CN114525534A - Active electrolytic water electrode and preparation method and application thereof - Google Patents

Abstract

The invention provides an amorphous alloy electrolytic water electrode catalytic material, which is characterized in that foam metal with excellent conductivity is selected as a substrate, a layer of multi-element amorphous alloy material is prepared on the surface of the foam metal, and the catalytic performance of a hydrogen evolution electrode is greatly improved through the synergistic effect of multiple elements. Meanwhile, the combination problem of the catalytic material and the substrate material is improved by an electrodeposition in-situ growth method. The prepared integral catalytic electrode realizes efficient hydrolysis hydrogen evolution catalysis, still keeps extremely high activity and stability under the working condition of high current density, and has good industrial application prospect and commercial value. Solves the problems of high cost, insufficient activity, poor conductivity, poor stability under high current density and the like of the existing electrolysis water hydrogen evolution catalyst.

Description

A kind of active electrolyzed water electrode and its preparation method and application

technical field

The invention belongs to the field of material science and technology, and in particular relates to a preparation method and application of an amorphous alloy monolithic catalytic electrode

Background technique

Because of its extremely high energy density (283kJ·mol-1) and clean combustion products (water), hydrogen can be used as a clean energy in the energy fields such as fuel cells, and is an ideal green fuel. The traditional hydrogen manufacturing industry is produced through the conversion of petrochemical energy, such as natural gas dehydrogenation, water gas and alcohol reforming technologies, etc., but such technologies not only consume a large amount of fossil energy, but also are often accompanied by high energy consumption, high pollution and high energy consumption. Disadvantages of inputs and low purity. Water electrolysis technology is a green, environmentally friendly and efficient renewable hydrogen production strategy. However, efficient water electrolysis requires the use of active catalytic electrode materials to reduce excess energy consumption during hydrogen production. At present, the catalysts used in electrolysis of water for hydrogen evolution (HER) are mainly platinum-based precious metal catalysts, and the resulting high cost greatly limits the popularization of water electrolysis hydrogen production technology. As of 2019, electrolysis water hydrogen production only accounts for 4% share of my country's hydrogen production industry. In addition, the activity and stability of catalytic materials under extreme conditions such as high current are also another important factor restricting their large-scale commercial use. Therefore, it is of great commercial value to develop a non-precious metal-based catalytic cathode for water electrolysis with high activity, high stability, and suitable for high-current operation.

Transition metal elements such as nickel and cobalt are extremely suitable as active hydrogen evolution cathode materials due to their unique electronic structure and relatively abundant crustal reserves. However, the surface adsorption energy of elemental transition metals in the hydrogen evolution process is low, which is not conducive to the hydrogen evolution reaction. It is necessary to prepare by multi-alloying to optimize the hydrogen absorption effect of its adsorbed intermediates. In addition, transition metal alloys are extremely easily oxidized during storage and use, causing poisoning and deactivation of catalytic materials and affecting their performance. Therefore, it is necessary to further improve the anti-oxidation ability of materials to ensure their lifespan. Moreover, since the electrochemical hydrogen evolution process is a reaction involving a liquid-solid-gas three-phase interface, the catalytic electrode itself not only needs to have good catalytic activity, but also requires the electrode to have good electrical conductivity and three-dimensional porous structure to improve the reactants, The mass transfer process of the product and the gas diffusion process. This feature is especially important under high current conditions, which requires optimization and treatment of the overall structure and surface of the catalytic electrode. Finally, the current electrolysis of water for hydrogen production is mainly carried out in alkaline electrolytes to improve its conductivity, but strong alkaline solutions have a large degree of corrosion on electrolyzers, pipelines, etc. Therefore, the development of suitable neutral or weak alkaline solutions The high-efficiency monolithic catalytic electrode of the system is another technical difficulty in the electrolysis of water for hydrogen production.

To sum up, there is still a lack of monolithic active electrodes that fully meet the above requirements, and the current preparation processes of active catalytic materials are complicated, such as high-temperature calcination, ion sputtering, multi-step chemical synthesis, etc., which are not suitable for large-scale commercial production.

SUMMARY OF THE INVENTION

In view of the above technical problems, the present invention provides a method for preparing an amorphous multi-element transition metal alloy catalytic monolithic electrode. Using foam metal as a conductive substrate, an active plating layer is prepared by an electrodeposition method, and the prepared monolithic catalytic electrode is applied to alkalis. In the hydrogen evolution reaction of neutral and neutral electrolysis of water, it has high catalytic activity, and the catalyst can ensure high activity for a long time under the condition of high current, and has good stability.

The technical means adopted in the present invention are as follows:

An electrolyzed water material, the electrolyzed water material is based on a conductive porous foam metal, and an alloy catalytic material is deposited on the surface of the substrate; the alloy catalytic material is an amorphous multi-element transition metal alloy. The alloy catalytic material is grown on the surface of the conductive porous metal foam substrate by an electrodeposition (electroplating) method, and is combined with the conductive substrate in the form of chemical bonding, and has strong adhesion and stability. The monolithic electrolyzed water material grows in a self-supporting form on a conductive substrate without the addition of binders.

Further, the foam metal is at least one of copper foam, nickel foam, titanium foam or foam alloy, the pore size of the foam metal is 50-700 PPI, and the thickness is 1-20 mm; the amorphous alloy is cobalt-based, nickel-based, molybdenum-based base or iron-based alloys.

Further, the amorphous alloy is amorphous nickel-cobalt alloy, amorphous nickel-iron alloy, amorphous nickel-molybdenum alloy, amorphous cobalt-iron alloy, amorphous cobalt-molybdenum alloy, amorphous molybdenum-iron alloy, amorphous Nickel-iron-phosphorus alloy, amorphous nickel-iron-sulfur alloy, amorphous nickel-iron-nitrogen alloy, amorphous nickel-cobalt-sulfur alloy, amorphous nickel-cobalt-phosphorus alloy, amorphous nickel-cobalt-nitrogen alloy, amorphous nickel-molybdenum-phosphorus alloy , amorphous nickel molybdenum sulfur alloy, amorphous nickel molybdenum nitrogen alloy, amorphous cobalt iron phosphorus alloy, amorphous cobalt iron sulfur alloy, amorphous cobalt iron nitrogen alloy, amorphous cobalt molybdenum phosphorus alloy, amorphous One or more of amorphous cobalt-molybdenum-sulfur alloys, amorphous cobalt-molybdenum-nitrogen alloys, amorphous molybdenum-iron-phosphorus alloys, amorphous molybdenum-iron-sulfur alloys, and amorphous molybdenum-iron-nitrogen alloys.

The present invention also provides a preparation method of the above-mentioned electrolyzed water material, comprising the following steps:

(1) Select porous metal foams with different parameters as electrode substrate materials; place the foam metal substrates in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, and ultrapure water for 10 ultrasonic waves respectively. ～30min, then placed in a vacuum drying oven at 50～70℃ for 1～12h to obtain a base material with clean surface, which is sealed and stored;

(2) dissolving the electroplating solution precursor in a solvent, and ultrasonically dispersing it for 30-90 min to obtain an electroplating solution; the solvent is one or more of ethanol, water, dimethyl sulfoxide or tartaric acid;

(3) place the base material with clean surface in the electroplating solution, and carry out electrodeposition (electroplating);

(4) The material obtained after electrodeposition is placed in ultrapure water for ultrasonic washing for 10 to 30 minutes, then vacuum dried at 50 to 70° C. for 1 to 12 hours, and sealed for storage.

Further, in step (1), the concentration of dilute hydrochloric acid is 1-5 mol·L ^-1 ; the resistance of ultrapure water is 18.2 MΩ·cm.

Further, in step (2), the electroplating solution precursor is cobalt sulfate, cobalt chloride, cobalt acetate, nickel sulfate, copper sulfate, nickel chloride, ferric sulfate, sodium molybdate, ammonium molybdate, sodium citrate, sulfuric acid At least one of sodium, potassium sulfate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen hypophosphite, ammonia water, sodium hydroxide or dilute sulfuric acid; the total molar concentration of the electroplating solution precursor is 0.01～ 20mol·L ^-1 .

Further, in step (3), the electroplating system is a two-electrode system or a three-electrode system; in the two-electrode system, the working cathode is a foam metal substrate, and the counter electrode comprises carbon plate, metal nickel, metal copper or metal titanium. One; in the three-electrode system, the working cathode is a foamed metal substrate, the counter electrode includes one of carbon plate, metallic nickel, metallic copper or metallic titanium, and the reference electrode includes saturated calomel, mercury-chromium oxide or silver - one of the silver chloride electrodes;

Electroplating is one of constant current electroplating, constant current pulse electroplating, constant potential electroplating or constant potential pulse electroplating; the applied current density of electroplating is 0.001～5A·cm ⁻² ; the applied voltage of electroplating is 0.001～10V; the electroplating temperature is 25～ 100℃; electroplating time is 0～720min;

When using constant current pulse electroplating or constant potential pulse electroplating, the time duty ratio is 1:1 to 1:500 (seconds), and the cycle period is 500-1000;

During the electroplating process, the electroplating solution is magnetically stirred, and the stirring speed is 100-1200 rpm.

The invention also provides the application of the above-mentioned electrolyzed water material as an integral active catalytic electrode in the cathode hydrogen evolution reaction of alkaline and neutral electrolyzed water. The electrolyzed water material is a non-precious metal material and has a multivariate amorphous structure, which can be used as an integral electrode in the catalytic reaction of alkaline and neutral electrolyzed water cathode for hydrogen evolution, and still maintains high activity and stability under the condition of high current density. sex.

Further, the alkaline hydrogen evolution electrolyte is one or more of sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution; neutral hydrogen evolution electrolyte is pure aqueous solution, sodium sulfate solution, potassium sulfate solution, disodium hydrogen phosphate- One or more of sodium dihydrogen phosphate buffer solution or dipotassium hydrogen sulfate-potassium dihydrogen phosphate buffer solution.

Further, the monolithic active catalytic electrode is suitable for the electrolyte system with pH≥7; the current density of hydrogen evolution in electrolyzed water is 0.001-10A·cm ^-2 , and the preferred current density is 0.001-5A·cm ^-2 .

beneficial effect

1. The present invention utilizes the unique synergistic effect of amorphous multi-element alloys to adjust and optimize the catalytic activity in the process of hydrogen evolution from electrolyzed water, and is applied to electrolyzed water hydrogen production equipment, which greatly improves the electrolysis efficiency and saves electricity costs in the process of hydrogen production.

2. The monolithic catalytic electrode provided by the present invention is based on conductive foam metal, which has the advantages of excellent conductivity and large specific surface area, which is beneficial to the electron transfer and mass transfer process in the reaction.

3. The monolithic electrode provided by the present invention does not need any external binder, and the active material and the base are combined by a strong chemical bond through the electroplating method, which greatly improves the stability and conductivity of the catalyst on the base.

4. The monolithic catalytic electrode provided by the present invention can be applied to a wide range of alkaline and neutral pH electrolyte systems, can effectively avoid the corrosion of hydrogen production equipment by strong alkali, and reduce the operational difficulty and difficulty in the process of electrolyzing water for hydrogen production. Equipment maintenance costs.

5. The catalytic material in the present invention does not use noble metal elements, the production cost is low, the operation is simple, the precursors are widely sourced, can be prepared in large quantities, and is easy to scale up production.

Description of drawings

Fig. 1 is the scanning electron microscope image (SEM) of the sample of Example 1 of the present invention;

Fig. 2 is the scanning electron microscope image (SEM) of nickel foam substrate adopted in Example 1 of the present invention;

Fig. 3 is the electron diffraction analysis figure (SAED) of the sample of Example 1 of the present invention;

4 is an analysis diagram of the hydrogen evolution activity of the sample in Example 1 of the present invention in alkaline and neutral electrolytes.

Detailed ways

The preparation process of the electrolyzed water material of the present application will be described in detail below by way of examples, and the raw materials used in the following examples are all conventional products that can be obtained from the market.

Example 1

Preparation of nickel foam supported ternary amorphous cobalt-molybdenum-phosphorus alloy monolithic catalytic electrode:

1. A certain size of nickel foam (4*2cm, 120PPI, 1mm), the conductive foam metal substrate is placed in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, and ultrapure water respectively. Ultrasonic for 10 min, then placed in a vacuum drying oven and dried at 70 °C for 12 h to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant current stabilized power supply after the exposed area of 2*2 cm to carry out a two-electrode system. Electroplating, the counter electrode is a carbon plate; the current density is 10mA·cm ^-2 , the electroplating solution is stirred for 1200rpm, and the electroplating time is 1min;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and seal it for storage.

The prepared electrode was analyzed by scanning electron microscope (Fig. 1), and compared with the smooth nickel foam substrate (Fig. 2), a rough coating was observed; the electron transmission microscope was analyzed by electron diffraction (Fig. 3), and it was a halo-shaped diffraction pattern. Explain its amorphous alloy structure; its catalytic activity for hydrogen evolution under alkaline and neutral conditions is characterized (Fig. 4), showing extremely high hydrogen evolution efficiency.

Example 2

Preparation of nickel foam supported ternary amorphous cobalt-molybdenum-phosphorus alloy monolithic catalytic electrode:

1. A certain size of nickel foam (4*2cm, 120PPI, 1mm), the conductive foam metal substrate is placed in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, and ultrapure water respectively. Ultrasonic for 10 min, then placed in a vacuum drying oven and dried at 70 °C for 12 h to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant-current stabilized power supply to a three-electrode system after the exposed area is 2*2 cm. For electroplating, the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; the applied voltage is 3V, the electroplating solution stirs the plastic at 1200rpm, and the electroplating time is 1min;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

Example 3

Preparation of ternary amorphous cobalt-molybdenum-phosphorus alloy monolithic catalytic electrode supported by foamed copper:

1. A certain size of copper foam (4*2cm, 120PPI, 1mm), place the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, and ultrapure water respectively. Ultrasonic for 10 min, then placed in a vacuum drying oven and dried at 70 °C for 12 h to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant-current stabilized power supply to a three-electrode system after the exposed area is 2*2 cm. For electroplating, the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; the applied voltage is 3V, the electroplating solution stirs the plastic at 1200rpm, and the electroplating time is 1min;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

Example 4

Preparation of foamed nickel-iron supported ternary amorphous cobalt-molybdenum-iron alloy monolithic catalytic electrode:

1. A certain size of nickel-iron foam 4*2cm, 120PPI, 1mm), place the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, and ultrapure water respectively. Ultrasonic for 10 min, then placed in a vacuum drying oven and dried at 70 °C for 12 h to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml dilute sulfuric acid, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol ferric sulfate in 50ml water are prepared into electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant-current stabilized power supply to a three-electrode system after the exposed area is 2*2 cm. For electroplating, the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; the applied voltage is 3V, the electroplating solution stirs the plastic at 1200rpm, and the electroplating time is 1min;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

Example 5

Preparation of titanium foam supported ternary amorphous cobalt-molybdenum-phosphorus alloy monolithic catalytic electrode:

1. A certain size of titanium foam (4*2cm, 120PPI, 1mm), the conductive foam metal substrate is placed in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, ultrapure water and ultrasonic 10min, then placed in a vacuum drying oven for 12h at 70°C to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant current stabilized power supply after the exposed area of 2*2 cm to carry out a two-electrode system. For electroplating, the counter electrode is a carbon plate; the pulse current density is 10mA·cm ^-2 , the duty cycle is 1s/2s, the cycle period is 1000, and the electroplating solution stirs the plastic at 1200rpm;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

Example 6

Preparation of ternary amorphous cobalt-molybdenum-phosphorus alloy monolithic catalytic electrode supported by copper-zinc foam:

1. A certain size of copper-zinc foam (4*2cm, 120PPI, 1mm), place the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, ultrapure water in turn Ultrasonic for 10 min, then placed in a vacuum drying oven and dried at 70 °C for 12 h to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant-current stabilized power supply to a three-electrode system after the exposed area is 2*2 cm. Electroplating, the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; the pulse voltage is 3V, the duty cycle is 2s/4s, the cycle period is 500, and the electroplating solution stirs the plastic at 1200rpm;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

Comparative Example 1

Preparation of nickel foam supported binary amorphous cobalt-phosphorus alloy monolithic catalytic electrode:

1. A certain size of nickel foam (4*2cm, 120PPI, 1mm), the conductive foam metal substrate is placed in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, ultrapure water and ultrasonic 10min, then placed in a vacuum drying oven for 12h at 70°C to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant current stabilized power supply after the exposed area of 2*2 cm to carry out a two-electrode system. Electroplating, the counter electrode is a carbon plate; the current density is 10mA·cm ^-2 , the electroplating solution is stirred for 1200rpm, and the electroplating time is 1min;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

Comparative Example 2

Preparation of Foam Nickel Supported Binary Amorphous Cobalt Phosphorus Alloy Monolithic Catalytic Electrode by Sintering Method:

1. A certain size of nickel foam (4*2cm, 120PPI, 1mm), the conductive foam metal substrate is placed in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, ultrapure water and ultrasonic 10min, then placed in a vacuum drying oven and dried at 70°C for 12h to obtain a substrate material with a clean surface, which is sealed and stored;

2. 3 mmol of cobalt sulfate, 1 mmol of ammonium fluoride, and 3 mol of urea were dissolved in 50 ml of water, placed in a hydrothermal kettle, and reacted at 120° C. for 6 hours to obtain a foam nickel-supported chromium hydroxide precursor integral electrode.

3. Transfer the electrode obtained in step (2) into the paper tube furnace, pass H ₂ (5%)/Ar (95%) mixed gas, and place 2g of sodium dihydrogen hypophosphite as the phosphorus source at the gas inlet, and place the Annealed at 350℃ for 2h.

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

5. Comparative Example 2 The monolithic electrode prepared by the sintering method has low mechanical strength and cannot complete the electrochemical evaluation of the monolithic electrode.

Comparative Example 3

Preparation of nickel foam supported ternary amorphous cobalt-molybdenum-phosphorus alloy monolithic catalytic electrode:

1. A certain size of nickel foam (4*2cm, 120PPI, 1mm), the conductive foam metal substrate is placed in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethanol, and ultrapure water respectively. Ultrasonic for 10 min, then placed in a vacuum drying oven and dried at 70 °C for 12 h to obtain a substrate material with a clean surface, which is sealed and stored;

2, 3mmol sodium sulfate, 1ml ammoniacal liquor, 2mmol cobalt sulfate, 5mmol sodium molybdate, 3mmol potassium sulfate, 3mmol sodium dihydrogen phosphate are dissolved in 50ml water to prepare electroplating solution;

3. Transfer the electroplating solution obtained in step (2) into a paper electroplating tank, and use raw material tape and resin glue to encapsulate the substrate obtained in step (1), and connect a constant current stabilized power supply after the exposed area of 2*2 cm to carry out a two-electrode system. For electroplating, the counter electrode is a carbon plate; the current density is 5.1A·cm ^-2 , the electroplating solution stirs the plastic at 1200rpm, and the electroplating time is 1min;

4. Transfer the monolithic electrode obtained in step (3) to ultrapure water for ultrasonic washing for 10 minutes, then place it in a vacuum drying box to dry at 60° C. for 1 hour, and store in a sealed container.

5. The electrode prepared in Comparative Example 3 at high current density has too thick catalytic layer, insufficient adhesion, and a large amount of detachment during electrochemical evaluation, which affects its stability.

Application example 1

The catalytic electrodes obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were used to evaluate the electrochemical hydrogen evolution activity under alkaline conditions.

1. The standard three-electrode electrochemical linear voltammetry was used for analysis. The reference electrode was a mercury-mercury oxide electrode, the counter electrode was a carbon sheet, the electrolyte was a 1M KOH solution, and the working electrode was the prepared integral catalytic electrode. The exposed area is 1*1cm;

2. Test temperature: 25℃;

3. The sequence of its hydrogen evolution activity is as follows (Table 1):

Nickel-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Example 1) > nickel-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Example 2) = copper-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (implementation Example 3)>Amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode on titanium base (Example 5)>Copper-zinc-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Example 6)>Amorphous cobalt-molybdenum-iron alloy on nickel-iron base Monolithic electrode (Example 4)>Nickel-based amorphous cobalt-phosphorus alloy monolithic electrode (Comparative Example 1);

The invention can adjust the catalytic activity by adjusting the components of the precursor of the electroplating solution and the electroplating process, and the catalytic activity of the ternary amorphous alloy monolithic electrode is generally better than that of the binary component catalytic electrode.

Application example 2

The catalytic electrodes obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were used to evaluate the electrochemical hydrogen evolution activity under neutral conditions.

1. The standard three-electrode electrochemical linear voltammetry was used for analysis. The reference electrode was a mercury-mercury oxide electrode, the counter electrode was a carbon sheet, the electrolyte was a 1M sodium dihydrogen phosphate-disodium hydrogen phosphate buffer, and the working electrode was For the prepared monolithic catalytic electrode, the effective exposure area is 1*1cm;

2. Test temperature: 25℃;

3. The sequence of its hydrogen evolution activity is as follows (Table 1):

Nickel-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Example 1) > nickel-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Example 2) = copper-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (implementation Example 3)>Amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode on titanium base (Example 5)>Copper-zinc-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Example 6)>Amorphous cobalt-molybdenum-iron alloy on nickel-iron base Monolithic electrode (Example 4)>Nickel-based amorphous cobalt-molybdenum-phosphorus alloy monolithic electrode (Comparative Example 1);

The invention can adjust the catalytic activity by adjusting the components of the precursor of the electroplating solution and the electroplating process, and the catalytic activity of the ternary amorphous alloy monolithic electrode is generally better than that of the binary component catalytic electrode.

Table 1 Catalyst activity evaluation results under alkaline conditions

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (10)

1. The water electrolysis material is characterized in that foam metal is used as a conductive substrate, and an alloy catalytic material is deposited on the surface of the conductive substrate; the alloy catalytic material is an amorphous alloy.

2. The water electrolysis material according to claim 1, wherein the foam metal is at least one of foam copper, foam nickel, foam titanium or foam alloy, the pore size of the foam metal is 50-700 PPI, and the thickness of the foam metal is 1-20 mm; the amorphous alloy is cobalt-based, nickel-based, molybdenum-based or iron-based.

3. The electrolytic water material of claim 2, wherein the amorphous alloy is one or more of amorphous nickel-cobalt alloy, amorphous nickel-iron alloy, amorphous nickel-molybdenum alloy, amorphous cobalt-iron alloy, amorphous cobalt-molybdenum alloy, amorphous ferromolybdenum alloy, amorphous nickel-iron-phosphorus alloy, amorphous nickel-iron-sulfur alloy, amorphous nickel-iron-nitrogen alloy, amorphous nickel-cobalt-sulfur alloy, amorphous nickel-cobalt-phosphorus alloy, amorphous nickel-cobalt-nitrogen alloy, amorphous nickel-molybdenum-phosphorus alloy, amorphous nickel-molybdenum-sulfur alloy, amorphous nickel-molybdenum-nitrogen alloy, amorphous cobalt-iron-phosphorus alloy, amorphous cobalt-iron-sulfur alloy, amorphous cobalt-iron-nitrogen alloy, amorphous cobalt-molybdenum-phosphorus alloy, amorphous cobalt-molybdenum-sulfur alloy, amorphous cobalt-molybdenum-iron-nitrogen alloy, amorphous molybdenum-iron-phosphorus alloy, amorphous molybdenum-iron-sulfur alloy, and amorphous molybdenum-iron-nitrogen alloy.

4. A method of producing an electrolytic water material according to claims 1-3, comprising the steps of:

(1) sequentially placing the foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10-30 min, and then performing vacuum drying at 50-70 ℃ for 1-12 h to obtain a substrate material with a clean surface;

(2) dissolving the plating solution precursor in a solvent, and performing ultrasonic dispersion for 30-90 min to obtain a plating solution; the solvent is one or more of ethanol, water, dimethyl sulfoxide or tartaric acid;

(3) placing the substrate material with a clean surface in electroplating solution, and electroplating in an electroplating system;

(4) and (3) placing the electroplated material in ultrapure water for ultrasonic washing for 10-30 min, then carrying out vacuum drying for 1-12 h at 50-70 ℃, and sealing for storage.

5. The method according to claim 4, wherein in the step (1), the concentration of the dilute hydrochloric acid is 1-5 mol-L^-1(ii) a The ultrapure water resistance was 18.2 M.OMEGA.cm.

6. The method according to claim 4, wherein in the step (2), the plating solution precursor is at least one of cobalt sulfate, cobalt chloride, cobalt acetate, nickel sulfate, copper sulfate, nickel chloride, iron sulfate, sodium molybdate, ammonium molybdate, sodium citrate, sodium sulfate, potassium sulfate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen hypophosphite, ammonia water, sodium hydroxide, or dilute sulfuric acid; the total molar concentration of the precursor of the electroplating solution is 0.01 to up20mol·L^-1。

7. The manufacturing method according to claim 4, wherein in the step (3), the electroplating system is a two-electrode system or a three-electrode system; in the two-electrode system, the working cathode is a foam metal substrate, and the counter electrode comprises one of a carbon plate, metal nickel, metal copper or metal titanium; in the three-electrode system, a working cathode is a foam metal substrate, a counter electrode comprises one of a carbon plate, metal nickel, metal copper or metal titanium, and a reference electrode comprises one of saturated calomel, mercury-chromium oxide or silver-silver chloride electrodes;

the electroplating is one of constant current electroplating, constant current pulse electroplating, constant potential electroplating or constant potential pulse electroplating; the current density applied in electroplating is 0.001-5A cm^-2(ii) a The applied voltage for electroplating is 0.001-10V; the electroplating temperature is 25-100 ℃; the electroplating time is 0-720 min;

when constant current pulse plating or constant potential pulse plating is adopted, the time duty ratio is 1: 1-1: 500 (seconds), and the cycle period is 500-;

and magnetically stirring the electroplating solution in the electroplating process, wherein the stirring speed is 100-1200 rpm.

8. Use of the water electrolysis material of claims 1-3 as an integral active catalytic electrode in the cathodic hydrogen evolution reaction of alkaline, neutral electrolyzed water.

9. The use of claim 8, wherein the alkaline hydrogen evolution electrolyte is one or more of a sodium hydroxide solution, a potassium hydroxide solution or a sodium carbonate solution; the neutral hydrogen-separating electrolyte is one or more of pure water solution, sodium sulfate solution, potassium sulfate solution, disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution or dipotassium hydrogen sulfate-potassium dihydrogen phosphate buffer solution.

10. The use according to claim 8, wherein the current density in the cathodic hydrogen evolution reaction of electrolyzed water is 0.001-10A-cm^-2Preferably electric currentThe density is 0.001 to 5A/cm^-2。

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