CN117512651A - An electrode for electrocatalytic oxygen reduction to prepare hydrogen peroxide - Google Patents

An electrode for electrocatalytic oxygen reduction to prepare hydrogen peroxide Download PDF

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CN117512651A
CN117512651A CN202311566851.8A CN202311566851A CN117512651A CN 117512651 A CN117512651 A CN 117512651A CN 202311566851 A CN202311566851 A CN 202311566851A CN 117512651 A CN117512651 A CN 117512651A
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周强
黄钊圣
李钊
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Wuzhou Hgp Advanced Materials Technology Corp ltd
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Abstract

本发明公开了一种用于电催化氧还原制备过氧化氢的电极，包括由催化剂载体和形成于催化剂载体表面的催化剂层。所述的催化剂载体为具有敞开式骨架的多孔金属，所述多孔金属由金属骨架和孔隙构成，所述金属骨架全部为敞开式骨架或者为敞开式骨架和中空骨架的混合物。通过将多孔金属的大部分或全部中空骨架内的封闭空间打开，增大表面积、提高有效孔隙率，进一步构建具备更高比表面积和孔隙率的催化电极，使其能为电催化反应提供更加多的化学反应活性位点，并且其丰富的孔结构将有助于电解质的高效输运，提升电催化氧还原制备过氧化氢的生产效率。

The invention discloses an electrode used for electrocatalytic oxygen reduction to prepare hydrogen peroxide, which includes a catalyst carrier and a catalyst layer formed on the surface of the catalyst carrier. The catalyst carrier is a porous metal with an open skeleton. The porous metal is composed of a metal skeleton and pores. The metal skeleton is all an open skeleton or a mixture of an open skeleton and a hollow skeleton. By opening most or all of the closed spaces in the hollow skeleton of the porous metal, the surface area is increased, the effective porosity is increased, and a catalytic electrode with a higher specific surface area and porosity is further constructed, so that it can provide more electrocatalytic reactions. It has active sites for chemical reactions, and its rich pore structure will contribute to the efficient transport of electrolytes and improve the production efficiency of electrocatalytic oxygen reduction to produce hydrogen peroxide.

Description

Electrode for preparing hydrogen peroxide by electrocatalytic oxygen reduction
The present application claims priority from the chinese invention application No. 2022114904608 filed on 25/11/2022, the entire contents of which are incorporated herein by reference.
Technical Field
The invention belongs to the technical field of electrocatalysis, and relates to an electrode for preparing hydrogen peroxide by electrocatalytic oxygen reduction.
Background
Hydrogen peroxide (H) 2 O 2 ) Is an important chemical substance, and is widely used as a clean strong oxidant in the fields of medical disinfection, industrial pulp bleaching, environmental management, semiconductor cleaning of electronic military industry and the like. Currently, more than 95% of H 2 O 2 Is produced in concentrated form by the anthraquinone process. Industrial synthesis of H by anthraquinone oxidation method 2 O 2 Requiring complex unit operations, including hydrogenation, O 2 Anthraquinone oxidation, extraction purification and the like are energy-intensive multi-step processes, large infrastructure investment is required, and the production process cost is very high. In addition, H is consumed in large quantities in the industrial application at the present stage 2 O 2 Concentrating and purifying H to obtain 30% aqueous solution 2 O 2 The large amount of waste generated in the process also presents a safety problem for storage and transportation in the product distribution process. Thus, H is reduced 2 O 2 Transportation cost, realize H 2 O 2 Is an urgent problem to be solved at present.
Electrochemical method for electrocatalytic oxygen reduction (ORR) is a substitute for anthraquinone method for H production 2 O 2 It can selectively produce hydrogen peroxide by both oxygen reduction and water oxidation in an electrolytic cell. Typically, in electrolytic cellsIn (2) H is produced by a two electron oxygen reduction reaction 2 O 2 Finally, large-scale cogeneration can be realized; and the double electrons are oxidized to generate H 2 O 2 Two valuable products can be produced in a single electrochemical device starting with water alone. In addition, the electrochemical hydrogen peroxide production process can be combined with renewable energy sources due to the simplicity of the electrochemical device, thereby reducing production costs. At the same time, the electrochemical device can be miniaturized conveniently and the production base can be built in H 2 O 2 Thereby reducing transportation costs; and raw materials and products in the electrochemical method production process are common chemicals such as water, oxygen, acid, alkali and the like, so that green and sustainable production is easy to realize, and the traditional anthraquinone method is expected to be completely replaced in the future.
During the ORR reaction, two reaction pathways occur on the catalyst, with the oxygen molecules first adsorbing on the catalyst surface to form an intermediate OOH, which then passes through 2e - Process desorption to H 2 O 2 Or OOH through 4e - The process dissociates the O-O bond forming intermediate O and is further converted to water. The final product of the electrocatalytic oxygen reduction reaction ORR reaction pathway depends largely on the electrode and catalyst materials selected. In the electrocatalytic process, the electrodes are the key elements. The electrodes can be divided into an anode and a cathode, which respectively carry different electron transfer processes. The anode is typically an oxidizing agent, which from a chemical point of view accepts electrons and participates in the oxidation reaction. The cathode is then typically a reducing agent that provides electrons and participates in the reduction reaction. In this way, the electrocatalytic reaction can be carried out efficiently.
The invention discloses a deep purification device for in-situ generation of hydrogen peroxide and ferrate coupling water treatment and a treatment method thereof (application number is 202010376143.8). The carbon-iron electrode or electrochemical cathode is prepared by mixing a promoter, a pore-forming agent and an electrode substrate, adding a binder, including on foam nickel, and performing vacuum sintering. The obtained electrochemical cathode can efficiently utilize oxygen to efficiently generate hydrogen peroxide in situ.
The Chinese patent application No. 201710100325.0 discloses a method for simultaneously producing hydrogen peroxide and hydrogen by using a self-oxygen-supply double-cathode device, wherein the device used in the technical scheme is provided with two cathodes and a shared anode, namely an oxygen reduction cathode, a hydrogen evolution cathode and an oxygen evolution anode, and oxygen generated by the shared anode is freely diffused to the oxygen reduction cathode in the device, and hydrogen peroxide is generated by in-situ reduction on the surface of an oxygen reduction cathode catalytic layer. The oxygen reduction cathode in the technical scheme consists of a catalyst, a conductive binder and a current collector, wherein the current collector is any one or a combination of at least two of carbon cloth, a stainless steel mesh, a titanium mesh and foam nickel, and hydrogen peroxide is generated on the surface of the catalytic layer of the oxygen reduction cathode by in-situ reduction.
In the solutions of both the above-mentioned patent inventions, foam nickel is used as a carrier for the catalyst, and the catalyst is provided on the surface thereof. The porous metal material not only has large specific surface area, excellent mass transfer performance and strong substance adsorption capacity due to a pore structure, but also has high conductivity, excellent ductility, catalytic activity and the like due to metal properties, is a novel functional porous structure material which is extremely rapidly developed, and has very important position for realizing a high-efficiency electrochemical catalytic technology.
Nickel foam is a typical porous metal that, as an electroformed replica of an organic foam, substantially retains the structural morphology of the original foam. The frames forming the foam nickel are crisscrossed vertically and horizontally, each node is generally formed by 3-5 frames which are crossed, after the organic foam matrix is removed, the metal frames can form fine hollow cavities in the frames, the fine hollow cavities are the spaces left by the original organic foam plastic after disappearing, therefore, the frames are all closed hollow prismatic structures, the fine hollow cavities in the frames are also a part of the whole porosity of the foam nickel, and the fine hollow cavities account for about 2% -20% of the whole porosity of the foam nickel. The pores in the framework have too small pore diameter, so that not only is the electrolyte difficult to transport in the framework, but also the resistivity of the battery can be increased, if the micropores can be utilized in the manufacturing process of the electrode material, the flow resistance of the electrolyte and a gas product in the electrode can be reduced by improving the porosity, and the rate of electrocatalytic reaction is improved.
The porous metal with the hollow prismatic rods has a skeleton with a fine hollow cavity, and the inner wall of the hollow cavity also has a large surface area, but the surface area of the part is difficult to be utilized because the hollow cavity is sealed inside the skeleton. If the surface of the part is exposed by a method, when the porous metal is used as an electrode, the electrolyte can have larger contact area with the current collector, more electrocatalytic reaction sites are provided, and the electrocatalytic preparation of H is improved 2 O 2 Is not limited in the production efficiency.
The porous metal prepared by the template method has the defects that the metal framework is hollow, the hollow cavity in the framework occupies more gaps but is almost unavailable, so that the advantages of the porous metal are difficult to fully develop, the closed hollow prismatic rod structure is required to be opened, the occupied gaps and the surface area are utilized, the porous metal material with higher specific surface area and porosity is further constructed, more chemical reaction active sites can be provided for the electrocatalytic reaction, the abundant pore structure can contribute to the efficient transportation of electrolyte, a better technical scheme can be provided for the design of an electrode structure and a high-efficiency electrocatalyst, and the Oxygen Reduction Reaction (ORR) method is further promoted to produce H 2 O 2 Is a development of (a).
Disclosure of Invention
The invention aims to provide a technical scheme and a corresponding product of an electrode for preparing hydrogen peroxide by electrocatalytic oxygen reduction, wherein a porous metal with an open framework is used as the electrode for preparing hydrogen peroxide by electrocatalytic oxygen reduction. The porous metal with the open framework can open most or all of the closed space in the hollow framework of the porous metal, increase the surface area, reduce the density and improve the effective porosity, so that the potential performance of the porous metal is further released, and the comprehensive performance of the electrocatalytic hydrogen peroxide preparation is improved. The effective porosity means a proportion of pores capable of functioning (absorbing an electrolyte, functioning as an ion channel, etc.) to all pores. The aim of the invention is achieved by the following technical scheme.
An electrode for electrocatalytic oxygen reduction to hydrogen peroxide comprises a catalyst carrier and a catalyst layer formed on the surface of the catalyst carrier;
the catalyst carrier is porous metal with an open type framework, the porous metal consists of a metal framework and pores, the metal framework is obtained by depositing metal on the surface of an organic high polymer porous material and then removing the organic high polymer porous material, and the metal framework is all the open type framework or a mixture of the open type framework and a hollow framework;
the open-type framework comprises a metal deposition layer and a space left after the organic polymer porous material is removed, wherein the left space is incompletely surrounded by the metal deposition layer and can be directly communicated with an external space; the hollow framework comprises a metal deposition layer and a space left after the organic polymer porous material is removed, wherein the left space is completely surrounded by the metal deposition layer and cannot be directly communicated with an external space.
In some embodiments, the porous metal comprises a porous metal with no roughening layer deposited on the surface and a roughening layer deposited on the surface, wherein the roughening layer is a roughened metal layer formed on the surface of the foam metal skeleton by at least one process selected from spraying, coating, electro-deposition, chemical precipitation and sintering.
In some embodiments, the open framework comprises 20% to 100%, preferably 80% to 100% of the total metal framework.
The proportion of the open framework in the invention to the whole metal framework can be measured by the following method: taking a piece of porous metal, filling the porous metal into resin (such as epoxy resin), polishing a test surface, selecting any one of four surfaces parallel to the direction of directional deposition metal on the test surface, selecting a test area with the width equal to the thickness of the porous metal and the length equal to twice the thickness of the porous metal on the test surface after polishing the test surface, calculating the number of open frameworks in the test area and the number of all the metal frameworks, and considering the open frameworks or a part of hollow frameworks as 1 open framework or hollow framework for accumulation if the open frameworks or a part of hollow frameworks are drawn into the test area.
The proportion of open frameworks to total metal frameworks = total number of open frameworks in the test area/(total number of total metal frameworks in the test area x 100%).
In some embodiments, the porous metal is a two-dimensional porous metal, and the metal framework is a continuous solid and is arranged in a polygonal two-dimensional manner; accordingly, the pores exist between the metal skeletons in a columnar and separated manner.
In some embodiments, the porous metal is a three-dimensional porous metal, the metal frameworks of which are continuous solids and have a three-dimensional network structure, and pores among the metal frameworks are mutually communicated.
In some embodiments, the pores have an average pore size of 0.05 to 5mm.
In some embodiments, the metal layer of the metal framework has a thickness of 1 to 1000 μm.
In some embodiments, the porous metal has a thickness of 0.005 to 65mm.
In some embodiments, the metal deposition layer is a bimodal metal deposition layer composed of two different sized grains or a multimodal metal deposition layer composed of a plurality of different sized grains.
In some embodiments, the metal deposition layer is a single metal material formed of any one of iron, nickel, copper, iron, aluminum, chromium, cadmium, germanium, tin, lead, zinc, gold, silver, titanium, cobalt, vanadium, niobium, hafnium, tantalum, bismuth, molybdenum, tungsten, manganese, platinum, palladium, ruthenium, rhodium, iridium, osmium, or a multi-layered metal material or alloy material formed of two or more of the foregoing metals.
The invention relates to a preparation method of porous metal with an open framework and the morphology of the open framework and a hollow framework, and refers to China application with the application number of 2023100140947 and the name of porous metal with an open framework and a manufacturing method thereof.
The space left by the hollow skeleton after the organic high molecular porous material is removed is surrounded by the metal layer, and the space inside the hollow skeleton and the area on the inner wall of the hollow cavity cannot be effectively utilized. The open type framework is communicated with the external environment after the organic high-molecular porous material is removed, the space can be used for filling active substances and the like, and the effective porosity and the surface area of the open type framework are larger than those of the hollow framework. The catalyst carrier is porous metal with an open framework, and as more than 20% of the framework is the open framework, the unavailable inner surface of the original inner cavity is changed into an effective outer surface, so that the surface area of the porous metal is greatly increased, part of the space surrounded by the metal framework is released, and the effective porosity of the porous metal is improved.
When the porous metal with an open framework is used, more catalysts can be loaded on the surface of the porous metal, the larger the surface area of the catalyst is, the more active centers are provided by a catalytic electrode, the more the number of the intermediates OOH formed by adsorbing oxygen molecules on the surface of the catalyst is, and the higher the reaction rate of electrocatalytic oxygen reduction to generate hydrogen peroxide is.
Although conventional porous metals, represented by nickel foam, can also achieve higher surface areas by reducing pore size. However, the adsorption of oxygen molecules to the catalyst is related not only to the specific surface area but also to the pore size. If the pores are too small, electrolyte and oxygen cannot enter the catalyst surface of the inner surface of the pores, and the specific surface area in the pores does not contribute to the activity. Thus, the precondition that the large specific surface area has promotion effect on the catalytic activity is that: the surface of the catalyst may be effective to provide a location where the reactants interact with the active sites. Unlike traditional porous metal comprising hollow skeleton, the porous metal with open skeleton has open closed space inside the porous metal, increased surface area, raised effective porosity, lowered electrolyte flow resistance, capacity of leading oxygen reactant to the surface of the catalyst, reduced mass transfer effect and raised electrode catalytic reaction rate.
Drawings
Fig. 1 is a schematic diagram of an electrode for electrocatalytic oxygen reduction to hydrogen peroxide according to the present invention.
FIG. 2 is a schematic view of the structure of the electrolytic cell in the examples and comparative examples.
Description of the embodiments
The technical scheme of the invention is clearly and completely described below with reference to the attached drawings. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Examples
In this example, an electrode for electrocatalytic oxygen reduction to hydrogen peroxide provided by the present invention was assembled into an electrolytic cell, which was compared with the performance of an electrolytic cell fabricated using conventional foam metal all composed of a hollow skeleton. In this embodiment, as shown in fig. 2, the structure of the electrolytic cell for comparison is that the positive electrode 12 and the negative electrode 13 inside the electrolytic chamber 11 are immersed in the electrolyte, and the positive electrode 12 and the negative electrode 13 are connected to the positive electrode and the negative electrode of the power source 14 respectively through wires. Electrolyte enters the anode chamber from inlet 15 and oxygen gas generated by the reaction flows out from outlet 16. Oxygen or air is fed by a conduit 17 to the vicinity of the cathode 13, where oxygen reduction takes place in the cathode 13 to produce hydrogen peroxide. And (3) after 120min of reaction, taking the electrolyte, and measuring the concentration of hydrogen peroxide by using a titanium potassium oxalate method.
The anode of the electrolytic cell in this example used foam nickel composed of a hollow skeleton in a proportion of 100% of the entire metal skeleton, the foam nickel had an overall thickness of 2.0mm and an average pore diameter of 450 μm, and the metal skeleton had a metal layer thickness of 22 μm, and the metal skeleton was composed of pure nickel.
The cathode of the electrolytic cell adopts an electrode for preparing hydrogen peroxide by electrocatalytic oxygen reduction, and as shown in figure 1, the electrode comprises a catalyst carrier and a catalyst layer formed on the surface of the catalyst carrier. The catalyst carrier is porous metal with an open framework and consists of the open framework and a hollow framework. The open type skeleton accounts for 85% of the total metal skeleton, the three-dimensional porous metal has an overall thickness of 2.0mm and an average pore diameter of 450 μm, the metal layer of the metal skeleton has a thickness of 22 μm, and the metal skeleton is composed of pure nickel. The catalyst is carbon nanotubes grown on the surface of the porous metal.
Using neutral Na 2 SO 4 In the solution as electrolyte, a power supply is used for supplying power to the anode and the cathode of the electrolytic cell, a constant voltage mode is adopted for the cathode, the constant voltage is 0.4V (relative to an Ag/AgCl reference electrode, converted, -0.21V relative to the standard hydrogen electrode potential), and the electrolyte is sampled and tested after 120min, so that the hydrogen peroxide concentration reaches 5.03mg/L.
Comparative example
In this comparative example, an electrolytic cell was assembled using conventional foam metal entirely composed of a hollow skeleton as an electrode, in comparison with the performance of the example. The structure of the electrolytic cell used in this comparative example is shown in FIG. 1.
The anode of the electrolytic cell in this comparative example used foam nickel composed of a hollow skeleton in a proportion of 100% of the entire metal skeleton, the foam nickel had an overall thickness of 2.0mm and an average pore diameter of 450 μm, and the metal skeleton had a metal layer thickness of 22 μm, and the metal skeleton was composed of pure nickel.
The cathode of the electrolytic cell includes a catalyst layer formed of a catalyst support and a catalyst support surface. The catalyst carrier used a nickel foam composed of a hollow skeleton, the hollow skeleton accounting for 100% of the total metal skeleton, the nickel foam having an overall thickness of 2.0mm and an average pore diameter of 450 μm, the metal skeleton having a metal layer thickness of 22 μm, the metal skeleton being composed of pure nickel. The catalyst is carbon nano tube growing on the surface of foam nickel.
Using neutral Na 2 SO 4 In the solution as electrolyte, a power supply is used for supplying power to the anode and the cathode of the electrolytic cell, a constant voltage mode is adopted for the cathode, the constant voltage is 0.4V (relative to an Ag/AgCl reference electrode, converted, -0.21V relative to a standard hydrogen electrode potential), the electrolyte is sampled and tested after 120min, and the hydrogen peroxide concentration is 3.58mg/L.
From experimental results, it can be seen that the electrode for preparing hydrogen peroxide by electrocatalytic oxygen reduction provided by the invention is used for preparing hydrogen peroxide in the examples, and the yield is improved by 40.5% compared with that of the electrode formed by the traditional foam nickel.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention. The protection scope of the present invention is defined by the claims and the equivalents thereof.

Claims (10)

1.一种用于电催化氧还原制备过氧化氢的电极，包括由催化剂载体和形成于催化剂载体表面的催化剂层，其特征在于，1. An electrode for electrocatalytic oxygen reduction to prepare hydrogen peroxide, comprising a catalyst carrier and a catalyst layer formed on the surface of the catalyst carrier, characterized in that, 所述的催化剂载体为具有敞开式骨架的多孔金属，所述多孔金属由金属骨架和孔隙构成，所述金属骨架是通过在有机高分子多孔材料表面沉积金属，然后去除有机高分子多孔材料得到，所述金属骨架全部为敞开式骨架或者为敞开式骨架和中空骨架的混合物；The catalyst carrier is a porous metal with an open skeleton. The porous metal is composed of a metal skeleton and pores. The metal skeleton is obtained by depositing metal on the surface of an organic polymer porous material and then removing the organic polymer porous material. The metal skeletons are all open skeletons or a mixture of open skeletons and hollow skeletons; 所述敞开式骨架包括金属沉积层和有机高分子多孔材料被去除后所留下的空间，所述留下的空间被金属沉积层不完全包围，能与外部空间直接连通；The open skeleton includes the space left after the metal deposition layer and the organic polymer porous material are removed. The remaining space is incompletely surrounded by the metal deposition layer and can be directly connected to the external space; 所述中空骨架包括金属沉积层和有机高分子多孔材料被去除后所留下的空间，所述留下的空间被金属沉积层完全包围，不能与外部空间直接连通。The hollow skeleton includes the space left after the metal deposition layer and the organic polymer porous material are removed. The remaining space is completely surrounded by the metal deposition layer and cannot be directly connected to the external space. 2.根据权利要求1所述的电极，其特征在于，所述的多孔金属包括表面未沉积粗糙化层和表面沉积有粗糙化层的多孔金属，其中：2. The electrode according to claim 1, characterized in that the porous metal includes porous metal without a roughened layer deposited on the surface and with a roughened layer deposited on the surface, wherein: 所述的粗糙化层是通过喷涂、涂覆、电沉积、化学沉淀、烧结中的至少一种工艺，在泡沫金属骨架表面形成的一层粗糙的金属层。The roughened layer is a rough metal layer formed on the surface of the foam metal skeleton through at least one process of spraying, coating, electrodeposition, chemical precipitation, and sintering. 3.根据权利要求1所述的电极，其特征在于，所述敞开式骨架占全部金属骨架的比例为20%~100%，优选80%-100%。3. The electrode according to claim 1, characterized in that the open skeleton accounts for 20% to 100% of the total metal skeleton, preferably 80% to 100%. 4.根据权利要求1所述的电极，其特征在于，所述孔隙的平均孔径为0.05～5mm。4. The electrode according to claim 1, wherein the average pore diameter of the pores is 0.05-5 mm. 5.根据权利要求1所述的电极，其特征在于，所述金属骨架的金属层厚度为1～1000μm。5. The electrode according to claim 1, wherein the thickness of the metal layer of the metal skeleton is 1 to 1000 μm. 6.根据权利要求1所述的电极，其特征在于，所述多孔金属的厚度为0.005～65mm。6. The electrode according to claim 1, wherein the thickness of the porous metal is 0.005-65 mm. 7.根据权利要求1所述的电极，其特征在于，所述金属沉积层是由两种不同尺寸晶粒构成的双模态金属沉积层或者是由多种不同尺寸晶粒构成的多模态金属沉积层。7. The electrode according to claim 1, characterized in that the metal deposition layer is a bimodal metal deposition layer composed of two types of grains of different sizes or a multimodal metal deposition layer composed of a plurality of grains of different sizes. Metal deposition layer. 8.根据权利要求1所述的电极，其特征在于，所述金属沉积层是由铁、镍、铜、铁、铝、铬、镉、锗、锡、铅、锌、金、银、钛、钴、钒、铌、铪、钽、铋、钼、钨、锰、铂、钯、钌、铑、铱、锇中的任意一种形成的单金属材料，或者是由上述金属中的两种以上形成的多层金属材料或者合金材料。8. The electrode according to claim 1, characterized in that the metal deposition layer is made of iron, nickel, copper, iron, aluminum, chromium, cadmium, germanium, tin, lead, zinc, gold, silver, titanium, A single metal material formed from any one of cobalt, vanadium, niobium, hafnium, tantalum, bismuth, molybdenum, tungsten, manganese, platinum, palladium, ruthenium, rhodium, iridium and osmium, or two or more of the above metals The formed multi-layer metal material or alloy material. 9.根据权利要求1所述的电极，其特征在于，所述多孔金属为三维多孔金属。9. The electrode according to claim 1, wherein the porous metal is a three-dimensional porous metal. 10.根据权利要求1所述的电极，其特征在于，所述多孔金属为二维多孔金属。10. The electrode according to claim 1, wherein the porous metal is a two-dimensional porous metal.
CN202311566851.8A 2022-11-25 2023-11-23 An electrode for electrocatalytic oxygen reduction to prepare hydrogen peroxide Pending CN117512651A (en)

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CN202211490460 2022-11-25
CN2022114904608 2022-11-25

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CN202310014094.7A Active CN116024619B (en) 2022-11-25 2023-01-05 Porous metal with open framework and method of making same
CN202311548365.3A Pending CN117535708A (en) 2022-11-25 2023-11-20 A catalytic electrode for electrolytic hydrogen production
CN202311548321.0A Active CN117717838B (en) 2022-11-25 2023-11-20 Filter material made of porous metal with open framework
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