A metal electrode sheet based on hydrogel material, its preparation method and application

Abstract

This invention discloses a metal electrode sheet based on hydrogel materials, its preparation method, and its application, belonging to the field of interface modification. The surface of the aforementioned metal electrode sheet has an active carboxyl layer, on which nano-hydrogel particles containing amino groups are loaded. The preparation method involves immersing the metal electrode sheet with the active carboxyl layer in a dispersion of nano-hydrogel particles containing amino groups. Through a dehydration condensation reaction, the nano-hydrogel particles are covalently bonded to the surface of the metal electrode sheet, completing the nano-hydrogel particle loading. The resulting metal electrode sheet can be used in the field of alkaline electrocatalytic hydrogen evolution. This invention, by attaching nano-hydrogel particles to the surface of the metal electrode sheet, significantly improves the electrocatalytic performance compared to pure electrodes. Experimental data show that at 100 mA / cm², [the performance is significantly improved]. 2 The overpotential can be reduced by up to 60mV under current density. Therefore, this invention achieves modification of the water structure on the surface of the alkaline electrocatalytic hydrogen evolution reaction (HER).

Description

Technical Field

[0001] This invention belongs to the field of interface modification technology, and particularly relates to a metal electrode sheet based on hydrogel material, its preparation method and application. Background Technology

[0002] Hydrogen has garnered widespread international attention due to its advantages such as zero pollution, recyclability, and high calorific value. Among the many hydrogen production methods, the hydrogen evolution reaction (HER) method offers advantages such as simple equipment, sustainability, and environmental friendliness.

[0003] Existing research has elucidated the process of acidic HER, and the adsorption behavior of hydrogen intermediates (H, * representing active sites) on various catalysts can accurately explain and predict the reaction. Current research indicates that the reaction kinetics of HER in alkaline environments are two to three orders of magnitude slower than those in acidic electrolytes. It is believed that in acidic HER, H* originates from H in the electrolyte. + In alkaline HER, H* originates from water dissociation ( The additional energy barrier introduced by water dissociation is the reason for the slow HER kinetics in alkaline environments.

[0004] Current research suggests that the orientation and "network" structure of water within the double-electron-layer (EDL) are the main factors influencing the catalytic rate. Water orientation studies indicate that changes in water orientation within the double layer lead to increased energy consumption; water network studies suggest that water in the double layer forms a network through hydrogen bonds. This hydrogen bond network is disrupted during the HER process due to charge transfer, and the disruption and reconstruction of the water network during charge transfer results in even greater energy consumption.

[0005] Therefore, how to regulate the water orientation and water structure in alkaline HER is a technical problem that needs to be solved. Summary of the Invention

[0006] Objectives of the Invention: The first objective of this invention is to provide a metal electrode sheet based on hydrogel materials that can change the water structure at the alkaline hydrogen evolution reaction surface, thereby reducing the reaction energy barrier and reaction difficulty. The second objective of this invention is to provide a method for preparing the aforementioned metal electrode sheet based on hydrogel materials. The third objective of this invention is to provide applications of the aforementioned metal electrode sheet based on hydrogel materials.

[0007] Technical solution: The metal electrode sheet based on hydrogel material described in this invention has an active carboxyl layer on its surface, and nano-hydrogel particles containing amino groups are loaded on the active carboxyl layer.

[0008] Furthermore, the metal electrode sheet is Pt, Ni, or Pd, and the particle size of the nano-hydrogel particles is less than 500 nm.

[0009] The above-described method for preparing a metal electrode sheet based on hydrogel materials includes the following steps:

[0010] (1) The metal electrode sheet is carboxylated to obtain a metal electrode sheet with an active carboxyl base layer;

[0011] (2) Preparation of a dispersion of nanohydrogel particles containing amino groups;

[0012] (3) The metal electrode sheet with active carboxyl base layer is immersed in a dispersion of nano-hydrogel particles containing amino groups. The nano-hydrogel particles are covalently bonded to the surface of the metal electrode sheet through a dehydration condensation reaction, thus completing the nano-hydrogel particle loading and obtaining a metal electrode sheet based on hydrogel material.

[0013] Further, in step (1), the carboxylation treatment step is as follows:

[0014] (11) After surface cleaning, the metal electrode sheet is fully immersed in an alcohol solution containing thiol compounds, and then taken out and rinsed.

[0015] (12) Immerse the rinsed metal electrode in a mixed aqueous solution containing 2-(N-morpholine)ethanesulfonic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, and remove it after the immersion is complete.

[0016] Further, in step (11), the molar concentration of the thiol compound in the alcohol solution is 0.01-0.02 mol / L, and the soaking time is 2-4 h; in step (12), in the mixed aqueous solution, the molar concentration of 2-(N-morpholine)ethanesulfonic acid is 0.001-0.002 mol / L, the molar concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 0.002-0.003 mol / L, the molar concentration of N-hydroxysuccinimide is 0.005-0.006 mol / L, and the soaking time is 24 h-48 h.

[0017] Further, in step (2), the preparation steps of the dispersion of the amino-group-containing nano-hydrogel particles are as follows:

[0018] (21) Dissolve the surfactant and initiator in an organic solvent and mix them to obtain an organic phase solution;

[0019] (22) Dissolve the alkenyl monomer, allylamine and crosslinking agent in water and mix them to obtain an aqueous solution;

[0020] (23) Add the aqueous solution to the organic solution, disperse by ultrasonication, deoxygenate after full dispersion, stir in a water bath, demulsify, stand, centrifuge, take the lower precipitate, wash repeatedly and mix with buffer solution to obtain a dispersion of nano-hydrogel particles containing amino groups.

[0021] Further, in step (21), the ratio of the active agent, initiator, and organic solvent is 9.18-10 g: 24 mg: 120-200 mL, the active agent includes Tween 80 and Span 80, and the initiator is azobisisobutyronitrile; in step (22), the ratio of the polymer monomer, allylamine, crosslinking agent, and water is 0.02-0.025 mol: 84.2 mg: 13.8 mg: 1.5-2 mL; the polymer monomer is an alkenyl monomer or a combination of an alkenyl monomer and a functional monomer for enhancing hydrophobic properties; the crosslinking agent is N,N′-methylenebisacrylamide; in step (23), the parameters for ultrasonic dispersion are: ultrasonication at below 40°C for 1-2 h; the parameters for water bath stirring are: stirring at 40-50°C for 24-28 h; the reagent used for demulsification is tetrahydrofuran, and the buffer solution is 0.01-0.02 mol / L phosphate buffer.

[0022] Preferably, the polymer monomer is a combination of an alkenyl monomer and a functional monomer for enhancing hydrophobic properties, wherein the molar ratio of the alkenyl monomer to the functional monomer for enhancing hydrophobic properties is 1:3.5-4.5.

[0023] More preferably, the alkenyl monomer is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide, and the functional monomer is vinyltriethoxysilane or octadecyl methyl vinylate.

[0024] Furthermore, in step (3), the conditions for the dehydration condensation reaction are: reacting at 40-50℃ for 24-30h.

[0025] The above-mentioned application of metal electrode sheets based on hydrogel materials in the field of alkaline electrocatalytic hydrogen evolution.

[0026] Invention Principle: This invention utilizes hydrogel adhesion as a method for regulating the interfacial water configuration. It innovatively connects nano-hydrogel particles to a metal electrode sheet via covalent bonds. Hydrogels are three-dimensional network gels with strong interactions with water, which can trigger significant changes in the water molecule structure. Furthermore, the nano-sized hydrogel particles attached to the electrode surface, due to their extremely small size, are precisely positioned within the electronic double layer (EDL) region. This allows for effective alteration of the water molecule orientation and the hydrogen bond network structure between water molecules within the EDL region, thereby influencing the electrocatalytic rate.

[0027] Beneficial effects: Compared with the prior art, the present invention has the following significant effects: (1) The preparation process of nano-hydrogel particles is mature and simple, with high raw material utilization and environmental friendliness. The preparation process will not cause environmental pollution or large-scale emission of harmful substances; (2) The present invention has a certain universality. It is not for a specific electrode sheet, but for all hydrogen evolution metal electrode sheets (such as Pt, Ni, Pd, etc.) to reduce the reaction overpotential and improve the electrocatalytic performance; (3) The present invention significantly improves the HER performance of metal electrode sheets and effectively reduces the reaction overpotential. Attached Figure Description

[0028] Figure 1 SEM image of the platinum metal electrode sheet based on hydrogel material prepared in Example 1;

[0029] Figure 2 A magnified SEM image of the amphiphilic nano-hydrogel particles in the platinum metal electrode sheet based on hydrogel material prepared in Example 1.

[0030] Figure 3 The LSV performance comparison diagram is shown between the platinum metal electrode sheet based on hydrogel material prepared in Example 1 and the pure platinum electrode in Comparative Example 1.

[0031] Figure 4 The LSV performance comparison diagram is shown between the platinum metal electrode sheet based on hydrogel material prepared in Example 2 and the pure platinum electrode in Comparative Example 1.

[0032] Figure 5 The LSV performance comparison diagram is shown between the platinum metal electrode sheet based on hydrogel material prepared in Example 3 and the pure platinum electrode in Comparative Example 1.

[0033] Figure 6 Comparison of LSV performance of platinum metal electrode sheets prepared in Comparative Examples 1-3. Detailed Implementation

[0034] The present invention will now be described in further detail with reference to the embodiments and accompanying drawings.

[0035] Example 1: The platinum metal electrode sheet based on hydrogel material provided in this example has an active carboxyl layer on its surface, and amphiphilic nano-hydrogel particles containing amino groups are loaded on the active carboxyl layer.

[0036] The preparation steps are as follows:

[0037] 1) Pretreatment of metal electrode sheets

[0038] A 10mm × 10mm platinum metal electrode sheet was cut and ultrasonically cleaned using anhydrous ethanol, acetone, 0.1 mol / L dilute hydrochloric acid, and deionized water, respectively, to remove surface impurities such as metal oxides and oil. Then, at room temperature, it was immersed in a 0.01 mol / L 6-mercaptohexanoic acid alcohol solution for 2-4 hours. After sufficient immersion, it was rinsed with anhydrous ethanol. The rinsed electrode sheet was then transferred to a mixed aqueous solution of 0.001 mol / L 2-(N-morpholine)ethanesulfonic acid (MES), 0.002 mol / L 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), and 0.005 mol / L N-hydroxysuccinimide (NHS) at room temperature and immersed for 24 hours. This pretreatment process yielded a platinum metal electrode sheet with an active carboxyl group (-COOH) bonded to its surface (i.e., an active carboxyl base layer).

[0039] 2) Preparation of nano-hydrogel particles

[0040] 4.26 g of Tween 80, 4.92 g of Span 80, and 24 mg of initiator azobisisobutyl cyanide (AIBN) were dissolved in 120 mL of n-hexane and then added to a 250 mL three-necked flask and stirred until homogeneous to obtain an organic phase solution. Then, 586.6 mg of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (DMAPS), 84.2 mg of allylamine (AH), and 13.8 mg of crosslinking agent N,N′-methylenebisacrylamide (MBA) were dissolved in 1.5 mL of deionized water and dissolved completely by stirring and sonication to obtain an aqueous phase solution. The aqueous phase solution was then added to the organic phase solution and sonicated for 1 hour at a temperature below 40 °C to ensure complete dispersion of the aqueous phase solution in the organic phase solution.

[0041] Then, argon inert gas was introduced into the portion of the three-necked flask below the liquid surface, and the gas was continuously introduced for 40 minutes with bubbles rising continuously and evenly to ensure that no oxygen was present inside the reactor and to ensure the smooth progress of the reaction. The stopper was then sealed tightly, and the mixture was slowly stirred for 24 hours at a water bath temperature of 40°C. Then, 120 mL of tetrahydrofuran (THF) was added to break the emulsion, and after standing for 12 hours, the mixture was centrifuged at 4500 rpm for 15 minutes. The lower precipitate was collected and washed repeatedly with THF 3-5 times. Finally, the lower precipitate was mixed with 60 mL of 0.01 mol / L phosphate buffer (PBS) to obtain a dispersion of nano-hydrogel particles.

[0042] 3) Preparation of metal electrode sheets loaded with nano-hydrogel particles

[0043] Platinum metal electrode sheet with active carboxyl groups (-COOH) obtained in step 1) is placed in the nano-hydrogel particle dispersion obtained in step 2) and soaked for 24 hours. This allows the -COOH on the surface of the metal electrode sheet and the -NH2 on the surface of the hydrogel particles to undergo a dehydration condensation reaction. The nano-hydrogel particles are then covalently bonded to the surface of the metal electrode sheet, thus completing the loading of the hydrogel particles.

[0044] Comparative Example 1: Pure platinum electrode was used.

[0045] Example 2: The platinum metal electrode sheet based on hydrogel material provided in this example has an active carboxyl layer on its surface, and nano-hydrogel particles containing amino groups and Si-O hydrophobic groups are loaded on the active carboxyl layer.

[0046] The preparation steps are as follows:

[0047] 1) Pretreatment of metal electrode sheets

[0048] A 10mm × 10mm platinum metal electrode sheet was cut and ultrasonically cleaned using anhydrous ethanol, acetone, 0.1 mol / L dilute hydrochloric acid, and deionized water, respectively, to remove impurities such as metal oxides and oil stains from its surface. Then, it was immersed in a 0.01 mol / L 6-mercaptohexanoic acid alcohol solution for 2-4 hours at room temperature. After sufficient immersion, it was rinsed with anhydrous ethanol. The rinsed electrode sheet was then transferred to a mixed aqueous solution of 0.001 mol / L 2-(N-morpholine)ethanesulfonic acid (MES), 0.002 mol / L 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), and 0.005 mol / L N-hydroxysuccinimide (NHS) at room temperature and immersed for 24 hours. This pretreatment process yielded a platinum metal electrode sheet with an active carboxyl group (-COOH) bonded to its surface.

[0049] 2) Preparation of nano-hydrogel particles

[0050] 4.26 g of Tween 80, 4.92 g of Span 80, and 24 mg of initiator azobisisobutyronitrile (AIBN) were dissolved in 120 mL of n-hexane and then added to a 250 mL three-necked flask and stirred until homogeneous to obtain an organic phase solution for later use. Then, 119.7 mg of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (DMAPS) and 313.9 mg of vinyltriethoxysilane (N... DMAPS :N 乙烯基三乙氧基硅烷=1:4), 84.2 mg allylamine (AH), and 13.8 mg crosslinking agent N,N′-methylenebisacrylamide (MBA) were dissolved in 1.5 mL of deionized water and stirred and sonicated to obtain an aqueous solution. The aqueous solution was then added to the organic solution and sonicated for 1 h at a temperature below 40 °C to ensure that the aqueous solution was fully dispersed in the organic solution.

[0051] Then, argon inert gas was introduced into the portion of the three-necked flask below the liquid surface, and the gas was continuously introduced for 40 minutes with bubbles rising continuously and evenly to ensure that there was no oxygen inside the reactor and to ensure that the reaction proceeded smoothly. The stopper was then sealed tightly, and the mixture was slowly stirred for 24 hours at a water bath temperature of 40°C. Then, 120 mL of tetrahydrofuran (THF) was added to break the emulsion, and after standing for 12 hours, the mixture was centrifuged at 4500 rpm for 15 minutes. The lower precipitate was collected and washed repeatedly with THF 3-5 times. Finally, the lower precipitate was mixed with 60 mL of 0.01 mol / L phosphate buffer (PBS) to obtain a dispersion of nano-hydrogel particles.

[0052] 3) Preparation of metal electrode sheets loaded with nano-hydrogel particles

[0053] The platinum metal electrode sheet with active carboxyl groups (-COOH) obtained in step 1) is placed in the nano-hydrogel particle dispersion obtained in step 2) and soaked for 24 hours. This allows the -COOH on the surface of the metal electrode sheet and the -NH2 on the surface of the hydrogel particles to undergo a dehydration condensation reaction, and the nano-hydrogel particles are covalently bonded to the surface of the metal electrode sheet, thus completing the attachment of the hydrogel particles.

[0054] Example 3: The platinum metal electrode sheet based on hydrogel material provided in this example has an active carboxyl layer on its surface, and nano-hydrogel particles containing amino groups and long-chain carbohydrophobic groups are loaded on the active carboxyl layer.

[0055] The preparation steps are as follows:

[0056] 1) Pretreatment of metal electrode sheets

[0057] A 10mm × 10mm platinum metal electrode sheet was cut and ultrasonically cleaned using anhydrous ethanol, acetone, 0.1 mol / L dilute hydrochloric acid, and deionized water, respectively, to remove impurities such as metal oxides and oil stains from its surface. Then, it was immersed in a 0.01 mol / L 6-mercaptohexanoic acid alcohol solution for 2-4 hours at room temperature. After sufficient immersion, it was rinsed with anhydrous ethanol. The rinsed electrode sheet was then transferred to a mixed aqueous solution of 0.001 mol / L 2-(N-morpholine)ethanesulfonic acid (MES), 0.002 mol / L 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), and 0.005 mol / L N-hydroxysuccinimide (NHS) at room temperature and immersed for 24 hours. This pretreatment process yielded a platinum metal electrode sheet with an active carboxyl group (-COOH) bonded to its surface.

[0058] 2) Preparation of nano-hydrogel particles

[0059] 4.26 g of Tween 80, 4.92 g of Span 80, and 24 mg of initiator azobisisobutyronitrile (AIBN) were dissolved in 120 mL of n-hexane and then added to a 250 mL three-necked flask and stirred until homogeneous to obtain an organic phase solution for later use. Then, 119.7 mg of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (DMAPS) and 541.7 mg of octadecyl methyl vinyl acetate (N...) were added. DMAPS :N 甲基乙烯酸十八烷基酯 =1:4), 84.2 mg allylamine (AH), and 13.8 mg crosslinking agent N,N′-methylenebisacrylamide (MBA) were dissolved in 1.5 mL of deionized water and stirred and sonicated to obtain an aqueous solution. The aqueous solution was then added to the organic solution and sonicated for 1 h at a temperature below 40 °C to ensure that the aqueous solution was fully dispersed in the organic solution.

[0060] Then, argon inert gas was introduced into the portion of the three-necked flask below the liquid surface, and the gas was continuously introduced for 40 minutes with bubbles rising continuously and evenly to ensure that no oxygen was present inside the reactor and to ensure the smooth progress of the reaction. The stopper was then sealed tightly, and the mixture was slowly stirred for 24 hours at a water bath temperature of 40°C. Then, 120 mL of tetrahydrofuran (THF) was added to break the emulsion, and after standing for 12 hours, the mixture was centrifuged at 4500 rpm for 15 minutes. The lower precipitate was collected and washed repeatedly with THF 3-5 times. Finally, the lower precipitate was mixed with 60 mL of 0.01 mol / L phosphate buffer (PBS) to obtain a dispersion of nano-hydrogel particles.

[0061] 3) Preparation of metal electrode sheets loaded with nano-hydrogel particles

[0062] The platinum metal electrode sheet with active carboxyl groups (-COOH) obtained in step 1) is placed in the nano-hydrogel particle dispersion obtained in step 2) and soaked for 24 hours. This allows the -COOH on the surface of the metal electrode sheet and the -NH2 on the surface of the hydrogel particles to undergo a dehydration condensation reaction, and the nano-hydrogel particles are covalently bonded to the surface of the metal electrode sheet, thus completing the attachment of the hydrogel particles.

[0063] Comparative Example 2: The difference from Example 1 is that steps 2) and 3) are not included.

[0064] Comparative Example 3: The difference from Example 1 is that step 1 is not performed.

[0065] The platinum metal electrode sheets based on hydrogel materials prepared in Examples 1-3 and the platinum metal electrode sheets prepared in Comparative Examples 1-3 were characterized and their performance was tested. The results are shown in the figure. Figures 1-6 .

[0066] Figure 1 The distribution of nano-hydrogel particles on the surface of the metal electrode can be observed. Figure 2 These are nano-hydrogel particles under high-magnification surface scanning electron microscopy.

[0067] Depend on Figure 3 It can be seen that the platinum metal electrode sheet based on hydrogel material prepared in Example 1, compared with the pure platinum electrode in Comparative Example 1, achieves a higher efficiency of 100 mA / cm². 2 The overpotential can be reduced by 60 mV at the current density. This shows that the electrocatalytic reaction is more likely to occur after attaching nano-hydrogel particles, and the electrocatalytic performance is significantly improved.

[0068] Depend on Figure 4 and Figure 5 It can be seen that by replacing the monomers of the nano-hydrogel particles in Example 1 with hydrophobic monomers in proportion, with Example 2 using monomers containing siloxy groups (-Si-O-) and Example 3 using monomers with long-chain carbon, the selection of Examples 2 and 3 demonstrates that it is not only hydrophilic monomers that affect the water result; nano-hydrogel particles containing hydrophobic groups can also change the water structure at the reaction interface, thereby affecting the electrochemical performance of the electrocatalytic reaction.

[0069] Depend on Figure 6It can be seen that Comparative Example 2 is the electrode sheet after being soaked in an alcoholic solution of 0.01 mol / L 6-mercaptohexanoic acid in step 1 for 2-4 h, and Comparative Example 3 is the electrode sheet of Comparative Example 2 after being soaked in a mixed aqueous solution of 0.001 mol / L 2-(N-morpholine)ethanesulfonic acid (MES), 0.002 mol / L 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), and 0.005 mol / L N-hydroxysuccinimide (NHS) for 24 h. Compared with Comparative Example 3, Comparative Example 1 did not show a significant change in electrochemical performance, proving that the pretreatment step did not affect the electrochemical performance of the electrode sheet. Therefore, it can be concluded that the presence of nano-hydrogel particles has an impact on electrochemical performance.

Claims

1. A metal electrode sheet based on a hydrogel material, characterized by, The surface of the metal electrode sheet has an active carboxyl layer, and the active carboxyl layer is loaded with nano-hydrogel particles containing amino groups.

2. The metal electrode tab of claim 1, wherein The metal electrode sheet is Pt, Ni, or Pd, and the nano-hydrogel particles have a particle size of less than 500 nm.

3. A method for producing the metal electrode sheet based on the hydrogel material according to any one of claims 1 to 2, characterized by, The method comprises the following steps: (1) performing carboxyl treatment on a metal electrode sheet to obtain a metal electrode sheet with an active carboxyl layer; (2) preparing a dispersion of nano-hydrogel particles containing amino groups; (3) immersing the metal electrode sheet with the active carboxyl layer in the dispersion of the nano-hydrogel particles containing amino groups, and forming the nano-hydrogel particles covalently connected to the surface of the metal electrode sheet through a dehydration condensation reaction to complete the loading of the nano-hydrogel particles and obtain a metal electrode sheet based on hydrogel materials.

4. The production method according to claim 3, characterized by, In step (1), the carboxyl treatment comprises the following steps: (11) immersing the metal electrode sheet after surface cleaning in an alcohol solution containing a mercaptan compound, and then taking out and washing; (12) immersing the washed metal electrode sheet in a mixed aqueous solution containing 2-(N-morpholine) ethanesulfonic acid, 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole hydrochloride, and N-hydroxysuccinimide, and then taking out after completion.

5. The production method according to claim 4, characterized by, In step (11), the mercaptan compound has a molar concentration of 0.01-0.02 mol / L in the alcohol solution, and the immersion time is 2-4 h; in step (12), in the mixed aqueous solution, the 2-(N-morpholine) ethanesulfonic acid has a molar concentration of 0.001-0.002 mol / L, the 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole hydrochloride has a molar concentration of 0.002-0.003 mol / L, and the N-hydroxysuccinimide has a molar concentration of 0.005-0.006 mol / L, and the immersion time is 24 h-48 h.

6. The preparation method according to claim 3, characterized in that, In step (2), the preparation of the dispersion of the nano-hydrogel particles containing amino groups comprises the following steps: (21) mixing an active agent and an initiator in an organic solvent to obtain an organic phase solution; (22) mixing a polymer monomer, an allylamine, and a crosslinking agent in water to obtain an aqueous phase solution; (23) adding the aqueous phase solution to the organic phase solution, ultrasonically dispersing, performing oxygen removal treatment, then water-bath stirring, performing demulsification treatment, standing, centrifuging, taking the lower precipitate, repeatedly washing, and mixing with a buffer solution to obtain the dispersion of the nano-hydrogel particles containing amino groups.

7. The production method according to claim 6, wherein The amount ratio of the active agent, initiator and organic solvent in step (21) is 9.18-10 g: 24 mg: 120-200 mL, the active agent includes Tween 80 and Span 80, and the initiator is azobisdimethylcyanamide; the amount ratio of the polymer monomer, allylamine, crosslinking agent and water in step (22) is 0.02-0.025 mol: 84.2 mg: 13.8 mg: 1.5-2 mL; the polymer monomer is a combination of alkenyl monomer and functional monomer for enhancing hydrophobicity; the crosslinking agent is N,N'-methylene bisacrylamide; in step (23), the parameters of ultrasonic dispersion are: ultrasonic for 1-2 h at below 40 ℃; the parameters of water bath stirring are: stirring for 24-28 h at 40-50 ℃; the reagent used in demulsification treatment is tetrahydrofuran, and the buffer solution is 0.01-0.02 mol / L phosphate buffer solution.

8. The production method according to claim 7, wherein The polymer monomer is a combination of alkenyl monomer and functional monomer for enhancing hydrophobicity, and the molar ratio of alkenyl monomer to functional monomer for enhancing hydrophobicity is 1:3.5-4.

5.

9. The preparation method according to claim 3, characterized in that, In step (3), the conditions of dehydration condensation reaction are: reaction for 24-30 h at 40-50 ℃.

10. Application of the metal electrode sheet based on hydrogel material in the field of alkaline electrocatalytic hydrogen evolution according to any one of claims 1-2.

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