A Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensional regulation of carbon carrier and a preparation method thereof

Abstract

The application belongs to the field of electro-reduction carbon dioxide catalysis, and particularly relates to a preparation method of a Gd-CuO electro-catalytic CO2 reduction catalyst based on dimension regulation of a carbon carrier. The application synthesizes a metal organic framework precursor at room temperature, obtains carbon materials with different dimensional structures through carbonization, and uses the carbon materials as carriers to synthesize copper-based catalysts loaded on the carriers through a hydrothermal method, so as to improve the performance of the carrier-loaded copper-based catalysts in electro-catalytic reduction of CO2 into C2H4. The carbon material with a two-dimensional sheet structure has a high specific surface area, and can make Gd-CuO flower-like microsphere structures broken, and then loaded on a two-dimensional carrier with nanoscale, so as to expose more edge and defect sites, better adsorb CO2, and the loaded copper-based catalyst has good catalytic performance.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalysis for carbon dioxide reduction, and specifically relates to a method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support. Background Technology

[0002] Fossil fuels are a vital, non-renewable energy source that drives technological progress; however, their use releases large amounts of CO2, causing serious environmental problems. Converting CO2 into high-value fuels is a promising strategy to reduce CO2 accumulation and replace fossil fuels. This method can provide sustainable energy, making the development of efficient CO2 conversion technologies both urgent and promising. Currently, CO2 catalytic conversion technologies include photochemical, thermochemical, enzymatic, and electrochemical methods. Considering factors such as energy efficiency, production rate, and economics, utilizing CO2RR (carbon dioxide reduction reaction) to produce valuable chemicals and fuels is a promising approach to achieving carbon neutrality and addressing the energy crisis, in which selective electrocatalysts are essential. Electrochemical conversion can generate electricity from renewable energy sources such as solar, wind, and tidal power, has mild reaction conditions, and can be carried out in an aqueous phase at room temperature and pressure; it also uses water and CO2 as feedstocks, avoiding pollution caused by the introduction of other chemicals. In particular, selective electrocatalysts for multi-carbon (C2+) products are highly promising because multi-carbon chemicals, such as ethylene (C2H4), ethanol (C2H5OH), and acetic acid (CH3COOH), are energy-intensive and utilize extensive existing infrastructure for storing and distributing carbon-based fuels. C2H4 is well-known as a versatile chemical feedstock among all CO2 electrocatalytic products, a key high-value-added raw material for various plastics and other chemicals, and a pioneer for many industrial products and fuels, representing one of the most promising opportunities to reduce greenhouse gas emissions. Furthermore, C2H4 can react with various reagents to produce different products such as ethanol, ethylene glycol, and polyethylene. Therefore, the idea of ​​electrochemically converting carbon dioxide in the environment into C2H4 not only reduces atmospheric carbon emissions and protects the environment but also enriches the global economy.

[0003] Because the process of CO2RR to C2H4 is quite complex, there is currently a lack of clear guidance on constructing reaction pathways to improve C2H4 selectivity. Therefore, there is an urgent need to develop an efficient strategy to achieve the directed electrochemical reduction of CO2 to high-value-added C2H4 products. Copper is a well-known heterogeneous catalyst that can successfully convert CO2 into various valuable hydrocarbons and oxygen-containing compounds. Many researchers believe that Cu(0) is the catalytically active site, and the presence of a certain oxidation state of Cu material enhances the performance of CO2RR to C2+ products regardless of the starting materials under reaction conditions. Furthermore, due to the ideal adsorption energy of the *CO and *H intermediates in the CC coupling reaction, Cu-based materials are the most suitable electrocatalysts for the conversion of CO2RR to various C2+ products. Copper-based materials have been extensively studied as catalysts to achieve high current density (j) and Faradaic efficiency (FE) for C2H4 products. To date, researchers have proposed various effective strategies to synthesize Cu-based catalysts for the electrocatalytic conversion of CO2RR to C2H4, such as crystal facet exposure, morphology / size control, alloying, and defect engineering.

[0004] However, the current electrocatalytic carbon dioxide reduction still suffers from problems such as poor selectivity, high overpotential, and low energy efficiency. Studies have shown that changes in the spatial environment around the catalytic active center can significantly affect the local charge density distribution and the exposure of metal sites, thereby significantly altering the free energy of various reaction intermediates adsorbed on the catalytic sites. For metal electrodes, the CO2 reduction performance has been shown to be closely related to the morphology, particle size, and loading of the catalyst. Changes in product distribution can be attributed to the following aspects: (1) the extended residence time of products and intermediates in the pores of the nanostructured catalyst layer; (2) the difference in mass transfer requirements between the hydrogen evolution reaction (HER) and the CO2 reduction reaction; (3) the improvement in CO2 transport efficiency due to gas evolution; (4) the surface coordination effect dependent on size and morphology; and (5) the change in reagent concentration caused by the field effect on the high curvature surface. Using different supports to load copper oxides can significantly affect the local charge density distribution and the exposure of metal sites. By rationally designing the physicochemical properties of the support, the performance bottleneck of a single catalyst can be overcome, promoting the efficient conversion of CO2 into high-value-added chemicals (such as ethylene and ethanol), and contributing to the achievement of carbon neutrality goals.

[0005] Therefore, existing copper-based materials generally suffer from the following problems in the electrocatalytic reduction of CO2: (1) Current copper-based materials have low product selectivity in the electrocatalytic reduction of CO2, especially for the high-value-added product ethylene. The hydrogen evolution reaction (HER), which strongly competes with CO2RR, always occurs. A large amount of electrical energy is used to generate low-value hydrogen (H2), resulting in a decrease in the "Faraday efficiency" of the target product. (2) Traditional nanoscale copper particles are prone to migration and agglomeration into large particles under high potential and exothermic reaction, resulting in a sharp reduction in active surface area, easy deactivation, and poor stability. (3) Under high current density, the selectivity and stability of traditional copper catalysts will drop sharply, which cannot meet the actual needs. Summary of the Invention

[0006] This invention addresses the shortcomings of existing technologies by providing a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally controlled carbon supports and its preparation method. It innovatively approaches the issue through a strategy of "dimensionally controlled supports," aiming to systematically reveal how carbon supports of different dimensions influence the dispersibility of Gd-CuO active components, surface oxygen vacancy concentration, and electron transport behavior, thereby regulating the adsorption strength and CC coupling pathway of the key intermediate (*CO). By establishing a clear structure-activity relationship of "support structure - active site state - reaction performance," this invention not only provides a new material system (such as two-dimensional carbon-supported Gd-CuO) for overcoming the challenges of low selectivity and poor stability in copper-based catalysts, but also lays a scientific foundation for designing efficient and long-life CO2RR catalysts from a theoretical perspective.

[0007] Carbon materials are ideal supports for CO2RR catalysts due to their high conductivity, tunable properties, stability, and cost advantages. Future research will focus on regulating the microstructure of carbon supports and their interfacial interactions with catalysts to improve reaction efficiency and selectivity. Catalyst distribution is closely related to the structure of the carbon support; active centers influence performance differences, and a large specific surface area is beneficial for mass transfer and dispersing active centers. Carbon-based materials developed from MOFs (metal-organic frameworks) have more exposed active sites, lower density, and a shorter time to complete connection with the reaction medium compared to other types of carbon materials. MOFs are a new class of porous crystalline nanomaterials, self-assembled from organic ligands (linkers) and inorganic metal ions / clusters (nodes), possessing well-defined crystal structures and regular channels, providing an ideal platform for revealing structure-performance relationships. Among them, zeolite-like imidazolium ester (ZIF) derivatives are widely used in the electroreduction of carbon dioxide. The nano-carbon materials derived from ZIFs calcination have zero-dimensional, one-dimensional, two-dimensional, and three-dimensional structures. Zero-dimensional structures include granular forms, one-dimensional structures include nanostructures, two-dimensional structures include lamellar structures, and three-dimensional structures include three-dimensional cubes, dodecahedrons, spheres, and tubular structures. The diameters of their particles and cavities range from tens of nanometers to hundreds of nanometers. By using these structures to load copper compounds, a synergistic effect at the carbon-copper interface can be achieved, stabilizing key reaction intermediates (such as CO), significantly increasing the probability of CC coupling, and thus directionally promoting the formation of multi-carbon products (such as ethylene).

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support includes the following steps: Step 1: Dissolve dimethylimidazole in deionized water to obtain a dimethylimidazole aqueous solution; Zinc nitrate hexahydrate (Zn(NO3)2·6H2O) and hexadecyltrimethylammonium bromide were dissolved in deionized water to obtain a zinc nitrate solution; Zinc nitrate solution was added to dimethylimidazole aqueous solution, and the reaction was carried out. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the metal-organic framework. Step 2: Pyrolysis treatment of the metal-organic framework. After the pyrolysis treatment is completed, the metal-organic framework is cooled to obtain carbide metal-organic framework. Step 3: Disperse gadolinium nitrate hexahydrate (Gd(NO3)3·6H2O) in ethanol to obtain solution A; A metal-organic carbide framework and copper acetate monohydrate (Cu(CH3COO)2·H2O) were dissolved in deionized water to obtain solution B. Solution A was added dropwise to solution B, and after stirring, a hydrothermal reaction was carried out. After the reaction was completed, the solution was cooled, filtered, washed, and dried to obtain a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support. The carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support includes three dimensional structures. The three dimensional structures are a two-dimensional sheet structure, a three-dimensional cube structure, and a dodecahedral structure.

[0009] Preferably, in step one, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is (0.58-2.724):(0.177-0.26):(0-0.003), and the reaction is carried out under the condition of stirring at room temperature for 0.5-4 hours.

[0010] Preferably, the room temperature is 26 °C.

[0011] Preferably, in step one, when preparing the dimethylimidazole aqueous solution, the mass ratio of dimethylimidazole to deionized water is (0.58-2.724):(20-42); when preparing the zinc nitrate solution, the mass ratio of zinc nitrate hexahydrate, hexadecyltrimethylammonium bromide, and deionized water is (0.177-0.266):(0-0.003):(6-20).

[0012] Preferably, in step two, the pyrolysis treatment conditions are as follows: under N2 atmosphere, the temperature is increased to 900 ℃ at a heating rate of 5 ℃ / min, and annealed at 900 ℃ for 2 hours.

[0013] Preferably, in step three, the mass ratio of gadolinium nitrate hexahydrate, metal-organic carbide framework, and copper acetate monohydrate is 0.1:0.03:0.5, and the hydrothermal reaction is carried out at 115-125 °C for 18-22 h.

[0014] Preferably, in step three, when preparing solution A, the ratio of gadolinium nitrate hexahydrate to ethanol is 0.1 g / 25 mL, and when preparing solution B, the mass ratio of metal-organic carbide, copper acetate monohydrate, and deionized water is 0.03:0.5:25.

[0015] Preferably, when the carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally controlled carbon support obtained in step three is a two-dimensional sheet structure, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 0.58:0.266:0, and the reaction condition is stirring at room temperature for 4 hours.

[0016] Preferably, when the carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support obtained in step three is a three-dimensional cubic structure, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 2.724:0.177:0.003, and the reaction condition is stirring at room temperature for 0.5 h.

[0017] Preferably, when the carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in step three is a dodecahedral structure, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 2.724:0.177:0, and the reaction condition is stirring at room temperature for 4 hours.

[0018] The present invention also discloses a Gd-CuO electrocatalytic CO2 reduction catalyst based on a dimensionally regulated carbon support, prepared by the above-described method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst based on a dimensionally regulated carbon support.

[0019] This invention synthesizes metal-organic framework precursors at room temperature, obtains carbon materials with different dimensional structures (two-dimensional sheets, three-dimensional cubes, and dodecahedrons) through carbonization, and uses them as supports to synthesize copper-based catalysts supported on the supports via a hydrothermal method, thereby improving the electrocatalytic reduction performance of the supported copper-based catalysts for CO2 to C2H4.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) By systematically regulating the morphology and dimensionality of carbon supports, the direct correlation between dimensional characteristics and catalytic performance was revealed. Among them, two-dimensional carbon supports such as activated carbon and carbon nanosheets showed unique advantages. By constructing two-dimensional carbon supports, the microenvironment of Gd-CuO active sites was precisely regulated, the adsorption energy of CO intermediate was optimized, and CC coupling was strongly promoted, which increased the ethylene Faraday efficiency to 27.84% and significantly improved the reaction selectivity. (2) A Gd-CuO / two-dimensional carbon composite catalyst was constructed. For the first time, rare earth element gadolinium (Gd) was introduced into the copper-based catalyst system. Combined with dimensional regulation, a multi-level synergistic effect was achieved. Utilizing the huge specific surface area and stable structure of two-dimensional carbon, Gd-CuO nanoparticles were highly dispersed and firmly anchored, inhibiting the aggregation, dissolution and shedding of active components, and achieving stable operation for up to 18 hours. (3) The deactivation problem of copper-based catalysts is solved by the strong confinement effect and chemical anchoring of the two-dimensional support. The carbon support strongly anchors Gd-CuO nanoparticles through π-d interactions, inhibiting migration and sintering under high temperature reaction. The two-dimensional carbon coating layer blocks the direct erosion of the active components by the electrolyte, reducing Cu 2+Despite the minimal dissolution loss, the ethylene selectivity remained above 20% throughout the 18-hour continuous reaction, with a performance degradation rate of less than 5%. This invention breaks away from the traditional approach of simply modifying copper-based active sites. By controlling the "supporting role" of the support, it achieves precise control over the electronic structure of the "protagonist" active sites and the reaction microenvironment, thereby synergistically solving the three major bottleneck problems of selectivity, stability, and activity. This provides a new paradigm and theoretical tool for the design of CO2RR catalysts. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the preparation of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support in this invention; Figure 2 SEM images of the carbide metal-organic frameworks prepared in Examples 1-3 of the present invention; Figure 3 SEM images of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in Examples 1-3 of the present invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1. Figure 4 The images are HRTEM images of the Gd-CuO electrocatalytic CO2 reduction catalysts based on dimensionally regulated carbon supports prepared in Examples 1-3 of the present invention and the Gd-CuO electrocatalytic CO2 reduction catalysts prepared in Comparative Example 1. Figure 5 The XRD patterns are of the metal carbide organic frameworks prepared in Examples 1-3 of the present invention. Figure 6 The XRD patterns are of the Gd-CuO electrocatalytic CO2 reduction catalysts based on dimensionally regulated carbon supports prepared in Examples 1-3 of the present invention and the Gd-CuO electrocatalytic CO2 reduction catalysts prepared in Comparative Example 1. Figure 7 TGA images of the Gd-CuO electrocatalytic CO2 reduction catalysts based on dimensionally regulated carbon supports prepared in Examples 1-3 of the present invention and the Gd-CuO electrocatalytic CO2 reduction catalysts prepared in Comparative Example 1. Figure 8 The LSV polarization curves of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in Example 1 of the present invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1 are shown in 0.1M KHCO3 solution saturated with N2 and CO2. Figure 9The graph shows the detection results of the reduction products when the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in Examples 1-3 of this invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1 are subjected to ECR reaction. Figure 10 The graph shows the energy efficiency of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in Examples 1-3 of this invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1 when performing ECR reaction to produce ethylene products. Figure 11 The graph shows the Cdl values ​​of the Gd-CuO electrocatalytic CO2 reduction catalysts based on dimensionally regulated carbon supports prepared in Examples 1-3 of this invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1. Figure 12 The Cdl values ​​of the Gd-CuO electrocatalytic CO2 reduction catalysts based on dimensionally regulated carbon supports prepared in Examples 1-3 of this invention and the Gd-CuO electrocatalytic CO2 reduction catalysts prepared in Comparative Example 1 were obtained in a series of cyclic voltammetry experiments with different scan rates in 0.1 M KHCO3 solution. Figure 13 The Tafel slope measurement results of the ethylene product during the ECR reaction of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in Examples 1-3 of the present invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1. Figure 14 The image shows the contact angle test results of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in Examples 1-3 of this invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1. Figure 15 The graph shows the H2 Faradaic efficiency test results of the Gd-CuO electrocatalytic CO2 reduction catalysts based on dimensionally regulated carbon supports prepared in Examples 1-3 of this invention and the Gd-CuO electrocatalytic CO2 reduction catalyst prepared in Comparative Example 1 at different potentials. Detailed Implementation

[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention. Example 1

[0023] This embodiment discloses a method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally controlled carbon support, comprising the following steps: Step 1: Dissolve dimethylimidazole in deionized water at a mass ratio of 0.58:20 to obtain a dimethylimidazole aqueous solution. Zinc nitrate hexahydrate was added to deionized water at a mass ratio of 0.26:20 to obtain a zinc nitrate solution. The mass ratio of dimethylimidazole to zinc nitrate hexahydrate is 0.58:0.26; Zinc nitrate solution was added to dimethylimidazole aqueous solution and stirred at 26 °C for 4 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min to remove the supernatant. The centrifuged precipitate was washed once with ethanol at 9000 r / min and twice with ethanol at 8000 r / min. The precipitate was then dried in a vacuum drying oven at 60 °C for 12 h to obtain the metal-organic framework, denoted as 2D-L. Step 2: Place the metal-organic framework in a quartz tube and heat it to 900 ℃ at a heating rate of 5 ℃ / min under N2 atmosphere. Maintain the temperature at 900 ℃ for annealing for 2 hours. After the pyrolysis treatment is completed, cool it to room temperature to obtain the carbide metal-organic framework, denoted as C-2D-L. Step 3: Disperse gadolinium nitrate hexahydrate in ethanol, with a gadolinium nitrate hexahydrate to ethanol ratio of 0.1 g / 25 mL, to obtain solution A; A metal-organic framework and copper acetate monohydrate were dissolved in deionized water in a mass ratio of 0.03:0.5:25 to obtain solution B. Solution A was added dropwise to solution B, and the mixture was stirred at 200 r / min for 1 h. The mixture was then transferred to a polytetrafluoroethylene stainless steel reactor, sealed, and reacted at 120 ℃ for 20 h. After the reaction was completed, the mixture was naturally cooled to room temperature, filtered, and the resulting precipitate was washed three times with ethanol and deionized water, respectively. The precipitate was then vacuum dried at 60 ℃ for 20 h to obtain a Gd-CuO electrocatalytic CO2 reduction catalyst based on a dimensionally regulated carbon support. The carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support has a two-dimensional sheet structure, denoted as Gd-CuO / C-2D-L. Example 2

[0024] This embodiment discloses a method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally controlled carbon support, comprising the following steps: Step 1: Dissolve dimethylimidazole in deionized water at a mass ratio of 2.724:42 to obtain a dimethylimidazole aqueous solution. Zinc nitrate hexahydrate and hexadecyltrimethylammonium bromide were added to deionized water in a mass ratio of 0.177:0.003:6 to obtain a zinc nitrate solution. The mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 2.724:0.177:0.003. Zinc nitrate solution was added to dimethylimidazole aqueous solution and stirred at 26 °C for 0.5 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min to remove the supernatant. The centrifuged precipitate was washed once with ethanol at 9000 r / min and twice with ethanol at 8000 r / min. The precipitate was then dried in a vacuum drying oven at 60 °C for 12 h to obtain the metal-organic framework, denoted as Cube-8. Step 2: Place the metal-organic framework in a quartz tube and heat it to 900 ℃ at a heating rate of 5 ℃ / min under N2 atmosphere. Maintain the temperature at 900 ℃ for annealing for 2 hours. After the pyrolysis treatment is completed, cool it to room temperature to obtain the carbide metal-organic framework, denoted as C-Cube-8. Step 3: Disperse gadolinium nitrate hexahydrate in ethanol, with a gadolinium nitrate hexahydrate to ethanol ratio of 0.1 g / 25 mL, to obtain solution A; A metal-organic framework and copper acetate monohydrate were dissolved in deionized water in a mass ratio of 0.03:0.5:25 to obtain solution B. Solution A was added dropwise to solution B, and the mixture was stirred at 200 r / min for 1 h. The mixture was then transferred to a polytetrafluoroethylene stainless steel reactor, sealed, and reacted at 120 ℃ for 20 h. After the reaction was completed, the mixture was naturally cooled to room temperature, filtered, and the resulting precipitate was washed three times with ethanol and deionized water, respectively. The precipitate was then vacuum dried at 60 ℃ for 20 h to obtain a Gd-CuO electrocatalytic CO2 reduction catalyst based on a dimensionally regulated carbon support. The carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support has a three-dimensional cubic structure, denoted as Gd-CuO / C-Cube-8. Example 3

[0025] This embodiment discloses a method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally controlled carbon support, comprising the following steps: Step 1: Dissolve dimethylimidazole in deionized water at a mass ratio of 2.724:20 to obtain a dimethylimidazole aqueous solution. Zinc nitrate hexahydrate was added to deionized water at a mass ratio of 0.177:20 to obtain a zinc nitrate solution. The mass ratio of dimethylimidazole to zinc nitrate hexahydrate is 2.724:0.177; Zinc nitrate solution was added to dimethylimidazole aqueous solution and stirred at 26 °C for 4 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min to remove the supernatant. The centrifuged precipitate was washed once with ethanol at 9000 r / min and twice with ethanol at 8000 r / min. The precipitate was then dried in a vacuum drying oven at 60 °C for 12 h to obtain the metal-organic framework, denoted as ZIF-8. Step 2: Place the metal-organic framework in a quartz tube and heat it to 900 ℃ at a heating rate of 5 ℃ / min under N2 atmosphere. Maintain the temperature at 900 ℃ for annealing for 2 hours. After the pyrolysis treatment is completed, cool it to room temperature to obtain the carbide metal-organic framework, denoted as C-ZIF-8. Step 3: Disperse gadolinium nitrate hexahydrate in ethanol, with a gadolinium nitrate hexahydrate to ethanol ratio of 0.1 g / 25 mL, to obtain solution A; A metal-organic framework and copper acetate monohydrate were dissolved in deionized water in a mass ratio of 0.03:0.5:25 to obtain solution B. Solution A was added dropwise to solution B, and the mixture was stirred at 200 r / min for 1 h. The mixture was then transferred to a polytetrafluoroethylene stainless steel reactor, sealed, and reacted at 120 ℃ for 20 h. After the reaction was completed, the mixture was naturally cooled to room temperature, filtered, and the resulting precipitate was washed three times with ethanol and deionized water, respectively. The precipitate was then vacuum dried at 60 ℃ for 20 h to obtain a Gd-CuO electrocatalytic CO2 reduction catalyst based on a dimensionally regulated carbon support. The carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support has a dodecahedral structure, denoted as Gd-CuO / C-ZIF-8.

[0026] Comparative Example 1 This comparative example discloses a method for preparing a Gd-CuO electrocatalytic CO2 reduction catalyst, comprising the following steps: Gadolinium nitrate hexahydrate was dispersed in ethanol at a ratio of 0.1 g / 25 mL to obtain solution A. Copper acetate monohydrate was dissolved in deionized water at a mass ratio of 0.5:25 to obtain solution B. Solution A was added dropwise to solution B, and the mixture was stirred at 200 r / min for 1 h. The mixture was then transferred to a polytetrafluoroethylene stainless steel reactor, sealed, and reacted at 120 ℃ for 20 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, filtered, and the resulting precipitate was washed three times with ethanol and deionized water, respectively. The precipitate was then vacuum dried at 60 ℃ for 20 h to obtain the Gd-CuO electrocatalyst for CO2 reduction, denoted as Gd-CuO.

[0027] Characterization tests: (1) The microstructure of the carbide metal-organic framework samples prepared in Examples 1-3 was observed by SEM (scanning electron microscopy), and the results are as follows: Figure 2 As shown. Figure 2 In the diagram, a is a SEM image of the metal-organic carbide (MOC) sample (C-2D-L) prepared in Example 1, b is a SEM image of the metal-organic carbide (MOC) sample (C-Cube-8) prepared in Example 2, and c is a SEM image of the metal-organic carbide (MOC) sample (C-ZIF-8) prepared in Example 3. Figure 2 It is known that C-2D-L exhibits an irregular blocky structure with multiple layers stacked together, with a size of about 3 μm; C-Cube-8 exhibits a regular cube structure with an average size of 250-500 nm; and C-ZIF-8 exhibits a regular dodecahedron structure with an overall size of 300-500 nm. The C-2D-L layered structure has a large specific surface area, which can effectively load a large amount of copper compounds, exposing more catalytic active sites and rapidly transferring electrons from the electrode to the active sites. In contrast, C-ZIF-8 and C-Cube-8, being at the nanoscale, can only intercalate with copper compounds.

[0028] (2) The microstructure of the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally controlled carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 were observed by SEM. The results are as follows: Figure 3 As shown. Figure 3In the diagram, a is a SEM image of the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO) prepared in Comparative Example 1; b is a SEM image of the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO / C-ZIF-8) based on dimensionally regulated carbon support prepared in Example 3; c is a SEM image of the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO / C-Cube-8) based on dimensionally regulated carbon support prepared in Example 2; and d is a SEM image of the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO / C-2D-L) based on dimensionally regulated carbon support prepared in Example 1. Figure 3 It can be seen that Gd-CuO in a exhibits an irregular nano-sized flower-like microsphere structure. This structure gives the microspheres a large specific surface area, which is beneficial for CO2 adsorption. However, the microsphere particle size is within 1... The size is approximately μm. In the Gd-CuO / C-2D-L composite system, after the Gd-CuO flower-like microsphere structure is broken, the specific surface area increases, exposing more edges and defect sites. Then, it is loaded onto the irregular blocky structure of C-2D-L, which can effectively disperse CuO nanoparticles, prevent agglomeration, and ensure that active sites are fully exposed. In the Gd-CuO / C-ZIF-8 composite system, the Gd-CuO flower-like microsphere structure exhibits local fragmentation. Some Gd-CuO microspheres have been completely deposited on the surface of the dodecahedral carrier and almost completely encapsulate the C-ZIF-8 substrate. Another certain proportion of microspheres are dispersed and loaded on the surface of C-ZIF-8, thus forming a heterogeneous composite structure of Gd-CuO and C-ZIF-8. In the Gd-CuO / C-Cube-8 composite system, the Gd-CuO flower-like microsphere structure is also partially broken and loaded on the cube. C-2D-L provides numerous anchoring sites, promoting uniform dispersion of the broken Gd-CuO nanoparticles, exposing more active sites, and enabling the synergistic effect between the broken particles and the C-2D-L to regulate the adsorption energy of intermediates (*COOH, *CO), enhancing CO2 adsorption capacity and increasing local reactant concentration. Furthermore, the micron-sized irregular blocky structure possesses high conductivity, promoting rapid electron transfer, and its mechanical strength can inhibit the aggregation or dissolution of Gd-CuO nanoparticles during the reaction. In contrast, Gd-CuO / C-ZIF-8 and Gd-CuO / C-Cube-8 typically have smooth surfaces, leading to uneven loading and easy aggregation of Gd-CuO nanoparticles, insufficient exposure of active sites, decreased effective specific surface area, weak interfacial bonding between the rigid surface of the regular carbon support and the Gd-CuO nanoparticles, and low electron transport efficiency.

[0029] (3) The microstructure of the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally regulated carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 were observed by HRTEM (high-resolution transmission electron microscopy). The results are as follows: Figure 4 As shown. Figure 4 In the diagram, a and b are HRTEM images and magnified views of the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO) prepared in Comparative Example 1; c and d are HRTEM images and magnified views of the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO / C-ZIF-8) based on dimensionally regulated carbon support prepared in Example 3; e and f are the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO / C-Cube-8) based on dimensionally regulated carbon support prepared in Example 2; and g and h are the Gd-CuO electrocatalytic CO2 reduction catalyst sample (i.e., Gd-CuO / C-2D-L) based on dimensionally regulated carbon support prepared in Example 1. Flower-like Gd-CuO nanoparticles and lattice fringes can be observed in a and b. Flower-like Gd-CuO nanoparticles loaded on two-dimensional sheets and irregular blocks composed of multiple two-dimensional sheets and lattice fringes can be observed in g and h. Flower-like Gd-CuO nanoparticles loaded on dodecahedrons and lattice fringes can be observed in c and d. Flower-like Gd-CuO nanoparticles loaded on cubes and lattice fringes can be observed in e and f.

[0030] (4) The carbide metal-organic framework samples prepared in Examples 1-3 were subjected to XRD (x-ray diffraction) tests, and the results are as follows: Figure 5 As shown. By Figure 5 It can be seen that the three carbide metal-organic frameworks all have only two high-intensity diffraction peaks, and their X-ray diffraction patterns are almost identical, indicating that these three carbon supports all have partially graphitized structures and are not different from each other.

[0031] (5) XRD tests were performed on the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 and the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Comparative Example 1. The results are as follows: Figure 6 As shown. From Figure 6 It can be seen that CuO diffraction peaks appeared in all four catalysts. The diffraction peaks at 2θ of 32.5 °, 35.5 °, 38.7 °, and 48.7 ° correspond to the (110), (...) diffraction peaks of CuO, respectively. ), (111) and ( The crystal planes perfectly match the CuO (PDF#48-1548) crystal planes in the standard card. The (1) and (111) crystal planes are the main crystal planes in CuO and are the main directional bonding planes of CuO grains. In addition, the specific angle between these two crystal planes helps CuO nanosheets to stratify and self-assemble, forming a unique flower-like structure. The (111) crystal plane usually has high surface energy, is rich in oxygen vacancies, and has a strong ability to adsorb and activate CO2, which is beneficial to the stable adsorption and desorption of intermediates (such as *COOH, *CO); and the electronic coupling between these two crystal planes can form an "active site gradient", which promotes charge transfer, reduces the reaction energy barrier, and improves the FE (Faraday efficiency) of C2H4. The slight offset between the crystal planes (lattice shrinkage) may be due to Gd doping, which leads to changes in the coordination environment, regulates the binding strength of specific intermediates, and thus changes the reaction path. However, no Gd diffraction peaks were found in the spectrum, which is due to the low amount of Gd doping.

[0032] (6) The BET specific surface area and BJH pore size distribution of the Gd-CuO electrocatalytic CO2 reduction catalyst samples based on dimensionally regulated carbon supports prepared in Examples 1-3 and the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Comparative Example 1 were measured. The results are shown in Table 1. Table 1 Sample SBET(m² / g) pore volume (cm³ / g) average pore size Gd-CuO 35.6846 0.049067 5.7049 nm Gd-CuO / C-ZIF-8 49.5682 0.056453 5.1132 nm Gd-CuO / C-Cube-8 67.4261 0.067622 5.2057 nm Gd-CuO / C-2D-L 26.0708 0.044101 7.1746 nm Table 1 shows that the specific surface area of ​​Gd-CuO is 35.6846 cm³ / g and the pore size distribution is 5.7049 nm; the specific surface area of ​​Gd-CuO / C-ZIF-8 is 49.5682 cm³ / g and the pore size distribution is 5.1132 nm; the specific surface area of ​​Gd-CuO / C-Cube-8 is 67.4261 cm³ / g and the pore size distribution is 5.2057 nm; and the specific surface area of ​​Gd-CuO / C-2D-L is 26.0708 cm³ / g and the pore size distribution is 7.1746 nm. This indicates that the catalyst is a mesoporous metallic material.

[0033] (7) Thermogravimetric analysis (TGA) was performed on the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 and the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Comparative Example 1. The results are as follows: Figure 7 As shown. By Figure 7It can be seen that from room temperature to 250 °C, the weight loss of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support is about 5%, which is attributed to physical adsorption and the release of coordinated water molecules. As the temperature rises above 350 °C, the carbide metal-organic framework gradually decomposes. C-Cube-8 almost decomposes from CuO at 400 °C with a weight loss of about 15%, and similarly, C-ZIF-8 almost decomposes from CuO at 400 °C with a weight loss of about 17.5%, while C-2D-L almost decomposes from CuO at 450 °C with a weight loss of about 20%. The large difference between the actual CuO content and the theoretical loading may be related to the surface area of ​​the carbon support or the micron- and nano-scale carbon supports. There is more CuO loaded at the nano-scale and less CuO loaded at the micron-scale. Therefore, C-2D-L is still detaching from CuO above 400 °C. At this time, what is detached is the CuO that is more firmly bound and loaded more than the nano-scale support. C-ZIF-8 continues to decompose at 450 °C until 500 °C, when the carbide metal-organic framework is almost completely decomposed.

[0034] (8) The linear sweep voltammetry (LSV) polarization curves of the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 and Comparative Example 1, based on dimensionally regulated carbon supports, were measured in 0.1 M KHCO3 solutions saturated with N2 and CO2. The results are as follows: Figure 8 As shown. Figure 8 As shown, the Gd-CuO electrocatalyst for CO2 reduction, based on dimensionally regulated carbon support, achieved a higher current density in CO2-saturated electrolyte than in N2-saturated electrolyte, indicating that the ECR activity is higher than that of the hydrogen evolution reaction (HER). Furthermore, Gd-CuO / C-2D-L exhibits a larger current density and a more positive reduction potential compared to other catalysts, demonstrating its superior catalytic activity for CO2 reduction.

[0035] (9) The Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally regulated carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 were subjected to ECR (electrocatalytic carbon dioxide reduction reaction) determination. A constant potential test was performed for 1 h at an applied potential of -1.0 to -1.4 V (vs. RHE), and the reduction products were detected by gas chromatography (GC). The results are as follows: Figure 9 As shown. Figure 9In the table, a represents the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 (i.e., Gd-CuO), b represents the Gd-CuO electrocatalytic CO2 reduction catalyst sample based on dimensionally regulated carbon support prepared in Example 3 (i.e., Gd-CuO / C-ZIF-8), c represents the Gd-CuO electrocatalytic CO2 reduction catalyst sample based on dimensionally regulated carbon support prepared in Example 2 (i.e., Gd-CuO / C-Cube-8), and d represents the Gd-CuO electrocatalytic CO2 reduction catalyst sample based on dimensionally regulated carbon support prepared in Example 1 (i.e., Gd-CuO / C-2D-L). Figure 11 It can be seen that the gaseous products contain H2, CO, CH4, and C2H4. With increasing potential, FE... CO Gradually decrease, FE C2H4 Gradually increasing, Gd-CuO / C-2D-L exhibits the highest total carbon-containing product Faradaic efficiency; at -1.2 V (vs. RHE), the dominant potential for each catalyst is observed, exhibiting the lowest hydrogen Faradaic efficiency and the highest carbon-containing product Faradaic efficiency. Gd-CuO shows the highest maximum FE. C2H4 The content was 22.75% when C-2D-L was loaded with Gd-CuO, and the FE content was 22.75%. C2H4 The increase was significant, at 27.84%, while C-ZIF-8 loaded with Gd-CuO, FE C2H4 However, it decreased by 16.82%, and after loading Gd-CuO onto C-Cube-8, FE C2H4 The reduction was even more pronounced, at 8.82%. This indicates that the stacking of two-dimensional sheet-like supports, with broken flower-like CuO nanoparticles loaded together, increases the interfacial contact area, improves their compatibility, forms defects, and exposes more active sites, thus significantly promoting CO2 permeability and enhancing CO2RR performance. In contrast, regular cubic and dodecahedral supported Cu-based catalysts weaken CO2RR performance.

[0036] (10) The energy efficiency (EE) of the Gd-CuO electrocatalytic CO2 reduction catalyst samples based on dimensionally regulated carbon support prepared in Examples 1-3 and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 during the ECR reaction to produce ethylene products was determined. The results are as follows: Figure 10 As shown. Figure 10 As shown, Gd-CuO / C-2D-L exhibits a maximum EE of 13.18% at -1.2V (vs. RHE). C2H4 In comparison, Gd-CuO, Gd-CuO / C-ZIF-8, and Gd-CuO / C-Cube-8 achieved EE values ​​of only 10.77%, 7.96%, and 4.18%, respectively. C2H4 .

[0037] (11) Measure the Cdl values (double-layer capacitance) of the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally regulated carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1. The results are as Figure 11 shown.

[0038] (12) Measure the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally regulated carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 in a 0.1 M KHCO3 solution for a series of cyclic voltammetry experiments at different scan rates (e.g., 0.1488 V - 0.2488 V (versus RHE) and 20 mV·s –1 -200 mV·s –1 ) to calculate the Cdl value. The results are as Figure 12 shown. Figure 12 In, (a) is the Cdl value of Gd-CuO, (b) is the Cdl value of Gd-CuO / C-ZIF-8, (c) is the Cdl value of Gd-CuO / C-Cube-8, and (d) is the Cdl value of Gd-CuO / C-2D-L.

[0039] It can be seen from Figure 11 that the trend of the Cdl value is as follows: Gd-CuO / C-Cube-8 < Gd-CuO / C-ZIF-8 < Gd-CuO < Gd-CuO / C-2D-L, indicating that the ECSA follows a similar pattern: Gd-CuO / C-Cube-8 < Gd-CuO / C-ZIF-8 < Gd-CuO < Gd-CuO / C-2D-L. Therefore, it can be inferred that Gd-CuO loaded on C-2D-L exposes more active sites, which is beneficial to the adsorption of CO2, thus showing higher ECR catalysis. It can be seen from Figure 12 that the control samples Gd-CuO / C-ZIF-8 and Gd-CuO / C-Cube-8 even have a smaller ECSA relative to Gd-CuO not loaded on any support, indicating that the Gd-CuO structure has been redistributed, resulting in the destruction or loss of some active sites, which instead reduces the performance of CO2RR.

[0040] (13) Measure the Tafel slope (Tafel) when generating ethylene products during the ECR reaction of the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally regulated carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1. The results are as Figure 13 shown. It can be seen from Figure 13 that the Tafel slope of Gd-CuO / C-2D-L is 295 mV·dec-1 The value was significantly lower than other samples, with Gd-CuO at 352 mV·dec. -1 The value of Gd-CuO / C-ZIF-8 is 352 mV·dec. -1 The value of Gd-CuO / C-Cube-8 is 371 mV·dec. -1 By comparing these Tafel slope values, it can be found that Gd-CuO / C-2D-L has the best kinetic performance in the ECR reaction, exhibiting a faster reaction rate.

[0041] (14) To further investigate the effect of support loading on catalyst surface properties, contact angle tests were conducted on Gd-CuO, Gd-Cu / C-ZIF-8, Gd-CuO / C-Cube-8, and Gd-CuO / C-2D-L, respectively. The results are as follows: Figure 14 As shown. Figure 14 In the diagram, a represents Gd-CuO, b represents Gd-CuO / C-ZIF-8, c represents Gd-CuO / C-Cube-8, and d represents Gd-CuO / C-2D-L.

[0042] (15) The H2 Faradaic efficiency of the Gd-CuO electrocatalytic CO2 reduction catalyst samples prepared in Examples 1-3 based on dimensionally regulated carbon supports and the Gd-CuO electrocatalytic CO2 reduction catalyst sample prepared in Comparative Example 1 was determined at different potentials. The results are as follows: Figure 15 As shown. Figure 15 In the diagram, a represents Gd-CuO, b represents Gd-CuO / C-ZIF-8, c represents Gd-CuO / C-Cube-8, and d represents Gd-CuO / C-2D-L.

[0043] In summary, this invention constructed Gd-CuO electrocatalysts supported on different carbon supports for application in CO2RR systems. The support structure can be effectively altered by changing the ratio of dimethylimidazolium to nitrate. Synthesizing a suitable support for Gd-CuO is beneficial for promoting CC coupling and improving ethylene selectivity. The results show that the optimal carbon support is C-2D-L, and at -1.2 V (relative to RHE), the FE in the H-cell is... C2H4 It can reach 27.84%, j C2H4 -37.6 mA·cm -2It exhibited excellent stability within 18 hours. Combining physical characterization, including XRD and contact angle testing, with electrochemical characterization such as Tafel slope and electrochemically active surface area, the results showed that in the CO2RR process, by changing the dimension and size of the support, the structure of the copper-based material expanded from isolated nanoparticles to confined clusters, single atoms, or three-dimensional interconnected networks, leading to changes in crystal plane peak intensity and affecting performance, thus overcoming the limitations of traditional catalysts. This strategy not only improves the efficiency of multi-carbon products but also provides a new paradigm for the design of low-cost, highly compatible catalytic systems, promoting the practical application of CO2 resource utilization.

[0044] In this invention, carbon supports with different dimensional morphologies were constructed using a hydrothermal method and loaded with Gd-CuO active components. The regulatory effect of these supports on catalytic performance was systematically studied. The results showed that changes in the dimensionality of the carbon support regulated the exposure of the CuO (111) crystal facets in Gd-CuO, significantly affecting the oxygen vacancy concentration on its surface, thereby regulating the adsorption behavior and conversion pathway of key intermediates (such as *CO). Performance tests indicated that the two-dimensional carbon support endowed the catalyst with superior ethylene generation capacity, achieving a maximum ethylene Faradaic efficiency (FE(C2H4)) of 27.84% at -1.2V (vs. RHE) and an ethylene bias current density (j(C2H4)) of -37.6 mA·cm⁻¹. -2 Furthermore, the selectivity of ethylene products remained at approximately 20% throughout the 18-hour reaction process.

[0045] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on dimensionally controlled carbon support, characterized in that, Includes the following steps: Step 1: Dissolve dimethylimidazole in deionized water to obtain a dimethylimidazole aqueous solution; Zinc nitrate hexahydrate and hexadecyltrimethylammonium bromide were dissolved in deionized water to obtain a zinc nitrate solution; Zinc nitrate solution was added to dimethylimidazole aqueous solution, and the reaction was carried out. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the metal-organic framework. Step 2: Pyrolysis treatment of the metal-organic framework. After the pyrolysis treatment is completed, the metal-organic framework is cooled to obtain carbide metal-organic framework. Step 3: Disperse gadolinium nitrate hexahydrate in ethanol to obtain solution A; Dissolve the metal carbide organic framework and copper acetate monohydrate in deionized water to obtain solution B; Solution A was added dropwise to solution B, and after stirring, a hydrothermal reaction was carried out. After the reaction was completed, the solution was cooled, filtered, washed, and dried to obtain a Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support. The carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support includes three dimensional structures. The three dimensional structures are a two-dimensional sheet structure, a three-dimensional cube structure, and a dodecahedral structure.

2. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, In step one, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is (0.58-2.724):(0.177-0.26):(0-0.003), and the reaction is carried out under the condition of stirring at room temperature for 0.5-4 hours.

3. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, In step one, when preparing the dimethylimidazole aqueous solution, the mass ratio of dimethylimidazole to deionized water is (0.58-2.724):(20-42); when preparing the zinc nitrate solution, the mass ratio of zinc nitrate hexahydrate, hexadecyltrimethylammonium bromide, and deionized water is (0.177-0.266):(0-0.003):(6-20).

4. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, In step two, the pyrolysis treatment conditions are as follows: under N2 atmosphere, the temperature is increased to 900 ℃ at a heating rate of 5 ℃ / min, and annealed at 900 ℃ for 2 hours.

5. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, In step three, the mass ratio of gadolinium nitrate hexahydrate, metal-organic carbide framework, and copper acetate monohydrate is 0.1:0.03:0.5, and the hydrothermal reaction is carried out at 115-125 °C for 18-22 h.

6. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, In step three, when preparing solution A, the ratio of gadolinium nitrate hexahydrate to ethanol is 0.1 g / 25 mL. When preparing solution B, the mass ratio of metal-organic carbide, copper acetate monohydrate, and deionized water is 0.03:0.5:

25.

7. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, When the carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in step three is a two-dimensional sheet structure, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 0.58:0.266:0, and the reaction condition is stirring at room temperature for 4 hours.

8. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, When the carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in step three is a three-dimensional cubic structure, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 2.724:0.177:0.003, and the reaction condition is stirring at room temperature for 0.5 h.

9. The method for preparing a Gd-CuO electrocatalyst for CO2 reduction based on a dimensionally controlled carbon support according to claim 1, characterized in that, When the carbon support of the Gd-CuO electrocatalytic CO2 reduction catalyst based on dimensionally regulated carbon support prepared in step three is a dodecahedral structure, the mass ratio of dimethylimidazole, zinc nitrate hexahydrate, and hexadecyltrimethylammonium bromide is 2.724:0.177:0, and the reaction condition is stirring at room temperature for 4 hours.

10. A Gd-CuO electrocatalytic CO2 reduction catalyst based on a dimensionally regulated carbon support, prepared by the method described in any one of claims 1-9.

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