CN110629249A - 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 PDFInfo
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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
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) sequentially dissolving anionic polyacrylamide with the concentration of 0.3 ~ 1.6.6 g/L and palladium acetate with the concentration of 0.1 ~ 0.5.5 g/L into deionized water, and stirring for 5 ~ 10 hours to obtain an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300 ten thousand ~ 1200 ten thousand;
(2) b, dissolving a composite complexing agent with the concentration of 1.6 ~ 18.0.0 g/L, silver nitrate with the concentration of 0.3 ~ 1.0.0 g/L, copper nitrate with the concentration of 1.0 ~ 5.0.0 g/L, nickel salt with the concentration of 0.8 ~ 6.0.0 g/L, cobalt salt with the concentration of 0.6 ~ 3.0.0 g/L and sodium tungstate with the concentration of 0.05 ~ 0.6.6 g/L in deionized water in sequence, adjusting the pH to 10.0 ~ 13.0.0 by using potassium hydroxide, and then aging for more than 12 hours to obtain a plating solution A, c, dissolving a reducing agent with the concentration of 0.5 ~ 8.0.0 g/L and a nonionic surfactant with the concentration of 0.01 ~ 0.5.5 g/L in deionized water in sequence to obtain a plating solution B;
(3) d, dissolving sulfuric acid with the concentration of 10 ~ 100 mL/L, citric acid with the concentration of 8 ~ 35 g/L and thiourea with the concentration of 10 ~ 80 g/L into deionized water at the temperature of 40 ~ 70 ℃ to complete the preparation of the copper pore-forming sulfide solution;
(4) f, respectively heating the plating solution A and the plating solution B prepared in the step (2) to 30 ~ 60 ℃, 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 equal amount by using a double-end spray gun, spraying the flocking steel plate activated in the step e 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 on the surface of the flocked steel plate;
(5) and 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 cleaning by tap water and deionized water for three times to complete pore-forming vulcanizing treatment, so that the porous film with excellent hydrogen evolution catalytic activity is obtained 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) sequentially dissolving anionic polyacrylamide with the concentration of 0.3 ~ 1.6.6 g/L and palladium acetate with the concentration of 0.1 ~ 0.5.5 g/L into deionized water, and stirring for 5 ~ 10 hours to obtain an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300 ten thousand ~ 1200 ten thousand;
(2) b, dissolving a composite complexing agent with the concentration of 1.6 ~ 18.0.0 g/L, silver nitrate with the concentration of 0.3 ~ 1.0.0 g/L, copper nitrate with the concentration of 1.0 ~ 5.0.0 g/L, nickel salt with the concentration of 0.8 ~ 6.0.0 g/L, cobalt salt with the concentration of 0.6 ~ 3.0.0 g/L and sodium tungstate with the concentration of 0.05 ~ 0.6.6 g/L in deionized water in sequence, adjusting the pH to 10.0 ~ 13.0.0 by using potassium hydroxide, and then aging for more than 12 hours to obtain a plating solution A, c, dissolving a reducing agent with the concentration of 0.5 ~ 8.0.0 g/L and a nonionic surfactant with the concentration of 0.01 ~ 0.5.5 g/L in deionized water in sequence to obtain a plating solution B;
(3) d, dissolving sulfuric acid with the concentration of 10 ~ 100 mL/L, citric acid with the concentration of 8 ~ 35 g/L and thiourea with the concentration of 10 ~ 80 g/L into deionized water at the temperature of 40 ~ 70 ℃ to complete the preparation of the copper pore-forming sulfide solution;
(4) f, respectively heating the plating solution A and the plating solution B prepared in the step (2) to 30 ~ 60 ℃, 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 equal amount by using a double-end spray gun, spraying the flocking steel plate activated in the step e 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 on the surface of the flocked steel plate;
(5) and 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 cleaning by tap water and deionized water for three times to complete pore-forming vulcanizing treatment, so that the porous film with excellent hydrogen evolution catalytic activity is obtained 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. Silver ions, nickel ions and molybdate ions in the plating solution A can be reduced on the surface of the flocked steel plate with catalytic activity simultaneously, so that the silver-nickel-molybdenum alloy with mirror luster and excellent corrosion resistance can be rapidly formed. 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 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. 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 1.0 MKOH 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 (6)
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) sequentially dissolving anionic polyacrylamide with the concentration of 0.3 ~ 1.6.6 g/L and palladium acetate with the concentration of 0.1 ~ 0.5.5 g/L into deionized water, and stirring for 5 ~ 10 hours to obtain an activating solution, wherein the molecular weight of the anionic polyacrylamide is 300 ten thousand ~ 1200 ten thousand;
(2) b, dissolving a composite complexing agent with the concentration of 1.6 ~ 18.0.0 g/L, silver nitrate with the concentration of 0.3 ~ 1.0.0 g/L, copper nitrate with the concentration of 1.0 ~ 5.0.0 g/L, nickel salt with the concentration of 0.8 ~ 6.0.0 g/L, cobalt salt with the concentration of 0.6 ~ 3.0.0 g/L and sodium tungstate with the concentration of 0.05 ~ 0.6.6 g/L in deionized water in sequence, adjusting the pH to 10.0 ~ 13.0.0 by using potassium hydroxide, and then aging for more than 12 hours to obtain a plating solution A, c, dissolving a reducing agent with the concentration of 0.5 ~ 8.0.0 g/L and a nonionic surfactant with the concentration of 0.01 ~ 0.5.5 g/L in deionized water in sequence to obtain a plating solution B;
(3) d, dissolving sulfuric acid with the concentration of 10 ~ 100 mL/L, citric acid with the concentration of 8 ~ 35 g/L and thiourea with the concentration of 10 ~ 80 g/L into deionized water at the temperature of 40 ~ 70 ℃ to complete the preparation of the copper pore-forming sulfide solution;
(4) f, respectively heating the plating solution A and the plating solution B prepared in the step (2) to 30 ~ 60 ℃, 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 equal amount by using a double-end spray gun, spraying the flocking steel plate activated in the step e for 10 ~ 300 seconds, cleaning the residual spraying plating solution by using deionized water, spraying the absolute ethyl alcohol, and chemically drying the surface of the flocked steel plate by using cold air to finish the alloy plating layer of the flocked steel plate;
(5) and 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 cleaning by tap water and deionized water for three times to complete pore-forming vulcanizing treatment, so that the porous film with excellent hydrogen evolution catalytic activity is obtained on the surface of the flocked steel plate.
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 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.
3. 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.
4. 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.
5. 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.
6. 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.
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