Electrolyzed water dehydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalysts, in particular to an electrolytic water dehydrogenation catalyst and a preparation method and application thereof. The preparation method of the electrolytic water dehydrogenation catalyst comprises the following steps: mixing a platinum source, a carrier material and a reducing agent to obtain a platinum-containing precursor solution, and carrying out first heating reduction treatment on the platinum-containing precursor solution to obtain a platinum nanoparticle-loaded carrier material; and mixing the platinum nanoparticle-loaded carrier material, an iridium source and a reducing agent to obtain a blended solution, carrying out second heating reduction treatment on the blended solution, and loading iridium nanoparticles on the surfaces of the platinum nanoparticles of the carrier material to obtain the electrolytic water dehydrogenation catalyst. The catalyst obtained by the preparation method and the dehydrogenation layer comprising the catalyst have hydroxide activity and oxygen evolution reaction activity, the utilization rate of the catalyst is high, and the preparation method is simple, convenient and rapid, does not need large instruments and equipment and complex processes, and is beneficial to large-scale industrial application.

Description

Technical Field

[0001] The present application belongs to the field of catalyst technology, and in particular relates to a water electrolysis hydrogen removal catalyst and a preparation method and application thereof. Background Art

[0002] As a key component of solid electrolyte water electrolysis, the solid electrolyte membrane transmits protons while blocking the cross-penetration of gases. Reducing the thickness of the proton exchange membrane can effectively reduce the proton transmission resistance, thereby improving the electrolysis performance and reducing the cost of electrolysis. However, the use of thinner solid electrolyte membranes will cause other problems, especially for high-pressure water electrolysis to produce hydrogen. When the membrane is thinner, due to the greater pressure on the hydrogen side, hydrogen tends to penetrate from the cathode side to the anode side, thereby reducing the purity of oxygen; at the same time, the higher hydrogen concentration in oxygen on the anode side will increase the safety risks of the electrolyzer. Therefore, eliminating hydrogen on the anode side and reducing the hydrogen concentration in oxygen is one of the key issues that need to be solved in the development of high-pressure water electrolysis.

[0003] At present, from the perspective of membrane electrode, the main methods to reduce hydrogen in oxygen on the anode side are: hydrogen blocking and hydrogen elimination. Hydrogen blocking is to prevent hydrogen from penetrating from the cathode side to the anode side. Generally, a high-strength, low-gas-permeability solid electrolyte membrane is used, or a hydrogen blocking layer is added on both sides of the solid electrolyte membrane. Hydrogen elimination is a digestion reaction that eliminates hydrogen that penetrates from the cathode side to the anode side, thereby reducing the concentration of hydrogen in oxygen.

[0004] Regarding the hydrogen permeation problem in solid electrolyte water electrolysis devices, studies have shown that adding a Pt interlayer to the anode catalyst layer, cathode catalyst layer and solid electrolyte membrane can reduce the hydrogen content in the anode oxygen, but such methods generally use Pt black nanoparticles, and the Pt nanoparticles in the interlayer are severely agglomerated, which greatly reduces the utilization rate of Pt. Another method is to use the precious metal iridium (Ir) as an oxygen evolution reaction catalyst at the anode. From the perspective of the intrinsic activity of the catalyst, titanium dioxide is generally used as a carrier to reduce the amount of precious metal. Although the electrochemical stability is excellent, it is non-conductive and cannot meet the conductivity requirements, resulting in a large amount of iridium metal, which limits the use of the catalyst.

[0005] Therefore, there is an urgent need to provide a method for preparing a catalyst to ensure that the problem of reducing the hydrogen concentration in the oxygen on the anode side of water electrolysis and improving the catalyst utilization rate can be effectively solved. Summary of the invention

[0006] The purpose of the present application is to provide a water electrolysis dehydrogenation catalyst and its preparation method and application, aiming to solve the problem that the prior art cannot effectively solve the problem of reducing the hydrogen concentration in the oxygen on the anode side of water electrolysis and improving the catalyst utilization rate.

[0007] In order to achieve the above application purpose, the technical solution adopted in this application is as follows:

[0008] In a first aspect, the present application provides a method for preparing a catalyst for dehydrogenation by electrolysis of water, comprising the following steps:

[0009] A platinum source, a carrier material and a reducing agent are mixed to obtain a platinum-containing precursor solution, and the platinum-containing precursor solution is subjected to a first heating reduction treatment to obtain a carrier material loaded with platinum nanoparticles;

[0010] The carrier material loaded with platinum nanoparticles, an iridium source and a reducing agent are mixed to obtain a mixed solution, and the mixed solution is subjected to a second heating reduction treatment to load iridium nanoparticles on the surface of the platinum nanoparticles of the carrier material to obtain a water electrolysis dehydrogenation catalyst.

[0011] In some embodiments, the platinum source is selected from H2PtCl6·4H2O, 2(C2H3O2).H 12 N4Pt、C 10 H 14 At least one of O4Pt.

[0012] In some embodiments, the iridium source is selected from at least one of IrCl3·3H2O, Cl4H3IrO, and IrCl4.

[0013] In some embodiments, the support material is selected from at least one of TiO2, TiN, and TiC.

[0014] In some embodiments, the reducing agent is selected from ethylene glycol or ethanol.

[0015] In some embodiments, the mass ratio of the platinum source, the support material, and the reducing agent is 1:1 to 10:200.

[0016] In some embodiments, the mass ratio of the support material loaded with platinum nanoparticles, the iridium source, and the reducing agent is 1:1 to 10:200.

[0017] In some embodiments, the first heating reduction treatment is performed at a temperature of 100 to 300° C. for a time of 1 to 12 hours.

[0018] In some embodiments, the second heating reduction treatment is performed at a temperature of 100 to 200° C. and for a time of 1 to 12 hours.

[0019] In a second aspect, the present application provides a water electrolysis dehydrogenation catalyst, which is prepared by the above-mentioned water electrolysis dehydrogenation catalyst preparation method, wherein the water electrolysis dehydrogenation catalyst includes a carrier, platinum nanoparticles are uniformly loaded on the surface of the carrier, and iridium nanoparticles are uniformly loaded on the surface of the platinum nanoparticles and the carrier; wherein the particle size of the platinum nanoparticles is 2 to 4 nm.

[0020] In some embodiments, the total mass of the water electrolysis hydrogen removal catalyst is 100%, the loading amount of the platinum nanoparticles is 1-30%, and the loading amount of the iridium nanoparticles is 1-70%.

[0021] In a third aspect, the present application provides a method for preparing a catalytic hydrogen removal layer for water electrolysis, comprising the following steps:

[0022] The above-mentioned water electrolysis hydrogen removal catalyst is provided,

[0023] The electrolytic water dehydrogenation catalyst is mixed with the ionomer solution and the solvent to obtain a catalyst slurry;

[0024] The catalyst slurry is coated on the surface of the proton exchange membrane to obtain a water electrolysis catalytic hydrogen removal layer.

[0025] In a fourth aspect, the present application provides a membrane electrode, which includes a water electrolysis catalytic hydrogen removal layer prepared by the above-mentioned water electrolysis catalytic hydrogen removal layer preparation method.

[0026] In a fifth aspect, the present application provides a water electrolysis hydrogen production device, which includes the above-mentioned membrane electrode.

[0027] The first aspect of the present application provides a method for preparing a catalyst for dehydrogenation by electrolysis of water. The preparation method is divided into two steps. In the first step, uniform platinum nanoparticles are prepared on the surface of a carrier by a heating reduction method using a reducing agent, and the uniformly loaded platinum nanoparticles form a conductive network, which is beneficial to improving the conductivity of the catalyst; further, iridium nanoparticles are prepared on the surface of the platinum nanoparticles to obtain a catalyst material of Ir@Pt@carrier, and the obtained catalyst has hydrogen oxidation activity and oxygen evolution reaction activity, thereby improving the catalytic activity of the catalyst. In addition, the preparation method is simple and quick, does not require large-scale instruments and equipment and complex processes, and is beneficial to large-scale industrial applications.

[0028] The electrolysis of water dehydrogenation catalyst provided in the second aspect of the present application forms a platinum nanoparticle conductive network on the carrier surface, which has excellent conductivity; and iridium nanoparticles are also loaded on the surface of the platinum nanoparticles, so that the electrolysis of water dehydrogenation catalyst has hydrogen oxidation activity and oxygen evolution reaction activity, has good catalytic effect, and can be widely used in various fields.

[0029] The third aspect of the present application provides a method for preparing a hydrogen-scavenging electrolytic water catalytic layer. The hydrogen-scavenging electrolytic water catalytic layer uses a water electrolytic hydrogen-scavenging catalyst as a raw material, mixes it with an ionomer solution and a solvent, and then coats it on the surface of a proton exchange membrane to obtain the water electrolytic hydrogen-scavenging layer. The obtained water electrolytic hydrogen-scavenging catalytic layer can be directly assembled into a water electrolytic device to reduce the hydrogen content in oxygen in the anode.

[0030] The membrane electrode provided in the fourth aspect of the present application comprises a water electrolysis catalytic hydrogen removal layer. The obtained membrane electrode can be assembled as a hydrogen removal layer into a proton exchange membrane, between an anode and a proton exchange membrane, in an anode catalyst layer interlayer, and between an anode catalyst layer and a porous transport layer. The membrane electrode has excellent catalytic effect and a wide range of applications.

[0031] The water electrolysis hydrogen production device provided in the present application includes the above-mentioned membrane electrode; therefore, in the obtained water electrolysis hydrogen production device, the content of hydrogen in oxygen in the anode can be effectively reduced, solving the hydrogen permeation problem in the water electrolysis device. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0033] Figure 1 It is a comparison chart of the LSV curves of the water electrolysis dehydrogenation catalyst provided in the examples of the present application and the commercial iridium black catalyst.

[0034] Figure 2 It is an impedance diagram of the water electrolysis hydrogen removal catalyst provided in the examples of the present application and the commercial iridium black catalyst.

[0035] Figure 3 It is a performance comparison chart of polarization curves of single-cell water electrolysis of the membrane electrode (including the water electrolysis catalytic hydrogen removal layer) provided in the embodiment of the present application and the commercial iridium black membrane electrode.

[0036] Figure 4 This is a comparison chart of the hydrogen content in the anode side of oxygen in a single water electrolysis cell of the membrane electrode (including a water electrolysis catalytic hydrogen removal layer) provided in the embodiment of the present application and a commercial iridium black membrane electrode. DETAILED DESCRIPTION

[0037] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail in conjunction with the embodiments below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0038] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0039] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0040] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0041] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0042] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass in the embodiment description of the present application can be μg, mg, g, kg and other mass units known in the chemical industry.

[0043] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0044] The first aspect of the present application provides a method for preparing a catalyst for dehydrogenation by electrolysis of water, comprising the following steps:

[0045] S01. The platinum source, the support material and the reducing agent are mixed to obtain a platinum-containing precursor solution, and the platinum-containing precursor solution is subjected to a first heating reduction treatment to obtain a support material loaded with platinum nanoparticles;

[0046] S02. The carrier material loaded with platinum nanoparticles, an iridium source and a reducing agent are mixed to obtain a mixed solution, and the mixed solution is subjected to a second heating reduction treatment to load iridium nanoparticles on the surface of the platinum nanoparticles of the carrier material to obtain a water electrolysis dehydrogenation catalyst.

[0047] The first aspect of the embodiment of the present application provides a method for preparing a catalyst for dehydrogenation by electrolysis of water. The preparation method is divided into two steps. In the first step, uniform platinum nanoparticles are prepared on the surface of a carrier by a heating reduction method using a reducing agent, and the uniformly loaded platinum nanoparticles form a conductive network, which is beneficial to improving the conductivity of the catalyst; further, iridium nanoparticles are prepared on the surface of the platinum nanoparticles to obtain a catalyst material of Ir@Pt@carrier, so that the obtained catalyst has hydrogen oxidation activity and oxygen evolution reaction activity, and the catalytic activity of the catalyst is improved. In addition, the preparation method is simple and fast, does not require large-scale instruments and equipment and complex processes, and is beneficial to large-scale industrial applications.

[0048] In step S01, a platinum source, a carrier material and a reducing agent are mixed to obtain a platinum-containing precursor solution, and the platinum-containing precursor solution is subjected to a first heating reduction treatment to obtain a carrier material loaded with platinum nanoparticles. In the first step, the Pt nanoparticles are uniformly loaded on the surface of the carrier material by the first heating reduction treatment method, so that the Pt nanoparticles can pre-construct an electron transport network on the surface of the carrier material, which can serve as a HOR catalytic site, effectively improve the utilization rate of Pt, and improve the conductivity of the material.

[0049] In some embodiments, the platinum source is selected from H2PtCl6·4H2O, 2(C2H3O2).H 12 N4Pt、C 10 H 14 At least one of O4Pt.

[0050] In some embodiments, the support material is selected from at least one of TiO2, TiN, and TiC.

[0051] In some embodiments, the reducing agent is selected from ethylene glycol or ethanol.

[0052] In some embodiments, the mass ratio of the platinum source, the carrier material and the reducing agent is 1:1 to 10:200. If the amount of the carrier material added is too much, the loading amount of the platinum nanomaterial will be too small, resulting in the inability to form a conductive network and affecting the conductivity.

[0053] In some specific embodiments, the mass ratio of the platinum source and the carrier material includes but is not limited to 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10 and the like typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values.

[0054] In some embodiments, in the step of mixing the platinum source, the carrier material and the reducing agent to obtain the platinum-containing precursor solution, the mixing method includes but is not limited to stirring and the like, the purpose of which is to blend the components uniformly.

[0055] In some embodiments, the temperature of the first heating reduction treatment is 100 to 300° C., and the time is 1 to 12 hours. The use of appropriate conditions for the first heating reduction treatment can ensure that the heating reduction reaction can react completely, which is conducive to completely reducing the platinum ions in the platinum source to prepare platinum atoms on the surface of the carrier. If the temperature of the heating reduction treatment is too low or the reaction time is too short, the reaction is incomplete and the platinum ions cannot be reduced to the maximum extent to obtain platinum atoms; if the temperature of the heating reduction treatment is too high or the reaction time is too long, the reaction efficiency will be reduced.

[0056] In some specific embodiments, the temperature of the first heating reduction treatment includes but is not limited to 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C, 300°C and other typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values.

[0057] In some specific embodiments, the time for the first heating reduction treatment includes but is not limited to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours and other typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values.

[0058] In step S02, a carrier material loaded with platinum nanoparticles, an iridium source and a reducing agent are mixed to obtain a mixed solution, and the mixed solution is subjected to a second heating reduction treatment to load iridium nanoparticles on the surface of the platinum nanoparticles of the carrier material to obtain a water electrolysis dehydrogenation catalyst.

[0059] In some embodiments, the mass ratio of the carrier material, iridium source and reducing agent loaded by the platinum nanoparticles is 1:1 to 10:200. If the amount of the iridium source added is too much, the loading amount of the iridium nanoparticles is too little, and excellent catalytic performance cannot be achieved.

[0060] In some specific embodiments, the mass ratio of the support material loaded with platinum nanoparticles to the iridium source includes but is not limited to 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10 and the like typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values.

[0061] In some embodiments, the iridium source is selected from at least one of IrCl3·3H2O, Cl4H3IrO, and IrCl4.

[0062] In some embodiments, in the step of mixing the carrier material loaded with platinum nanoparticles, the iridium source and the reducing agent to obtain a blended solution, the mixing method includes but is not limited to stirring and the like, the purpose of which is to blend the components uniformly.

[0063] In some embodiments, the temperature of the second heating reduction treatment is 100 to 200°C, and the time is 1 to 12 hours. The use of appropriate conditions for the second heating reduction treatment can ensure that the heating reduction reaction can react completely, which is conducive to the complete reduction of the iridium ions in the iridium source, so as to prepare iridium atoms on the surface of platinum atoms, and obtain an OER catalyst with HOR activity, thereby obtaining an OER and HOR catalyst at the same time. If the temperature of the heating reduction treatment is too low or the reaction time is too short, the reaction is incomplete, and the iridium ions cannot be reduced to the maximum extent to obtain iridium atoms; if the temperature of the heating reduction treatment is too high or the reaction time is too long, the reaction efficiency will be reduced.

[0064] In some specific embodiments, the temperature of the second heating reduction treatment includes but is not limited to 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C, 300°C, etc. typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values.

[0065] In some specific embodiments, the time for the second heating reduction treatment includes but is not limited to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours and other typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values.

[0066] In a second aspect, the present application provides a water electrolysis dehydrogenation catalyst, which is prepared by the above-mentioned water electrolysis dehydrogenation catalyst preparation method, wherein the water electrolysis dehydrogenation catalyst includes a carrier, platinum nanoparticles are uniformly loaded on the surface of the carrier, and iridium nanoparticles are uniformly loaded on the surface of the platinum nanoparticles; wherein the particle size of the platinum nanoparticles is 2 to 4 nm.

[0067] The electrolysis of water dehydrogenation catalyst provided in the second aspect of the embodiment of the present application forms a platinum nanoparticle conductive network on the carrier surface, which has excellent conductivity; and iridium nanoparticles are also loaded on the surface of the platinum nanoparticles, so that the electrolysis of water dehydrogenation catalyst has hydrogen oxidation activity and oxygen evolution reaction activity, has good catalytic effect, and can be widely used in various fields.

[0068] In some embodiments, the particle size of the platinum nanoparticles includes, but is not limited to, 2 nm, 2.2 nm, 2.5 nm, 2.8 nm, 3 nm, 3.2 nm, 3.5 nm, 3.8 nm, 4 nm, and other typical but non-limiting arbitrary point values ​​or interval values ​​between any two point values. Since the obtained platinum nanoparticles have a small particle size, the platinum nanoparticles can cover the surface of the carrier to the greatest extent, forming a conductive network on the surface of the carrier to improve the overall conductivity of the material.

[0069] In some embodiments, the total mass of the water electrolysis hydrogen removal catalyst is 100%, the loading amount of the platinum nanoparticles is 1-30%, and the loading amount of the iridium nanoparticles is 1-70%.

[0070] In a third aspect, the present application provides a method for preparing a catalytic layer for hydrogen removal and water electrolysis, comprising the following steps:

[0071] G01. Providing the above-mentioned water electrolysis hydrogen removal catalyst,

[0072] G02. The electrolytic water dehydrogenation catalyst is mixed with the ionomer solution and the solvent to obtain a catalyst slurry;

[0073] G03. Coat the catalyst slurry on the surface of the proton exchange membrane to obtain a hydrogen removal and water electrolysis catalytic layer.

[0074] A third aspect of an embodiment of the present application provides a method for preparing a water electrolysis catalytic hydrogen removal layer. The water electrolysis catalytic layer uses a water electrolysis hydrogen removal catalyst as a raw material, which is mixed with an ionomer solution and a solvent, and then coated on the surface of a proton exchange membrane to obtain the water electrolysis catalytic hydrogen removal layer. The obtained water electrolysis catalytic hydrogen removal layer can be directly assembled into a water electrolysis device to reduce the hydrogen content in oxygen in the anode.

[0075] In step G01, the above-mentioned water electrolysis dehydrogenation catalyst is provided. The provided water electrolysis dehydrogenation catalyst is as described above and will not be described in detail here.

[0076] In step G02, the water electrolysis dehydrogenation catalyst is mixed with the ionomer solution and the solvent to obtain a catalyst slurry.

[0077] In some embodiments, the ionomer includes, but is not limited to, at least one of Solvy-D790, Du Pont-D2020, Du Pont-D520.

[0078] In some embodiments, the solvent includes but is not limited to at least one of n-propanol, isopropanol, anhydrous ethanol, dipropylene glycol, ethylene glycol, n-hexane, and cyclohexane.

[0079] In some embodiments, uniform mixing includes, but is not limited to, stirring and the like, the purpose of which is to mix the mixture of each component.

[0080] In step G03, the catalyst slurry is coated on the surface of the proton exchange membrane to obtain a water electrolysis catalytic hydrogen removal layer.

[0081] In some embodiments, coating includes, but is not limited to, spray coating or knife coating.

[0082] In some embodiments, after the catalyst slurry is coated on the surface of the proton exchange membrane, the method further comprises: performing a drying process, wherein the drying process is performed at a temperature of 50 to 90° C. and for a time of 10 to 60 minutes.

[0083] In a fourth aspect, the present application provides a membrane electrode, which includes a water electrolysis catalytic hydrogen removal layer prepared by the above-mentioned water electrolysis catalytic hydrogen removal layer preparation method.

[0084] The membrane electrode provided in the fourth aspect of the embodiment of the present application comprises a water electrolysis catalytic hydrogen removal layer, and the obtained hydrogen removal layer can be assembled into the proton exchange membrane, between the anode and the proton exchange membrane, in the anode catalyst layer interlayer, and between the anode catalyst layer and the porous transport layer; the catalytic effect is excellent and the application range is wide.

[0085] In a fifth aspect, the present application provides a water electrolysis hydrogen production device, which includes the above-mentioned membrane electrode.

[0086] The fifth aspect of the embodiment of the present application provides a hydrogen production device by electrolysis of water, which includes the above-mentioned membrane electrode; therefore, in the obtained hydrogen production device by electrolysis of water, the content of hydrogen in oxygen in the anode can be effectively reduced, thereby solving the hydrogen permeation problem in the water electrolysis device.

[0087] The following describes the invention in conjunction with specific embodiments.

[0088] Example 1

[0089] Membrane electrode including catalytic layer and method for preparing the same

[0090] (1) Add 0.2 g of TiO2 carrier and 100 ml of ethylene glycol into a sample bottle and disperse them evenly. Then add 0.1 g of H2PtCl6·4H2O into the solution and stir well to obtain a Pt precursor solution.

[0091] (2) The Pt precursor solution is transferred to a reaction bottle and reacted at 100° C. for 10 hours using a metal bath. The sample after the reaction is centrifuged, washed with ethanol, and vacuum dried to obtain Pt nanoparticle-loaded TiO2 powder.

[0092] (3) The TiO2 loaded with Pt nanoparticles is dispersed again in ethylene glycol, dispersed evenly, 0.2 g of IrCl3·H2O is added, and stirred and mixed thoroughly to obtain an Ir precursor solution.

[0093] (4) The Ir precursor solution was transferred to a reaction bottle and reacted at 100° C. for 10 hours using a metal bath. The sample after the reaction was centrifuged, washed with ethanol, and vacuum dried to obtain an Ir@Pt@TiO2 catalyst.

[0094] (5) The ionomer solution and solvent were added to the Ir@Pt@TiO2 catalyst respectively, dispersed evenly, and then drop-coated onto carbon paper for three-electrode OER performance characterization.

[0095] (6) Adding an ionomer solution and a solvent to the Ir@Pt@TiO2 catalyst respectively and dispersing them evenly to prepare a catalyst slurry, and spraying the catalyst slurry evenly on the proton exchange membrane using a sprayer on a clean horizontal operating table.

[0096] (7) Using a hot press transfer machine, the cathode catalyst layer was transferred to the other side of the proton exchange membrane sprayed with the Ir@Pt@TiO2 catalyst layer at a temperature of 150°C, a pressure of 40 / 40PSI, and a rotation speed of 6FPM. After packaging, the membrane electrode was prepared and the water electrolysis performance test and the hydrogen in oxygen analysis on the anode side were carried out.

[0097] Example 2

[0098] Membrane electrode including catalytic layer and method for preparing the same

[0099] (1) Add 0.2% TiO2 carrier and 100 ml ethylene glycol into a sample bottle and disperse them evenly. Then add 0.2% H2PtCl6·4H2O into the solution and stir well to obtain a Pt precursor solution.

[0100] (2) The Pt precursor solution is transferred to a reactor and reacted at 150° C. for 18 hours. The sample after the reaction is centrifuged, washed with ethanol, and vacuum dried to obtain Pt nanoparticle-loaded TiO2 powder.

[0101] (3) The TiO2 loaded with Pt nanoparticles is dispersed again in ethylene glycol, evenly dispersed, 0.8% IrCl3·H2O is added, and the mixture is stirred and mixed to obtain an Ir precursor solution.

[0102] (4) The Ir precursor solution was transferred to a reactor and reacted at 150° C. for 18 hours. The sample after the reaction was centrifuged, washed with ethanol, and vacuum dried to obtain an Ir@Pt@TiO2 catalyst.

[0103] (5) The ionomer solution and solvent were added to the Ir@Pt@TiO2 catalyst respectively, dispersed evenly, and then drop-coated onto carbon paper or glassy carbon electrode for three-electrode OER performance characterization.

[0104] (6) Adding an ionomer solution and a solvent to the Ir@Pt@TiO2 catalyst respectively and dispersing them evenly to prepare a catalyst slurry, and spraying the catalyst slurry evenly on the proton exchange membrane using a sprayer on a clean horizontal operating table.

[0105] (7) Using a hot press transfer machine, the cathode catalyst layer was transferred to the other side of the proton exchange membrane sprayed with the Ir@Pt@TiO2 catalyst layer at a temperature of 150°C, a pressure of 40 / 40PSI, and a rotation speed of 6FPM. After packaging, the membrane electrode was prepared and the water electrolysis performance test and the hydrogen in oxygen analysis on the anode side were carried out.

[0106] Example 3

[0107] Membrane electrode including catalytic layer and method for preparing the same

[0108] (1) Add 0.2 g of TiO2 carrier and 100 ml of ethanol into a sample bottle and disperse them evenly. Then add 0.4 g of H2PtCl6·4H2O into the solution and stir well to obtain a Pt precursor solution.

[0109] (2) The Pt precursor solution is transferred to a reactor and reacted at 200° C. for 12 hours. The sample after the reaction is centrifuged, washed with ethanol, and vacuum dried to obtain Pt nanoparticle-loaded TiO2 powder.

[0110] (3) The TiO2 loaded with Pt nanoparticles was dispersed again in ethanol, evenly dispersed, 0.5 g of IrCl3·H2O was added, and the mixture was stirred and mixed to obtain an Ir precursor solution.

[0111] (4) The Ir precursor solution was transferred to a reactor and reacted at 200° C. for 12 hours. The sample after the reaction was centrifuged, washed with ethanol, and vacuum dried to obtain an Ir@Pt@TiO2 catalyst.

[0112] (5) The ionomer solution and solvent were added to the Ir@Pt@TiO2 catalyst respectively, dispersed evenly, and then drop-coated onto carbon paper or glassy carbon electrode for three-electrode OER performance characterization.

[0113] (6) Adding an ionomer solution and a solvent to the Ir@Pt@TiO2 catalyst respectively and dispersing them evenly to prepare a catalyst slurry, and spraying the catalyst slurry evenly on the proton exchange membrane using a sprayer on a clean horizontal operating table.

[0114] (7) Using a hot press transfer machine, the cathode catalyst layer was transferred to the other side of the proton exchange membrane sprayed with the Ir@Pt@TiO2 catalyst layer at a temperature of 150°C, a pressure of 40 / 40PSI, and a rotation speed of 6FPM. After packaging, the membrane electrode was prepared and the water electrolysis performance test and the hydrogen in oxygen analysis on the anode side were carried out.

[0115] Performance Testing

[0116] (1) The catalysts obtained in Examples 1 to 3 were subjected to three-electrode OER performance characterization. The specific experimental methods include linear sweep voltammetry experiment and electrical impedance scanning imaging experiment.

[0117] (2) The membrane electrodes obtained in Examples 1 to 3 were subjected to water electrolysis performance test and anode side oxygen hydrogen analysis. The water electrolysis performance test method was to assemble the prepared hydrogen removal membrane electrode into a water electrolysis cell with an active area of ​​4 square centimeters, apply a stepwise constant current to the cell and record the corresponding voltage to obtain a polarization curve of water electrolysis; the anode side oxygen hydrogen analysis test method was to use a gas chromatograph to detect the hydrogen concentration in the anode side gas.

[0118] Results Analysis

[0119] (1) The catalysts obtained in Examples 1 to 3 were subjected to three-electrode OER performance characterization.

[0120] in, Figure 1 This is a comparison chart of the LSV curves of the water electrolysis dehydrogenation catalyst provided in the embodiment of the present application and the commercial iridium black catalyst; it can be seen that the water electrolysis dehydrogenation catalyst provided in the embodiment of the present application has a more excellent OER activity.

[0121] Figure 2 The impedance diagram of the water electrolysis dehydrogenation catalyst provided in the embodiment of the present application and the commercial iridium black catalyst; it can be seen that the water electrolysis dehydrogenation catalyst provided in the embodiment of the present application has a smaller impedance than the commercial iridium black catalyst, indicating that the introduction of platinum nanoparticles can improve the conductivity of the TiO2 carrier catalyst. (2) The membrane electrodes obtained in Examples 1 to 3 were respectively subjected to water electrolysis performance tests and anode side oxygen hydrogen analysis.

[0122] Among them, the electrolysis water performance results are as follows Figure 3 It can be seen that compared with the commercial iridium black film electrode, the hydrogen removal membrane electrode requires a lower working voltage at the same current density, indicating that the catalyst utilization rate of the synthesized hydrogen removal catalyst is improved and the corresponding water electrolysis efficiency is higher.

[0123] The results of hydrogen analysis in oxygen on the anode side are as follows Figure 4 It can be seen that compared with the commercial iridium black film electrode, the hydrogen content in the oxygen detected by the hydrogen removal membrane electrode at the same current density is lower, indicating that the catalytic hydrogen removal layer provided in the embodiment of the present application can effectively remove the hydrogen that penetrates from the cathode side to the anode side, reduce the hydrogen content in the oxygen on the anode side, and improve the operating safety of the water electrolysis device.

[0124] In summary, the preparation method of the electrolytic water dehydrogenation catalyst provided in the embodiment of the present application is divided into two steps. In the first step, uniform platinum nanoparticles are prepared on the surface of the carrier by a heating reduction method using a reducing agent, and the uniformly loaded platinum nanoparticles form a conductive network, which is beneficial to improving the conductivity of the catalyst; further, iridium nanoparticles are prepared on the surface of the platinum nanoparticles to obtain a catalyst material of Ir@Pt@carrier, so that the obtained catalyst has hydrogen oxidation activity and oxygen evolution reaction activity, and the catalytic activity of the catalyst is improved. In addition, the preparation method is simple and fast, does not require large-scale instruments and equipment and complex processes, and is conducive to large-scale industrial applications.

[0125] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a catalyst for dehydrogenation by electrolysis of water, characterized in that: The steps include: A platinum source, a carrier material and a reducing agent are mixed to obtain a platinum-containing precursor solution, and the platinum-containing precursor solution is subjected to a first heating reduction treatment to obtain a carrier material loaded with platinum nanoparticles; The carrier material loaded with the platinum nanoparticles, an iridium source and a reducing agent are mixed to obtain a mixed solution, and the mixed solution is subjected to a second heating reduction treatment to load iridium nanoparticles on the surface of the platinum nanoparticles of the carrier material to obtain a water electrolysis dehydrogenation catalyst.

2. The method for preparing a water electrolysis hydrogen removal catalyst according to claim 1, characterized in that: The platinum source is selected from H2PtCl6·4H2O, 2(C2H3O2).H 12 N4Pt、C 10 H 14 At least one of O4Pt; and / or, The iridium source is selected from at least one of IrCl3·3H2O, Cl4H3IrO, and IrCl4; and / or, The carrier material is selected from at least one of TiO2, TiN and TiC; and / or, The reducing agent is selected from ethylene glycol or ethanol.

3. The method for preparing a water electrolysis hydrogen removal catalyst according to claim 1, characterized in that: The mass ratio of the platinum source, the carrier material and the reducing agent is 1:1 to 10:200; and / or, The mass ratio of the carrier material loaded with the platinum nanoparticles, the iridium source and the reducing agent is 1:1 to 10:

200.

4. The method for preparing a water electrolysis hydrogen removal catalyst according to claim 1, characterized in that: The temperature of the first heating reduction treatment is 100 to 300° C., and the time is 1 to 12 hours.

5. The method for preparing a water electrolysis hydrogen removal catalyst according to claim 1, characterized in that: The temperature of the second heating reduction treatment is 100 to 200° C., and the time is 1 to 12 hours.

6. A catalyst for dehydrogenation by water electrolysis, characterized in that: The electrolytic water dehydrogenation catalyst is prepared by the preparation method of the electrolytic water dehydrogenation catalyst according to any one of claims 1 to 5, wherein the electrolytic water dehydrogenation catalyst comprises a carrier, platinum nanoparticles are uniformly loaded on the surface of the carrier, and iridium nanoparticles are uniformly loaded on the surfaces of the platinum nanoparticles and the carrier; wherein the particle size of the platinum nanoparticles is 2 to 4 nm.

7. The water electrolysis hydrogen removal catalyst according to claim 6, characterized in that: Taking the total mass of the water electrolysis hydrogen removal catalyst as 100%, the loading amount of the platinum nanoparticles is 1-30%, and the loading amount of the iridium nanoparticles is 1-70%.

8. A method for preparing a catalytic hydrogen removal layer for water electrolysis, characterized in that: The steps include: Provide the water electrolysis hydrogen removal catalyst according to claim 6 or 7, The water electrolysis hydrogen removal catalyst is mixed with an ionomer solution and a solvent to obtain a catalyst slurry; The catalyst slurry is coated on the surface of the proton exchange membrane to obtain a water electrolysis catalytic hydrogen removal layer.

9. A membrane electrode, characterized in that: The membrane electrode comprises a water electrolysis catalytic hydrogen removal layer prepared by the method for preparing a water electrolysis catalytic hydrogen removal layer according to claim 8.

10. A hydrogen production device by electrolysis of water, characterized in that: The water electrolysis hydrogen production device comprises the membrane electrode according to claim 9.

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