Preparation method and application of adhesive with catalytic water dissociation function

Abstract

The invention discloses a preparation method and application of an adhesive with a catalytic water dissociation function, and belongs to the field of new energy, the preparation method of the adhesive with the catalytic water dissociation function comprises the following steps: S1, fully stirring acrylic acid, methyl acrylate, N, N-methylenebisacrylamide, an emulsifier and pure water, raising the temperature to 40-60 DEG C, and stirring for 20-30 minutes; the preparation method comprises the following steps: S1, dissolving an initiator into pure water to obtain a solution A, dissolving a metal ion compound into pure water to obtain a solution B, and S3, dropwise adding the solution A and the solution B into the monomer solution in a slow and continuous dropwise adding manner for 0.5-2 hours, heating to 50-75 DEG C, and reacting for 1-5 hours to obtain the adhesive with the catalytic water dissociation function. According to the prepared adhesive, through internal active catalytic particles, the activation energy barrier of water molecule dissociation is remarkably reduced, the dissociation efficiency of water in the electrolytic hydrogen production process is improved, and then the hydrogen production energy efficiency is improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of new energy, and particularly relates to a preparation method and application of an adhesive with a catalytic water dissociation function. BACKGROUND

[0002] Under the background of global energy transformation and the "double carbon" target, green hydrogen production has become one of the core paths for building a low-carbon economic system. Among them, water electrolysis hydrogen production is considered as the most potential renewable energy conversion method due to its advantages of wide raw material sources (abundant water resources), high product purity and zero carbon emissions. However, the traditional water electrolysis technology has long been plagued by the key bottleneck of high energy consumption and low efficiency - the water splitting reaction needs to overcome a high activation energy barrier, which limits the conversion efficiency of electrical energy to chemical energy, and restricts the economic feasibility of large-scale industrial application. Under this background, developing efficient and stable catalysts to accelerate the dissociation of water molecules has become a key research direction. SUMMARY

[0003] The purpose of the present application is to provide a preparation method and application of an adhesive with a catalytic water dissociation function to overcome at least one of the above-mentioned defects in the prior art.

[0004] To achieve this purpose, the present application adopts the following technical solutions:

[0005] The preparation method of the adhesive with a catalytic water dissociation function provided by the present application comprises the following steps: S1: acrylic acid, methyl acrylate, N-N-methylene bisacrylamide, emulsifier and pure water are fully stirred, heated to 40-60℃, and the stirring time is 0.5-2h to obtain a monomer solution, S2: the initiator is dissolved in pure water to obtain solution A, and the metal ion compound is dissolved in pure water to obtain solution B, S3: solution A and solution B are added to the monomer solution in a slow and continuous dropwise manner, the dropwise adding time is 0.5-2h, the temperature is raised to 50-75℃, and the reaction is carried out for 1-5h to obtain the adhesive with a catalytic water dissociation function.

[0006] Preferably, the mass ratio of acrylic acid, methyl acrylate, N-N-methylene bisacrylamide, emulsifier and pure water is 1:0.1-0.5:0.01-0.1:0.01-0.05:0.05-0.5.

[0007] Preferably, in solution A, the content of the initiator is 4-20%.

[0008] Preferably, the mass ratio of the initiator to acrylic acid is 0.01-0.1:1.

[0009] Preferably, in solution B, the content of the metal ion compound is 20-50%.

[0010] Preferably, the mass ratio of the metal ion compound to the acrylic acid is 0.01-0.1:1

[0011] Preferably, the emulsifier is an anionic surfactant, and the initiator is an aqueous initiator.

[0012] Preferably, the anionic surfactant is at least one of sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium dodecyl benzene sulfonate, and sodium ethoxyl phenol ether sulfate.

[0013] Preferably, the aqueous initiator is at least one of potassium persulfate, ammonium persulfate, and sodium persulfate.

[0014] Preferably, the metal ion compound is at least one of ferric chloride, ferric sulfate, ferric nitrate, zinc chloride, zinc sulfate, zinc nitrate, tin chloride, chromium chloride, cadmium chloride, and aluminum chloride.

[0015] The application also provides application of the adhesive with the catalytic hydrolysis function prepared by the preparation method to electrolytic water hydrogen production.

[0016] The application has the following advantages:

[0017] 1. The prepared adhesive significantly reduces the activation energy barrier of water molecule dissociation through internal active catalytic particles, promotes the dissociation efficiency of water in the electrolytic hydrogen production process, and further improves the hydrogen production energy efficiency.

[0018] 2. The acrylic monomer is used as the main polymer monomer, and the water solubility of the acrylic acid is good, which can effectively reduce the use of the emulsifier and solve the problem of excessive use of the emulsifier.

[0019] 3. The prepared adhesive has good hydrophilicity and can be used for the bonding of nickel electrodes, platinum electrodes, titanium electrodes, microporous membranes, ion membranes, non-woven fabrics, microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, and the like in a wet state.

[0020] 4. The metal ion compound is used as a secondary crosslinking agent in the preparation process, which has the effect of promoting water ionization, thereby improving the kinetic rate of cathode hydrogen evolution (HER) and anode oxygen evolution (OER). BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a running voltage comparison curve of an electrolytic cell assembled by a surface modified electrode of an embodiment of the application and an unmodified electrode.

[0022] Figure 2 is a hydrolysis partial pressure comparison curve of a composite membrane prepared by a zinc-containing adhesive of an embodiment of the application and a zinc-free adhesive. DETAILED DESCRIPTION

[0023] The application will be further described in conjunction with the drawings and specific embodiments.

[0024] Example One

[0025] The preparation method of the adhesive with the catalytic hydrolysis function provided in this embodiment includes the following steps:

[0026] S1: 10g of acrylic acid (AA), 1g of methyl acrylate (MAA), 1g of N,N-methylenebisacrylamide (MBA), 0.1g of sodium dodecyl benzene sulfonate, and 2g of pure water were put into a flask, and fully stirred, and gradually heated to 45℃, and the stirring time was 1.5h, to obtain a monomer solution.

[0027] S2: 0.4g of potassium persulfate was dissolved in 10g of pure water to obtain solution A, and 0.4g of iron chloride was dissolved in 1g of pure water to obtain solution B.

[0028] S3: Solution A and solution B were added to the monomer solution in a slow and continuous dropwise manner, the dropwise adding time was 1h, and the temperature was raised to 60℃, and the reaction was carried out for 1h, to obtain the adhesive with the catalytic hydrolysis function.

[0029] The application also provides the use of the adhesive with the catalytic hydrolysis function prepared by the preparation method of the adhesive with the catalytic hydrolysis function in the electrolysis of water to produce hydrogen.

[0030] The adhesive was coated on the surface of the nickel foam electrode, and transferred to a 70℃ oven. After 12h, when the solvent was completely volatilized, the modified nickel foam electrode was used as the cathode and the anode respectively for the alkaline electrolysis to produce hydrogen. As shown in the formula (I), under the same test conditions, compared with the electrolytic cell composed of the unmodified electrode, the voltage of the electrolytic cell assembled by the electrode with the modified surface was reduced by 360-530mV. It can be seen that after the electrode surface is modified, the operating voltage is obviously reduced. Figure 1

[0031] Example Two

[0032] The preparation method of the adhesive with the catalytic hydrolysis function provided in this embodiment includes the following steps:

[0033] S1: 15g of acrylic acid (AA), 3g of methyl acrylate (MAA), 1.2g of N,N-methylenebisacrylamide (MBA), 0.2g of sodium dodecyl benzene sulfonate, and 2g of pure water were put into a flask, and fully stirred, and gradually heated to 50℃, and the stirring time was 2h, to obtain a monomer solution.

[0034] S2: 0.6g of potassium persulfate was dissolved in 12g of pure water to obtain solution A, and 0.8g of zinc chloride was dissolved in 3g of pure water to obtain solution B. ​

[0035] S3: Solution A and solution B are added to the monomer solution in a slow continuous dropwise manner, the dropwise time is 1.5 h, the temperature is increased to 55℃, and the reaction is carried out for 2 h to obtain the adhesive with the catalytic water splitting function.

[0036] The embodiment also provides application of the adhesive with the catalytic water splitting function prepared by the preparation method of the adhesive with the catalytic water splitting function in electrolytic water hydrogen production.

[0037] The adhesive is applied between two ion exchange membranes, dried, and then soaked in pure water again, the composite membrane is placed between the positive electrode and the negative electrode (the effective area is 0.05 m 2 ), a platinum sheet is used as a working electrode, and 5% sodium sulfate solution is introduced into the cathode chamber and the anode chamber as an electrode solution. The water splitting partial pressure is tested under a current density of 500 A / m 2 , and compared with the composite membrane prepared by the adhesive without adding zinc chloride, as shown in Figure 2 , the water splitting partial pressure of the composite membrane prepared by the adhesive containing zinc chloride in the embodiment is 1.22-1.35 V, and the water splitting partial pressure of the composite membrane prepared by the adhesive without adding zinc chloride is 1.65-1.72 V.

[0038] It is illustrated that the adhesive prepared by the application has a catalytic water splitting effect on water entering the adhesive under the action of a direct current electric field after the adhesive is used for bonding between two ion exchange membranes. Moreover, the acrylic monomer is used as a main polymer monomer in the application, the water solubility of the acrylic acid is very good, the use of the emulsifier can be effectively reduced, and the problem of excessive use of the emulsifier is solved. The adhesive prepared by the application has good hydrophilicity, and can be used for bonding of nickel electrodes, platinum electrodes, titanium electrodes, microporous membranes, ion exchange membranes, non-woven fabrics, microfiltration membranes, ultrafiltration membranes, nanofiltration membranes and the like in a wet state.

[0039] The adhesive prepared by the application significantly reduces the activation energy barrier of water molecule dissociation through internal active catalytic particles, and strengthens the kinetics process of cathode hydrogen evolution reaction (HER) and anode oxygen evolution reaction (OER). The core advantage lies in realizing in-situ integration of the interface, promoting water splitting, optimizing ion transmission channels and improving current density. Experiments show that the electrode / membrane sheet modified by the adhesive has a significantly reduced voltage under the same operating current. The application provides a new material strategy for developing a high-performance electrolytic water hydrogen production system, and has important practical significance for promoting the large-scale development of green hydrogen industry. The application breaks through the functional boundary of traditional adhesives which only provide physical connection, introduces specific metal ions to endow the material with high catalytic properties, and can form a continuous and uniform catalytic layer at the interface. The core mechanism is that when the adhesive contacts with an electrolyte, the built-in catalytic particles can significantly reduce the Gibbs free energy barrier of water molecule dissociation, promote H +and rapid generation of OH-, thereby directly increasing the kinetic rate of the cathodic hydrogen evolution reaction (HER) and the anodic oxygen evolution reaction (OER) in the electrolysis process.

[0040] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that; it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a catalyst-hydrolytic dissociation functional adhesive, characterized in that, Includes the following steps: S1: Acrylic acid, methyl acrylate, NN-methylenebisacrylamide, emulsifier, and pure water are thoroughly stirred, heated to 40-60℃, and stirred for 0.5-2 hours to obtain a monomer solution; S2: Dissolve the initiator in pure water to obtain solution A, and dissolve the metal ion compound in pure water to obtain solution B; S3: Add solution A and solution B to the monomer solution by slow and continuous dripping for 0.5-2 hours, heat to 50-75℃, and react for 1-5 hours to obtain an adhesive with catalytic water dissociation function.

2. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: The mass ratio of acrylic acid, methyl acrylate, N,N-methylenebisacrylamide, emulsifier, and pure water is 1:0.1-0.5:0.01-0.1:0.01-0.05:0.05-0.

5.

3. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: In solution A, the initiator content is 4-20%.

4. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: The mass ratio of initiator to acrylic acid is 0.01-0.1:

1.

5. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: In solution B, the content of metal ion compounds is 20-50%.

6. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: The mass ratio of the metal ion compound to acrylic acid is 0.01-0.1:

1.

7. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: The emulsifier is an anionic surfactant; The initiator is an aqueous initiator.

8. The method for preparing the adhesive with catalytic water dissociation function according to claim 7, characterized in that: The anionic surfactant is at least one of sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium dodecylbenzene sulfonate, and sodium ethoxyphenol ether sulfate. The aqueous initiator is at least one of potassium persulfate, ammonium persulfate, and sodium persulfate.

9. The method for preparing the adhesive with catalytic water dissociation function according to claim 1, characterized in that: The metal ion compound is at least one of ferric chloride, ferric sulfate, ferric nitrate, zinc chloride, zinc sulfate, zinc nitrate, tin chloride, chromium chloride, cadmium chloride, and aluminum chloride.

10. The application of the adhesive with catalytic water dissociation function prepared by the preparation method of the adhesive with catalytic water dissociation function according to any one of claims 1-9 in the electrolysis of water to produce hydrogen.

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