 g/L and palladium acetate with the concentration of 0.1-0.5 g/L in deionized water, and stirring for 5-10 hours to obtain an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300-1200 ten thousand;
(2) preparing a plating solution: b. sequentially dissolving 1.6-18.0 g/L composite complexing agent, 0.3-1.0 g/L silver nitrate, 1.0-5.0 g/L copper nitrate, 0.8-6.0 g/L nickel salt, 0.6-3.0 g/L cobalt salt and 0.05-0.6 g/L sodium tungstate in deionized water, adjusting the pH to 10.0-13.0 by using potassium hydroxide, and aging for more than 12 hours to prepare a plating solution A; c. sequentially dissolving a reducing agent with the concentration of 0.5-8.0 g/L and a non-ionic surfactant with the concentration of 0.01-0.5 g/L in deionized water to prepare a plating solution B;
(3) preparing a pore-forming vulcanizing liquid: d. dissolving 10-100 mL/L sulfuric acid, 8-35 g/L citric acid and 10-80 g/L thiourea in deionized water at the temperature of 40-70 ℃ to complete preparation of a copper pore-forming vulcanizing liquid;
(4) chemical spraying of alloy coating: e. uniformly and equivalently spraying the activating solution prepared in the step (1) and absolute ethyl alcohol on the surface of a clean flocked steel plate by using a double-head spray gun, and naturally drying to obtain the flocked steel plate with the activated surface; f. respectively heating the plating solution A and the plating solution B prepared in the step (2) to 30-60 ℃, simultaneously spraying the plating solutions on the surface of the flocked steel plate activated in the step e in an equivalent manner by using a double-head spray gun, spraying for 10-300 seconds, cleaning the residual spraying plating solution by using deionized water, spraying absolute ethyl alcohol, and drying by cold air to finish the alloy plating layer sprayed on the surface of the flocked steel plate;
(5) pore-forming vulcanization treatment: g. and (3) immersing the flocked steel plate/alloy coating prepared in the step (4) into the copper pore-forming vulcanizing liquid prepared in the step (3) for 2-180 minutes at a constant temperature of 40-70 ℃, and then completing pore-forming vulcanizing treatment after one-time tap water cleaning and three-time deionized water cleaning, so as to obtain a porous film with excellent hydrogen evolution catalytic activity on the surface of the flocked steel plate.
The composite complexing agent in the step (2) is a combination of any four of ammonia water, ethylenediamine, disodium ethylenediamine tetraacetate, sodium citrate, sodium adipate, sodium potassium tartrate, sodium scallop and sodium gluconate, the nickel salt is one of nickel acetate or nickel nitrate, the cobalt salt is one of cobalt acetate or cobalt nitrate, the reducing agent is one of sodium hypophosphite, hydrazine hydrate or sodium borohydride, and the nonionic surfactant is one of OP-10, glucoside or PPE.
The method for preparing the high-activity hydrogen evolution electrode by chemically plating and pore-forming the surface of the flocked steel plate utilizes the fluff on the surface of the flocked steel plate as a template to provide a huge catalytic surface. In the activation process, the activating solution can be adsorbed on the surface of the flocked steel plate through the adsorptive anionic polyacrylamide in the activating solution, and palladium ions are fixed by using electrostatic attraction to complete the activation of the flocked steel plate. During the spraying process, the fixed palladium ions are reduced to generate palladium nano particles, so that the surface of the flocked steel plate becomes a surface which can be oxidized by a catalytic reducing agent, a chemical spraying reaction is initiated to be carried out spontaneously, and a copper-silver-nickel-cobalt-tungsten alloy coating is formed on the surface of the flocked steel plate, so that the flocked steel plate is conductive and has excellent hydrogen evolution catalytic activity. In the subsequent pore-forming sulfuration process, the formed copper-silver-nickel-cobalt-tungsten alloy coating can be subjected to complex dissolution in the pore-forming sulfuration solution, wherein the copper element has the highest activity and is dissolved preferentially, so that the pore-forming silver-nickel-cobalt-tungsten-sulfur alloy coating is formed. The silver element can greatly improve the conductivity of the plating layer, the nickel and cobalt elements have good hydrogen evolution catalytic activity, and the tungsten and sulfur elements can further improve the hydrogen evolution catalytic activity of the nickel and cobalt in a synergistic manner, so that the prepared composite film has excellent hydrogen evolution performance, and the preparation method is beneficial to improving the capacity of hydrogen production by electrolysis and reducing the energy consumption.
Drawings
FIG. 1 shows a test in which a hydrogen evolution electrode prepared by a chemical plating-pore-forming method is placed on the surface of a flocked steel plate in a 1.0M KOH solution, and the cathode current density is 250 mA/cm2The time-potential curve measured under the conditions of (1).
Detailed Description
The first embodiment is as follows: the method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate comprises the following steps of:
(1) preparing an activating solution: a. sequentially dissolving anionic polyacrylamide with the concentration of 0.3-1.6 g/L and palladium acetate with the concentration of 0.1-0.5 g/L in deionized water, and stirring for 5-10 hours to obtain an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300-1200 ten thousand;
(2) preparing a plating solution: b. sequentially dissolving 1.6-18.0 g/L composite complexing agent, 0.3-1.0 g/L silver nitrate, 1.0-5.0 g/L copper nitrate, 0.8-6.0 g/L nickel salt, 0.6-3.0 g/L cobalt salt and 0.05-0.6 g/L sodium tungstate in deionized water, adjusting the pH to 10.0-13.0 by using potassium hydroxide, and aging for more than 12 hours to prepare a plating solution A; c. sequentially dissolving a reducing agent with the concentration of 0.5-8.0 g/L and a non-ionic surfactant with the concentration of 0.01-0.5 g/L in deionized water to prepare a plating solution B;
(3) preparing a pore-forming vulcanizing liquid: d. dissolving 10-100 mL/L sulfuric acid, 8-35 g/L citric acid and 10-80 g/L thiourea in deionized water at the temperature of 40-70 ℃ to complete preparation of a copper pore-forming vulcanizing liquid;
(4) chemical spraying of alloy coating: e. uniformly and equivalently spraying the activating solution prepared in the step (1) and absolute ethyl alcohol on the surface of a clean flocked steel plate by using a double-head spray gun, and naturally drying to obtain the flocked steel plate with the activated surface; f. respectively heating the plating solution A and the plating solution B prepared in the step (2) to 30-60 ℃, simultaneously spraying the plating solutions on the surface of the flocked steel plate activated in the step e in an equivalent manner by using a double-head spray gun, spraying for 10-300 seconds, cleaning the residual spraying plating solution by using deionized water, spraying absolute ethyl alcohol, and drying by cold air to finish the alloy plating layer sprayed on the surface of the flocked steel plate;
(5) pore-forming vulcanization treatment: g. and (3) immersing the flocked steel plate/alloy coating prepared in the step (4) into the copper pore-forming vulcanizing liquid prepared in the step (3) for 2-180 minutes at a constant temperature of 40-70 ℃, and then completing pore-forming vulcanizing treatment after one-time tap water cleaning and three-time deionized water cleaning, so as to obtain a porous film with excellent hydrogen evolution catalytic activity on the surface of the flocked steel plate.
According to the method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate, the anionic polyacrylamide with adsorbability is added into the activating solution, so that the anionic polyacrylamide can be uniformly adsorbed on the surface of the flocked steel plate under the action of absolute ethyl alcohol and a composite nonionic surfactant in the activation process, palladium ions can be fixed on the surface of the flocked steel plate through electrostatic attraction, and the activation of the flocked steel plate is completed. Then, the plating solutions A and B are uniformly sprayed on the surface of the flocked steel plate, and the fixed palladium ions can be reduced to generate palladium nano particles under the action of a reducing agent in the plating solution B, so that the surface of the flocked steel plate becomes a surface capable of catalyzing the oxidation of the reducing agent, and the chemical spraying reaction is initiated to be carried out spontaneously. The method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate not only can obtain the same appearance as pure silver, but also can greatly prolong the service life.
The second embodiment is as follows: the difference between the embodiment and the specific embodiment is that the composite complexing agent in the step (2) is a combination of any four of ammonia water, ethylenediamine, disodium ethylenediamine tetraacetate, sodium citrate, sodium adipate, sodium potassium tartrate, sodium scallop or sodium gluconate. The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is that the nickel salt in step (2) is one of nickel acetate and nickel nitrate. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: this embodiment is different from the first to third embodiments in that the cobalt salt in the step (2) is one of cobalt acetate and cobalt nitrate. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to the fourth embodiments is that the reducing agent in step (2) is one of sodium hypophosphite, hydrazine hydrate or sodium borohydride. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: this embodiment is different from one of the first to fifth embodiments in that the nonionic surfactant in the step (2) is one of OP-10, glucoside or PPE. The other is the same as one of the first to fifth embodiments.
The beneficial effects of the invention were verified by the following tests:
test one: the method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate in the test comprises the following steps:
(1) preparing an activating solution: a. sequentially dissolving anionic polyacrylamide with the concentration of 0.9 g/L and palladium acetate with the concentration of 0.6 g/L in deionized water, and stirring for 8 hours to prepare an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300 ten thousand;
(2) preparing a plating solution: b. sequentially dissolving a composite complexing agent with the concentration of 6.0 g/L, silver nitrate with the concentration of 0.5 g/L, copper nitrate with the concentration of 5.0 g/L, nickel nitrate with the concentration of 2.0 g/L, cobalt nitrate with the concentration of 1.2 g/L and sodium tungstate with the concentration of 0.2 g/L in deionized water, adjusting the pH value to 12.0 by using potassium hydroxide, and then aging for more than 12 hours to prepare a plating solution A; c. sequentially dissolving hydrazine hydrate with the concentration of 5.0 g/L and glucoside with the concentration of 0.2 g/L in deionized water to prepare plating solution B;
(3) preparing a pore-forming vulcanizing liquid: d. dissolving 50 mL/L sulfuric acid, 15 g/L citric acid and 60 g/L thiourea in deionized water at 60 ℃ to complete the preparation of the copper pore-forming sulfide solution;
(4) spraying an alloy coating: e. uniformly and equivalently spraying the activating solution prepared in the step (1) and absolute ethyl alcohol on the surface of a clean flocked steel plate by using a double-head spray gun, and naturally drying to obtain the flocked steel plate with the activated surface; f. respectively heating the plating solution A and the plating solution B prepared in the step (2) to 50 ℃, simultaneously spraying the plating solution A and the plating solution B on the surface of the flocked steel plate activated in the step e in an equivalent manner by using a double-head spray gun, spraying for 100 seconds, cleaning the residual spraying plating solution by using deionized water, spraying absolute ethyl alcohol, and drying by cold air to finish the alloy plating layer sprayed on the surface of the flocked steel plate;
(5) pore-forming vulcanization treatment: g. and (3) immersing the flocked steel plate/alloy coating prepared in the step (4) into the copper pore-forming vulcanizing liquid prepared in the step (3) for 80 minutes at a constant temperature of 45 ℃, and then completing pore-forming vulcanizing treatment after one-time tap water cleaning and three-time deionized water cleaning, so as to obtain a porous film with excellent hydrogen evolution catalytic activity on the surface of the flocked steel plate.
The composite complexing agent in the step (2) is a combination of ammonia water, ethylenediamine, potassium sodium tartrate and scallop element.
This experiment utilizes the fine hair on flocking steel sheet surface to act as the template and provides huge catalytic surface, and at the activation in-process, through the adsorptivity anion type polyacrylamide in the activation liquid, makes it can adsorb on flocking steel sheet surface and utilize the fixed palladium ion of electrostatic attraction, accomplishes the activation of flocking steel sheet. During the spraying process, the fixed palladium ions are reduced to generate palladium nano particles, so that the surface of the flocked steel plate becomes a surface which can be oxidized by a catalytic reducing agent, a chemical spraying reaction is initiated to be carried out spontaneously, and a copper-silver-nickel-cobalt-tungsten alloy coating is formed on the surface of the flocked steel plate, so that the flocked steel plate is conductive and has excellent hydrogen evolution catalytic activity. In the subsequent pore-forming sulfuration process, the formed copper-silver-nickel-cobalt-tungsten alloy coating can be subjected to complex dissolution in the pore-forming sulfuration solution, wherein the copper element has the highest activity and is dissolved preferentially, so that the pore-forming silver-nickel-cobalt-tungsten-sulfur alloy coating is formed. The silver element can greatly improve the conductivity of the plating layer, the nickel and cobalt elements have good hydrogen evolution catalytic activity, and the tungsten and sulfur elements can further synergistically improve the hydrogen evolution catalytic activity of the nickel and cobalt, so that the prepared composite filmThe layer has excellent hydrogen evolution performance, and is beneficial to improving the productivity of hydrogen production by electrolysis and reducing the energy consumption. The test is carried out by putting hydrogen evolution electrode prepared by spray plating-pore-forming method on the surface of flocked steel plate in 1.0M KOH solution, and cathode current density is 250 mA/cm2The time-potential curve measured under the conditions of (1) is shown in FIG. 1. As can be seen from FIG. 1, the hydrogen evolution electrode prepared by the electroless plating-pore forming method on the surface of the flocked steel sheet is in a 1.0M KOH solution, and the cathode current density is 250 mA/cm2The overpotential for hydrogen evolution under the condition (1) is only about 163 mV, which shows that the prepared hydrogen evolution material has excellent activity.

Claims (5)

1. The method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate is characterized in that the method for preparing the high-activity hydrogen evolution electrode by surface chemical plating-pore forming of the flocked steel plate is carried out according to the following steps:
(1) preparing an activating solution: a. sequentially dissolving anionic polyacrylamide with the concentration of 0.3-1.6 g/L and palladium acetate with the concentration of 0.1-0.5 g/L in deionized water, and stirring for 5-10 hours to obtain an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300-1200 ten thousand;
(2) preparing a plating solution: b. sequentially dissolving 1.6-18.0 g/L composite complexing agent, 0.3-1.0 g/L silver nitrate, 1.0-5.0 g/L copper nitrate, 0.8-6.0 g/L nickel salt, 0.6-3.0 g/L cobalt salt and 0.05-0.6 g/L sodium tungstate in deionized water, adjusting the pH to 10.0-13.0 by using potassium hydroxide, and aging for more than 12 hours to prepare a plating solution A; c. sequentially dissolving a reducing agent with the concentration of 0.5-8.0 g/L and a non-ionic surfactant with the concentration of 0.01-0.5 g/L in deionized water to prepare a plating solution B;
(3) preparing a pore-forming vulcanizing liquid: d. dissolving 10-100 mL/L sulfuric acid, 8-35 g/L citric acid and 10-80 g/L thiourea in deionized water at the temperature of 40-70 ℃ to complete preparation of a copper pore-forming vulcanizing liquid;
(4) chemical spraying of alloy coating: e. uniformly and equivalently spraying the activating solution prepared in the step (1) and absolute ethyl alcohol on the surface of a clean flocked steel plate by using a double-head spray gun, and naturally drying to obtain the flocked steel plate with the activated surface; f. respectively heating the plating solution A and the plating solution B prepared in the step (2) to 30-60 ℃, simultaneously spraying the plating solutions on the surface of the flocked steel plate activated in the step e in an equivalent manner by using a double-head spray gun, spraying for 10-300 seconds, cleaning the residual spraying plating solution by using deionized water, spraying absolute ethyl alcohol, and drying by cold air to finish the chemical spraying of an alloy plating layer on the surface of the flocked steel plate;
(5) pore-forming vulcanization treatment: g. immersing the flocked steel plate/alloy coating prepared in the step (4) into the copper pore-forming vulcanizing liquid prepared in the step (3) for 2-180 minutes at a constant temperature of 40-70 ℃, and then completing pore-forming vulcanizing treatment after one-time tap water cleaning and three-time deionized water cleaning, so as to obtain a porous film with excellent hydrogen evolution catalytic activity on the surface of the flocked steel plate;
the composite complexing agent in the step (2) is a combination of any four of ammonia water, ethylenediamine, disodium ethylene diamine tetraacetate, sodium citrate, sodium adipate, potassium sodium tartrate, scallop extract or sodium gluconate.
2. The method for preparing the high-activity hydrogen evolution electrode by chemically plating and pore-forming the surface of the flocked steel plate according to claim 1, wherein the nickel salt in the step (2) is one of nickel acetate or nickel nitrate.
3. The method for preparing a high-activity hydrogen evolution electrode by chemically plating and pore-forming the surface of the flocked steel plate according to claim 1, wherein the cobalt salt in the step (2) is one of cobalt acetate or cobalt nitrate.
4. The method for preparing the high-activity hydrogen evolution electrode by chemically plating and pore-forming the surface of the flocked steel plate according to claim 1, wherein the reducing agent in the step (2) is one of sodium hypophosphite, hydrazine hydrate or sodium borohydride.
5. The method for preparing a high-activity hydrogen evolution electrode by surface chemical plating-pore-forming on a flocked steel plate according to claim 1, wherein the non-ionic surfactant in the step (2) is one of OP-10, glucoside or PPE.
CN201910936965.4A 2019-09-29 2019-09-29 Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate Active CN110629249B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910936965.4A CN110629249B (en) 2019-09-29 2019-09-29 Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910936965.4A CN110629249B (en) 2019-09-29 2019-09-29 Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate

Publications (2)

Publication Number Publication Date
CN110629249A CN110629249A (en) 2019-12-31
CN110629249B true CN110629249B (en) 2021-07-13

Family

ID=68973831

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910936965.4A Active CN110629249B (en) 2019-09-29 2019-09-29 Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate

Country Status (1)

Country Link
CN (1) CN110629249B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881991B (en) * 2021-11-19 2023-08-11 山东省路桥集团有限公司 Pretreatment method for coating steel structure bridge

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6797312B2 (en) * 2003-01-21 2004-09-28 Mattson Technology, Inc. Electroless plating solution and process
CN100534671C (en) * 2006-12-27 2009-09-02 上海海联润滑材料科技有限公司 Nano core-shell type copper-nickel bimetal powder body and preparing method and application thereof
CN104018142B (en) * 2014-06-19 2016-03-30 林忠华 Electroless plating nickel-tin-phosphorus alloy plating liquid
CN104561961A (en) * 2014-12-27 2015-04-29 广东致卓精密金属科技有限公司 Chemical cobalt-nickel plating alloy liquid and process
CN104561943B (en) * 2014-12-27 2017-05-10 广东致卓精密金属科技有限公司 Chemical nickel-palladium alloy plating process for circuit boards

Also Published As

Publication number Publication date
CN110629249A (en) 2019-12-31

Similar Documents

Publication Publication Date Title
CN111575729B (en) Nickel phosphide compound with multi-level hole structure and preparation method and application thereof
CN106191916A (en) A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof
CN111705332B (en) Simple electrodeposited Co-Ce/NF electrode material and preparation and application thereof
CN108075144B (en) Core-shell structure catalyst for fuel cell and preparation and application thereof
CN112520818B (en) Preparation method and application of metal electrode for reducing nitrate nitrogen in wastewater
CN110331415B (en) Three-dimensional bimetal oxide current collector electrode material, preparation method and application thereof
WO2023143578A1 (en) Porous nickel-molybdenum-cobalt hydrogen evolution electrode, preparation method therefor and application thereof
CN106334561A (en) Non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride and preparation method of non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride
CN113908870B (en) Controllable preparation of double-function non-noble metal nitride catalyst and high-current electrolytic urea hydrogen production application
CN110629249B (en) Method for preparing high-activity hydrogen evolution electrode by surface chemical plating-pore forming of flocked steel plate
CN102616739A (en) Device and application for photocatalytic water decomposition
CN106319558A (en) Efficient and porous MoS2-Zn hydrogen evolution electrode and preparation method thereof
CN116377501B (en) Electrocatalytic hydrogen evolution material and preparation method and application thereof
CN103103562A (en) Ni-Co-W-Cu-B multicomponent cathode material, and preparation method and application thereof
CN110983373A (en) Supported composite sulfide hydrogen evolution catalyst and preparation method and application thereof
CN114045509B (en) Seawater electrolysis device with sodium ion conduction and application thereof
CN114318361B (en) Preparation method of vanadium oxide modified Raney nickel alloy electrode, electrode and application
US7879750B2 (en) Anodes for alkaline electrolysis
CN113249743B (en) Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof
CN110923737A (en) Nano porous hydrogen production catalyst and preparation method thereof
CN115466979A (en) Preparation method of nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution
CN110548527B (en) Preparation of load type Ni-Fe-P-MnFeO by chemical plating 3 Method of electrocatalyst
CN113502495A (en) Simple and low-cost preparation method of water hydrogen production energy material
CN101191237B (en) Method for preparing hydrogen-preparing hydrogen-storing integrated electrode
CN113430557B (en) Multifunctional power layer electrode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant