All-solid-state electrolysis reaction device for electrocatalytic reduction of carbon dioxide to produce carbon monoxide

Abstract

The present invention relates to an all-solid-state electrolysis reaction device for preparing carbon monoxide by electrocatalytic reduction of carbon dioxide, comprising a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane, and a gas diffusion anode arranged in sequence; the gas diffusion cathode comprises a cathode current collector, a cathode macroporous diffusion layer, and a microporous diffusion-catalysis integrated layer arranged in sequence; the microporous diffusion-catalysis integrated layer is arranged close to the anion exchange membrane; the gas diffusion anode comprises an anode macroporous diffusion layer and an anode current collector arranged in sequence; the anode macroporous diffusion layer is arranged close to the cation exchange membrane; the cathode macroporous diffusion layer and the anode macroporous diffusion layer both comprise nanocomposite porous materials; and the microporous diffusion-catalysis integrated layer comprises carrageenan-derived porous carbon deposited with metal atom clusters and a covalent organic framework.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy technologies, and in particular to an all-solid-state electrolysis reaction device for preparing carbon monoxide by electrocatalytic reduction of carbon dioxide. Background Art

[0002] The full solid-state of carbon dioxide electrocatalytic reduction devices can not only bring many advantages such as compact structure, safety and reliability, but its convenience of mass production is an indispensable condition for industrialization. At present, derived porous carbon materials based on covalent organic frameworks (COFs) have been used in this field as catalyst supports, but COFs are not only expensive and unfavorable for mass production, but their overly regular pore size is conducive to the design of porous structures, but the lack of hierarchical porous structures is not conducive to the ion diffusion required for electrocatalytic reduction, especially the lack of one-dimensional ion channels with large aspect ratios, which is obviously unfavorable for all-solid-state devices that do not use liquid electrolytes. In addition, lamination is required in the fully automatic process, and the simple rigid three-dimensional porous structure lacks a network formed by a one-dimensional structure as support, which is very easy to be destroyed in the process. The present invention introduces carrageenan into COF-derived porous carbon. Carrageenan, due to its natural molecular structure, can form a double helix one-dimensional structure by natural cooling under the conditions of hot water temperature treatment, and forms a one-dimensional carbon structure under pyrolysis conditions, providing one-dimensional ion channels and enhancing the mechanical properties of the porous matrix, forming a synergistic effect with the regular porous structure of COF to solve this problem. Summary of the Invention

[0003] In light of this, the present invention provides an all-solid-state electrolysis reaction device for producing carbon monoxide by the electrocatalytic reduction of carbon dioxide. The resulting reaction device not only enables highly selective electrocatalytic reduction of carbon dioxide to produce carbon monoxide, but also addresses carbon dioxide loss caused by the carbonate shuttling effect during the reaction, thereby improving its utilization rate.

[0004] The technical solutions provided by the present invention are as follows:

[0005] An all-solid-state electrolytic reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide, characterized by comprising a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane, and a gas diffusion anode arranged in sequence;

[0006] The gas diffusion cathode comprises a cathode current collector, a cathode macroporous diffusion layer, and a microporous diffusion-catalytic integrated layer arranged in sequence; the microporous diffusion-catalytic integrated layer is arranged close to the anion exchange membrane;

[0007] The gas diffusion anode comprises an anode macroporous diffusion layer and an anode current collector which are arranged in sequence; the anode macroporous diffusion layer is arranged close to the cation exchange membrane;

[0008] The cathode macroporous diffusion layer and the anode macroporous diffusion layer both comprise nanocomposite porous materials;

[0009] The microporous diffusion-catalysis integrated layer comprises carrageenan-derived porous carbon deposited with metal atom clusters and a covalent organic framework.

[0010] The cathode current collector is composed of a nickel mesh; the anode current collector is composed of an iridium oxide coated titanium mesh.

[0011] The nanocomposite porous material includes a fluorine-silicon nanocomposite porous material.

[0012] The fluorine-silicon nanocomposite porous material is obtained by mixing the following substances in parts by weight and then heating and stirring:

[0013]

[0014] The silicon nanowire aggregates are prepared by placing metallurgical-grade silicon powder in a mixed solution of silver nitrate, hydrofluoric acid, and hydrogen peroxide, reacting under ultrasound, filtering, washing, and vacuum drying; wherein the concentration of silver nitrate is 0.5mM-1mM, the concentration of hydrofluoric acid is 4M-5M, and the concentration of hydrogen peroxide is 0.05M-0.1M;

[0015] The mass concentration of the polytetrafluoroethylene emulsion is 50% to 60%, the length of the carbon nanotubes is 3-5 μM, and the diameter of the carbon nanotubes is 50-100 nM;

[0016] The heating temperature is 75-80°C.

[0017] The fluorine-silicon nanocomposite porous material is coated on a nickel mesh and then hot-pressed to obtain a cathode current collector-macroporous diffusion composite layer.

[0018] The gas diffusion cathode is prepared by placing a microporous diffusion-catalytic integrated layer on the side of a cathode current collector-macroporous diffusion composite layer close to the cathode macroporous diffusion layer, and hot pressing and cooling at 20-30 MPa and 120-160° C.

[0019] The metal atom is one of a gold atom, a platinum atom and a palladium atom.

[0020] The method for preparing the gas diffusion anode comprises the following steps:

[0021] A fluorine-silicon nanocomposite porous material is placed on an iridium oxide-coated titanium mesh, and then a perfluorosulfonic acid polymer is coated on the surface of the fluorine-silicon nanocomposite porous material. A flat plate vulcanizer is used to hot-press and cool the material at 20-30 MPa and 120-160°C to obtain a gas diffusion anode.

[0022] The microporous diffusion-catalysis integrated layer is obtained by mixing a covalent organic framework, a carrageenan nanocomposite, a 10wt% Nafion resin solution, and ethanol, followed by ultrasonic dispersion and vacuum drying. The covalent organic framework accounts for 6-10 parts, the Nafion resin solution accounts for 50-60 parts, the ethanol accounts for 80-100 parts, and the carrageenan nanocomposite accounts for 20-30 parts by weight.

[0023] The carrageenan nanocomposite is prepared by dispersing carrageenan-derived porous carbon in an aqueous solution of tetrachloroauric acid and sodium citrate, followed by heating for reaction, filtering, washing, and vacuum drying. The concentration of the tetrachloroauric acid is 0.8 mM to 1.2 mM, and the concentration of the sodium citrate is 2.4 mM to 3.6 mM. The heating reaction temperature is 85-90° C., and the heating time is 20-30 minutes.

[0024] The carrageenan-derived porous carbon is obtained by heating carrageenan in an inert atmosphere (tube furnace), washing with sulfuric acid, and then vacuum drying. The inert gas atmosphere refers to one of argon and nitrogen, and the heating temperature is 800-900° C. for 10-12 hours.

[0025] The anion exchange membrane is composed of a polystyrene random copolymer electrolyte;

[0026] The solid electrolyte is composed of hydrogen-type ion exchange resin;

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. By using a composite porous matrix of carrageenan-derived porous carbon and COF (covalent organic framework) as a metal catalyst carrier, the problem of lack of one-dimensional ion channels in the three-dimensional regular porous structure was solved, achieving the beneficial effects of improved electrocatalytic performance and compatibility with the lamination process.

[0029] 2. By introducing silicon nanowires and carbon nanotubes into the macro-controlled diffusion layer based on polytetrafluoroethylene, the problem that the pure PTFE porous substrate is easily damaged under lamination pressure and temperature is solved, and the beneficial effect of improving the mechanical properties of the macroporous diffusion layer is achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Other features, objects and advantages of the present invention will become more apparent upon reading the detailed description of non-limiting embodiments with reference to the following drawings:

[0031] Figure 1 An all-solid-state electrolysis reaction device for preparing carbon monoxide by the carbon dioxide electrocatalytic reduction method of the present invention;

[0032] Figure 2The hydrogen reduction current and carbon monoxide reduction current of the all-solid-state electrolysis reaction device for preparing carbon monoxide by the carbon dioxide electrocatalytic reduction method of the present invention at different potentials (electrode area 2.25cm 2 );

[0033] Figure 3 The Faraday efficiency and current stability of the all-solid-state electrolysis reaction device for preparing carbon monoxide by the carbon dioxide electrocatalytic reduction method of the present invention (electrode area 2.25cm 2 ). DETAILED DESCRIPTION

[0034] The present invention will be described in detail below with reference to the examples. The following examples will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that those skilled in the art may make several adjustments and improvements without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0035] like Figure 1 The present invention provides a fully solid-state electrolysis reaction device for preparing carbon monoxide by the electrocatalytic reduction of carbon dioxide, comprising: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a gas diffusion anode, a cation exchange membrane, a cathode gas chamber flow channel plate, and an anode gas chamber flow channel plate.

[0036] Example 1

[0037] This embodiment provides an all-solid-state electrolysis reaction device for producing carbon monoxide by the electrocatalytic reduction of carbon dioxide. The device comprises a cathode gas chamber flow channel plate, a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane, a gas diffusion anode, and an anode gas chamber flow channel plate. (The cathode and anode gas chamber flow channel plates are standard serpentine flow channel fuel cell plates, and the cation exchange membrane uses Nafion 117, both commercially available products.)

[0038] 1. Gas diffusion cathode

[0039] The gas diffusion cathode comprises a cathode current collector, a cathode macroporous diffusion layer, and a microporous diffusion-catalytic integrated layer arranged in sequence; the microporous diffusion-catalytic integrated layer is arranged close to the anion exchange membrane;

[0040] The cathode current collector is composed of nickel mesh;

[0041] The cathode macroporous diffusion layer is made of fluorine-silicon nanocomposite porous material;

[0042] The cathode current collector and the cathode macroporous diffusion layer are prepared by coating a fluorine-silicon nanocomposite porous material on a nickel mesh and then hot-pressing the material using a flat vulcanizer to obtain a cathode current collector-macroporous diffusion composite layer;

[0043] The pore size of the nickel mesh is 200 mesh, the pressure of the flat vulcanizing press is 5 MPa, and the temperature is 100°C.

[0044] The microporous diffusion-catalysis integrated layer is composed of carrageenan-derived porous carbon deposited with gold atomic clusters and a covalent organic framework.

[0045] The gas diffusion cathode is prepared by placing a microporous diffusion-catalytic integrated layer on the side of the cathode current collector-macroporous diffusion composite layer close to the cathode macroporous diffusion layer, and hot pressing and cooling at 20 MPa and 120° C. using a flat vulcanizer.

[0046] Specifically, the microporous diffusion-catalysis integrated layer is obtained by mixing a covalent organic framework, a carrageenan nanocomposite with a 10wt% Nafion resin solution and ethanol, ultrasonically dispersing the mixture, and vacuum drying the mixture; wherein, by weight, the covalent organic framework is 6 parts, the Nafion resin solution is 50 parts, the ethanol is 80 parts, and the carrageenan nanocomposite is 20 parts.

[0047] The covalent organic framework was prepared according to the method described in Chinese patent CN201510268041.3;

[0048] The carrageenan nanocomposite is obtained by dispersing carrageenan-derived porous carbon in an aqueous solution of tetrachloroauric acid and sodium citrate, heating the mixture at 85° C. for 20 minutes, filtering, washing, and vacuum drying.

[0049] The concentration of tetrachloroauric acid was 0.8 mM, and the concentration of sodium citrate was 2.4 mM.

[0050] Carrageenan-derived porous carbon is obtained by heating carrageenan in an inert atmosphere in a tube furnace for a period of time, washing with sulfuric acid for a period of time, and then vacuum drying. The vacuum drying treatment conditions are 80°C for 18-24 hours. The inert atmosphere (argon, nitrogen can also be used) is heated at a temperature of 800°C for 10 hours.

[0051] The perfluorosulfonic acid polymer is Nafion 117 resin.

[0052] 2. Anion exchange membrane

[0053] The anion exchange membrane is composed of a polystyrene random copolymer electrolyte and is Sustainion X37-50.

[0054] 3. Solid electrolyte

[0055] The solid electrolyte is composed of hydrogen-type ion exchange resin and Dowex 50W X8 with a particle size of 400 mesh.

[0056] 4. Gas diffusion anode

[0057] The gas diffusion anode comprises an anode macroporous diffusion layer and an anode current collector; the anode macroporous diffusion layer is arranged close to the cation exchange membrane;

[0058] The anode current collector is composed of an iridium oxide coated titanium mesh;

[0059] The anode macroporous diffusion layer is made of fluorine-silicon nanocomposite porous material;

[0060] A fluorine-silicon nanocomposite porous material is placed on an iridium oxide-coated titanium mesh, and then a perfluorosulfonic acid polymer is coated on the surface of the fluorine-silicon nanocomposite porous material. After hot pressing and cooling at 20 MPa and 120°C using a flat vulcanizer, a gas diffusion anode is obtained.

[0061] The fluorine-silicon nanocomposite porous material of the cathode macroporous diffusion layer and the anode macroporous diffusion layer is obtained by heating and stirring in a hot water bath (by weight, 5 parts of silicon nanowire aggregates, 100 parts of polytetrafluoroethylene emulsion, 100 parts of anhydrous ethanol, and 5 parts of carbon nanotubes in a certain proportion);

[0062] The silicon nanowire aggregates are prepared by placing metallurgical-grade silicon powder in a mixed solution of silver nitrate, hydrofluoric acid and hydrogen peroxide, reacting under ultrasound, filtering, washing and vacuum drying;

[0063] The concentration of silver nitrate was 0.5 mM, the concentration of hydrofluoric acid was 4 M, and the concentration of hydrogen peroxide was 0.05 M.

[0064] The mass concentration of PTFE emulsion (polytetrafluoroethylene) is 50%, the length of the carbon nanotube is 3-5 μM, the diameter of the carbon nanotube is 50-100 nM, and the temperature of the hot water bath is 75-80° C.

[0065] Example 2

[0066] This embodiment provides an all-solid-state electrolysis reaction device for producing carbon monoxide by the electrocatalytic reduction of carbon dioxide. The device comprises a cathode gas chamber flow channel plate, a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane, a gas diffusion anode, and an anode gas chamber flow channel plate. (The cathode and anode gas chamber flow channel plates are standard serpentine flow channel fuel cell plates, and the cation exchange membrane uses Nafion 117, both commercially available products.)

[0067] 1. Gas diffusion cathode

[0068] The gas diffusion cathode comprises a cathode current collector, a cathode macroporous diffusion layer, and a microporous diffusion-catalytic integrated layer arranged in sequence; the microporous diffusion-catalytic integrated layer is arranged close to the anion exchange membrane;

[0069] The cathode current collector is composed of nickel mesh;

[0070] The cathode macroporous diffusion layer is made of fluorine-silicon nanocomposite porous material;

[0071] The cathode current collector and the cathode macroporous diffusion layer are prepared by coating a fluorine-silicon nanocomposite porous material on a nickel mesh and then hot-pressing the material using a flat vulcanizer to obtain a cathode current collector-macroporous diffusion composite layer;

[0072] The pore size of the nickel mesh is 400 mesh, the pressure of the flat vulcanizing press is 10 MPa, and the temperature is 120°C.

[0073] The microporous diffusion-catalysis integrated layer is composed of carrageenan-derived porous carbon deposited by platinum atomic clusters and a covalent organic framework.

[0074] The microporous diffusion-catalytic integrated layer is placed on the side of the cathode current collector-macroporous diffusion composite layer close to the cathode macroporous diffusion layer, and a flat plate vulcanizer is used to hot press and cool at 20-30 MPa and 120-160°C to obtain a gas diffusion cathode.

[0075] Furthermore, the microporous diffusion-catalysis integrated layer is obtained by mixing a covalent organic framework, a carrageenan nanocomposite with a 10wt% Nafion resin solution and ethanol, ultrasonically dispersing the mixture and vacuum drying the mixture; wherein, by weight, the covalent organic framework is 10 parts, the Nafion resin solution is 60 parts, the ethanol is 100 parts, and the carrageenan nanocomposite is 30 parts.

[0076] The covalent organic framework was prepared according to the method described in Chinese patent CN201510268041.3;

[0077] The carrageenan nanocomposite is obtained by dispersing carrageenan-derived porous carbon in an aqueous solution of potassium hexachloroplatinate and sodium citrate, heating and reacting for a period of time, filtering, washing and vacuum drying.

[0078] The concentration of tetrachloroauric acid was 1.2 mM, and the concentration of sodium citrate was 3.6 mM.

[0079] The heating reaction temperature is 90°C and the heating time is 30 minutes;

[0080] The carrageenan-derived porous carbon is obtained by heating carrageenan in an inert atmosphere in a tube furnace for a period of time, washing with sulfuric acid for a period of time, and then vacuum drying. The vacuum drying treatment conditions are 90°C for 24 hours. The inert atmosphere refers to argon (nitrogen can also be used), and the heating temperature is 900°C for 12 hours.

[0081] The perfluorosulfonic acid polymer is Nafion 117 resin.

[0082] 2. Anion exchange membrane

[0083] The anion exchange membrane is composed of a polystyrene random copolymer electrolyte and is Sustainion X37-50.

[0084] 3. Solid electrolyte

[0085] The solid electrolyte is composed of hydrogen-type ion exchange resin and Dowex 50W X8 with a particle size of 400 mesh.

[0086] 4. Gas diffusion anode

[0087] The gas diffusion anode comprises an anode macroporous diffusion layer and an anode current collector; the anode macroporous diffusion layer is arranged close to the cation exchange membrane;

[0088] The anode current collector is composed of an iridium oxide coated titanium mesh;

[0089] The anode macroporous diffusion layer is made of fluorine-silicon nanocomposite porous material;

[0090] A fluorine-silicon nanocomposite porous material is placed on an iridium oxide-coated titanium mesh, and then a perfluorosulfonic acid polymer is coated on the surface of the fluorine-silicon nanocomposite porous material. After hot pressing and cooling at 30 MPa and 160°C using a flat vulcanizer, a gas diffusion anode is obtained.

[0091] The fluorine-silicon nanocomposite porous material of the cathode macroporous diffusion layer and the anode macroporous diffusion layer is obtained by mixing (by weight, 5 parts of silicon nanowire aggregates, 100 parts of polytetrafluoroethylene emulsion, 100 parts of anhydrous ethanol, and 5 parts of carbon nanotubes) and heating and stirring in a hot water bath;

[0092] The silicon nanowire aggregates are prepared by placing metallurgical-grade silicon powder in a mixed solution of silver nitrate, hydrofluoric acid and hydrogen peroxide, reacting under ultrasound, filtering, washing and vacuum drying;

[0093] The concentration of silver nitrate was 1 mM, the concentration of hydrofluoric acid was 5 M, and the concentration of hydrogen peroxide was 0.1 M.

[0094] The mass concentration of PTFE emulsion (polytetrafluoroethylene) is 60%, the length of the carbon nanotube is 5 μM, the diameter of the carbon nanotube is 100 nM, and the temperature of the hot water bath is 80°C.

[0095] Example 3

[0096] This embodiment provides an all-solid-state electrolysis reaction device for producing carbon monoxide by the electrocatalytic reduction of carbon dioxide. The device comprises a cathode gas chamber flow channel plate, a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane, a gas diffusion anode, and an anode gas chamber flow channel plate. (The cathode and anode gas chamber flow channel plates are standard serpentine flow channel fuel cell plates, and the cation exchange membrane uses Nafion 117, both commercially available products.)

[0097] 1. Gas diffusion cathode

[0098] The gas diffusion cathode comprises a cathode current collector, a cathode macroporous diffusion layer, and a microporous diffusion-catalytic integrated layer arranged in sequence; the microporous diffusion-catalytic integrated layer is arranged close to the anion exchange membrane;

[0099] The cathode current collector is composed of nickel mesh;

[0100] The cathode macroporous diffusion layer is made of fluorine-silicon nanocomposite porous material;

[0101] The cathode current collector and the cathode macroporous diffusion layer are prepared by coating a fluorine-silicon nanocomposite porous material on a nickel mesh and then hot-pressing the material using a flat vulcanizer to obtain a cathode current collector-macroporous diffusion composite layer;

[0102] The pore size of the nickel mesh is 200 mesh, the pressure of the flat vulcanizing press is 5 MPa, and the temperature is 100°C.

[0103] The microporous diffusion-catalysis integrated layer is composed of carrageenan-derived porous carbon deposited by palladium atomic clusters and a covalent organic framework.

[0104] The microporous diffusion-catalytic integrated layer is placed on the side of the cathode current collector-macroporous diffusion composite layer close to the cathode macroporous diffusion layer, and a flat plate vulcanizer is used to hot press and cool at 20-30 MPa and 120-160°C to obtain a gas diffusion cathode.

[0105] The microporous diffusion-catalysis integrated layer is obtained by mixing a covalent organic framework, a carrageenan nanocomposite, a 10wt% Nafion resin solution, and ethanol, followed by ultrasonic dispersion and vacuum drying. The covalent organic framework comprises 6 parts, the Nafion resin solution comprises 50 parts, the ethanol comprises 80 parts, and the carrageenan nanocomposite comprises 20 parts by weight.

[0106] The covalent organic framework was prepared according to the method described in Chinese patent CN201510268041.3;

[0107] The carrageenan nanocomposite is prepared by dispersing carrageenan-derived porous carbon in an aqueous solution of potassium tetrachloropalladate and sodium citrate, heating the mixture for a period of time (the heating temperature is 85° C. and the heating time is 20 minutes), filtering, washing and vacuum drying.

[0108] The concentration of tetrachloroauric acid was 0.8 mM, and the concentration of sodium citrate was 2.4 mM.

[0109] The carrageenan-derived porous carbon is obtained by heating carrageenan in an inert atmosphere in a tube furnace for a period of time, washing with sulfuric acid for a period of time, and then vacuum drying. The vacuum drying treatment conditions are 80°C for 24 hours. The inert atmosphere is argon, the heating temperature is 900°C, and the heating time is 10 hours.

[0110] The perfluorosulfonic acid polymer is Nafion 117 resin.

[0111] 2. Anion exchange membrane

[0112] The anion exchange membrane is composed of a polystyrene random copolymer electrolyte and is Sustainion X37-50.

[0113] 3. Solid electrolyte

[0114] The solid electrolyte is composed of hydrogen-type ion exchange resin and Dowex 50W X8 with a particle size of 400 mesh.

[0115] 4. Gas diffusion anode

[0116] The gas diffusion anode comprises an anode macroporous diffusion layer and an anode current collector; the anode macroporous diffusion layer is arranged close to the cation exchange membrane;

[0117] The anode current collector is composed of an iridium oxide coated titanium mesh;

[0118] The anode macroporous diffusion layer is made of fluorine-silicon nanocomposite porous material;

[0119] A fluorine-silicon nanocomposite porous material is placed on an iridium oxide-coated titanium mesh, and then a perfluorosulfonic acid polymer is coated on the surface of the fluorine-silicon nanocomposite porous material. After hot pressing and cooling at 30 MPa and 140°C using a flat vulcanizer, a gas diffusion anode is obtained.

[0120] The cathode macroporous diffusion layer and the anode macroporous diffusion layer are prepared by mixing (by weight) 5 parts of silicon nanowire aggregates, 100 parts of polytetrafluoroethylene emulsion, 100 parts of anhydrous ethanol, and 5 parts of carbon nanotubes, and heating and stirring in a hot water bath;

[0121] The silicon nanowire aggregates are prepared by placing metallurgical-grade silicon powder in a mixed solution of silver nitrate, hydrofluoric acid and hydrogen peroxide, reacting under ultrasound, filtering, washing and vacuum drying;

[0122] The concentration of silver nitrate is 0.5mM-1mM, the concentration of hydrofluoric acid is 4M, and the concentration of hydrogen peroxide is 0.1M.

[0123] The mass concentration of PTFE emulsion (polytetrafluoroethylene) is 50%, the length of the carbon nanotube is 5 μM, the diameter of the carbon nanotube is 100 nM, and the temperature of the hot water bath is 75-80° C.

[0124] Comparative Example 1

[0125] The difference between Comparative Example 1 and Example 1 is:

[0126] The microporous diffusion-catalysis integrated layer is composed of carrageenan-derived porous carbon deposited with gold atomic clusters.

[0127] The microporous diffusion-catalysis integrated layer is obtained by mixing carrageenan nanocomposite with 10wt% Nafion resin solution and ethanol, ultrasonically dispersing and vacuum drying; wherein, by weight, the Nafion resin solution is 50 parts, the ethanol is 80 parts, and the carrageenan nanocomposite is 20 parts.

[0128] The preparation method of carrageenan nanocomposite is the same as that in Example 1.

[0129] Comparative Example 2

[0130] The difference between Comparative Example 2 and Example 2 is:

[0131] The microporous diffusion-catalysis integrated layer is composed of carrageenan-derived porous carbon deposited with platinum atomic clusters.

[0132] The microporous diffusion-catalysis integrated layer is obtained by mixing carrageenan nanocomposite with 10wt% Nafion resin solution and ethanol, ultrasonically dispersing and vacuum drying; wherein, by weight, the Nafion resin solution is 60 parts, the ethanol is 100 parts, and the carrageenan nanocomposite is 30 parts.

[0133] The preparation method of carrageenan nanocomposite is the same as that in Example 2.

[0134] Comparative Example 3

[0135] The difference between Comparative Example 3 and Example 3 is that the microporous diffusion-catalysis integrated layer is composed of carrageenan-derived porous carbon deposited by palladium atomic clusters.

[0136] The microporous diffusion-catalysis integrated layer is obtained by mixing carrageenan nanocomposite with 10wt% Nafion resin solution and ethanol, ultrasonically dispersing and vacuum drying; wherein, by weight, the Nafion resin solution is 50 parts, the ethanol is 80 parts, and the carrageenan nanocomposite is 20 parts.

[0137] The preparation method of carrageenan nanocomposite is the same as that in Example 3.

[0138] Performance Testing

[0139] Linear sweep voltammetry was used to measure the hydrogen reduction current and carbon monoxide reduction current at different potentials, and the time-ampere method was used to measure the Faradaic efficiency and current stability.

[0140] Figure 2 The figures show the hydrogen reduction current and carbon monoxide reduction current of the device described in Example 1 at different potentials (electrode area 2.25 cm 2 );

[0141] Figure 3 The Faradaic efficiency and current stability of the device (electrode area 2.25cm 2 ).

[0142] Table 1 shows the reduction currents of the examples and comparative examples at different potentials.

[0143]

[0144] Table 2 shows the reduction current stability of the examples and comparative examples at a potential of -0.7 V (vs RHE).

[0145]

[0146]

[0147] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various variations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. An all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide, characterized in that: It includes a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane, and a gas diffusion anode which are arranged in sequence; The gas diffusion cathode comprises a cathode current collector, a cathode macroporous diffusion layer, and a microporous diffusion-catalytic integrated layer arranged in sequence; the microporous diffusion-catalytic integrated layer is arranged close to the anion exchange membrane; The gas diffusion anode comprises an anode macroporous diffusion layer and an anode current collector which are arranged in sequence; the anode macroporous diffusion layer is arranged close to the cation exchange membrane; The cathode macroporous diffusion layer and the anode macroporous diffusion layer both comprise nanocomposite porous materials; The microporous diffusion-catalysis integrated layer comprises carrageenan-derived porous carbon deposited with metal atom clusters and a covalent organic framework; The cathode current collector is composed of a nickel mesh; the anode current collector is composed of an iridium oxide coated titanium mesh.

2. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 1, characterized in that: The nano composite porous material is a fluorine-silicon nano composite porous material.

3. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 2, characterized in that: The fluorine-silicon nanocomposite porous material is obtained by mixing the following substances in parts by weight and then heating and stirring: 5-10 parts of silicon nanowire aggregates 80-100 parts of polytetrafluoroethylene emulsion 80-100 parts of anhydrous ethanol 5-10 parts of carbon nanotubes; The silicon nanowire aggregates are prepared by placing metallurgical-grade silicon powder in a mixed solution of silver nitrate, hydrofluoric acid, and hydrogen peroxide, reacting under ultrasound, filtering, washing, and vacuum drying; wherein the concentration of silver nitrate is 0.5 mM-1 mM, the concentration of hydrofluoric acid is 4 M-5 M, and the concentration of hydrogen peroxide is 0.05 M-0.1 M; The mass concentration of the polytetrafluoroethylene emulsion is 50% to 60%, the length of the carbon nanotubes is 3 to 5 μm, and the diameter of the carbon nanotubes is 50 to 100 nm; The heating temperature is 75-80°C.

4. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 2, characterized in that: The fluorine-silicon nanocomposite porous material is coated on a nickel mesh and then hot-pressed to obtain a cathode current collector-macroporous diffusion composite layer.

5. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 4, characterized in that: The gas diffusion cathode is prepared by placing a microporous diffusion-catalytic integrated layer on the side of a cathode current collector-macroporous diffusion composite layer close to the cathode macroporous diffusion layer, and hot pressing and cooling at 20-30 MPa and 120-160°C.

6. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 2, characterized in that: The method for preparing the gas diffusion anode comprises the following steps: A fluorine-silicon nanocomposite porous material is placed on an iridium oxide-coated titanium mesh, and then a perfluorosulfonic acid polymer is coated on the surface of the fluorine-silicon nanocomposite porous material. After hot pressing and cooling at 20-30 MPa and 120-160°C using a vulcanizer, a gas diffusion anode is obtained.

7. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 1, characterized in that: The metal atom includes one of a gold atom, a platinum atom, and a palladium atom.

8. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 1, characterized in that: The microporous diffusion-catalysis integrated layer is obtained by mixing a covalent organic framework, a carrageenan nanocomposite, a 10wt% Nafion resin solution, and ethanol, followed by ultrasonic dispersion and vacuum drying. The covalent organic framework accounts for 6-10 parts, the Nafion resin solution accounts for 50-60 parts, the ethanol accounts for 80-100 parts, and the carrageenan nanocomposite accounts for 20-30 parts by weight.

9. The all-solid-state electrolysis reaction device for producing carbon monoxide by electrocatalytic reduction of carbon dioxide according to claim 8, characterized in that: The carrageenan nanocomposite is obtained by dispersing carrageenan-derived porous carbon in an aqueous solution of tetrachloroauric acid and sodium citrate, heating for reaction, filtering, washing and vacuum drying. The carrageenan-derived porous carbon is obtained by heating carrageenan in an inert atmosphere, washing with sulfuric acid, and then vacuum drying.

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