Copper-carbon composite material, its preparation method and use

Abstract

The present invention relates to a copper-carbon composite material, its preparation, and its use. The copper-carbon composite material has the advantages of high catalytic activity and high stability. The copper-carbon composite material according to the present invention comprises an active component and a support. The active component comprises a combination of Cu and CuO, and the support is a porous carbonaceous material. The Cu content of the combination is 1% to 50% by weight, based on 100% by weight of the composite, and the R1 value of the composite is 0.4 to 2:1.

Description

[Technical Field]

[0001] The present application belongs to the field of new energy technology, and relates to carbon-based materials and their preparation, and in particular to copper-carbon composite materials, their preparation and applications. [Background technology]

[0002] In recent years, with the rapid development of industry and human activities, carbon dioxide (CO2) emissions have been increasing year by year, and excessive CO2 emissions are a major cause of global warming. Statistics show that the global average temperature from 2016 to 2018 was 0.9 to 1.1°C higher than during the industrial period. Rising temperatures can lead to sea level rise, storm surges in coastal areas, and urban flooding, while extreme weather events can cause illness, death, and grain shortages. Therefore, the challenge of reducing CO2 emissions is daunting. China has set carbon peak and carbon neutrality targets: peaking CO2 emissions by 2030 and achieving carbon neutrality by 2060. To achieve these goals, China must transform its economy, which relies primarily on high consumption and high emissions, into an intensive economy, while developing CO2 capture and recycling technologies. One method for CO2 conversion and utilization is the hydroconversion of CO2 into high-energy-density organic fuels, such as carbon monoxide, methane, formic acid, formaldehyde, methanol, and other low-carbon energy sources. Among these, methanol is an important chemical feedstock and can be used to synthesize various chemical products. It can also be used as a clean alternative to fossil fuels, such as methanol gasoline and methanol fuel cells. Therefore, CO2 hydrogenation for methanol production has become a research focus in recent years. Currently, catalysts used for CO2 hydrogenation to produce methanol are mainly copper-based catalysts. Copper species are believed to be able to effectively catalyze the selective hydrogenation of carbon-oxygen bonds, and therefore copper species are widely used in the hydrogenation reaction to synthesize methanol. Existing commercially available catalysts include Cu / ZnO-Al2CO3, but these catalysts have poor catalytic activity and stability.

[0003] CN Patent CN112121805A discloses a catalyst for producing methanol by hydrogenating carbon dioxide, and its preparation and application. This disclosure involves adding a certain amount of alcohol solvent to a copper salt, a zinc salt, and a zirconium salt. The mixture is stirred and ultrasonically dispersed, then transferred to a reactor and subjected to a solvothermal reaction under sealed conditions to obtain a catalyst for producing methanol by hydrogenating carbon dioxide. CN Patent CN111215084A discloses a copper-based catalyst for producing methanol by hydrogenating carbon dioxide, and its preparation and application. This catalyst contains copper, zinc, and aluminum as active components. The zinc and aluminum components are first precipitated, aged, and calcined at a low temperature to obtain a zinc-aluminum hydrotalcite precursor, which has advantages in terms of higher stability and copper dispersibility. The active component, copper, and its precursor are then subjected to precipitation and precipitation reactions to finally obtain a novel copper-zinc-aluminum catalyst suitable for producing methanol by hydrogenating carbon dioxide.

[0004] Currently, copper-based catalysts prepared by existing methods are usually bulk phase catalysts, which have high copper consumption, low copper utilization rates, and high economic costs, limiting the large-scale industrial application of such copper-based catalysts. Supported catalysts have attracted more and more attention from researchers due to their characteristics, such as high dispersion of metal components, low content, and high effective utilization rate. Therefore, the development of metal-supported catalyst materials is currently one of the problems that need to be solved urgently. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present application aims to provide a copper-carbon composite material, its preparation, and its applications. The inventors of the present application have discovered that a copper-carbon composite material with high catalytic activity and high stability can be produced by pre-dispersing a copper active component on a carbonaceous material support, then forming pore channels in situ in the support, and further dispersing the copper active component in the newly formed pore channels. The present application was completed based on this discovery.

[0006] In one aspect, the present application is directed to a copper-carbon composite material comprising an active component and a support, wherein the active component comprises a combination of Cu and CuO, the support is a porous carbonaceous material, the combination is present in an amount of 1 wt % to 50 wt %, preferably 5 wt % to 35 wt %, calculated by mass on a Cu element basis, relative to 100 wt % of the composite, and the composite has an R1 value of 0.4 to 2:1, preferably 0.5 to 1.5:1, the R1 value being the height ratio between the CuO peak and the Cu peak in an XRD pattern of the composite.

[0007] In another aspect, the present application is directed to a method for producing a copper-carbon composite material, comprising the steps of: (1) contacting a carbonaceous material, a copper-containing compound, and an organic solvent under heat treatment conditions to obtain a pre-composite material (referred to as material A); (2) contacting the material A with an alkaline activator to carry out an activation reaction, thereby obtaining the copper-carbon composite material; Here, the carbonaceous material is a solid carbon-based material having a carbon content of more than 80% by weight, and is at least one selected from the group consisting of graphite precursors and activated carbon precursors.

[0008] In yet another aspect, the present application is directed to the use of the copper-carbon composite material according to the present application in the preparation of methanol by hydrogenation of carbon dioxide, adsorptive separation of CO, preparation of lower hydrocarbons by hydrogenation of carbon dioxide, photocatalytic conversion of carbon dioxide, electrocatalytic conversion of carbon dioxide, etc. [Effects of the Invention]

[0009] Compared with the prior art, the copper-carbon composite material and its preparation and application have one of the following advantages, or a combination of some or all of them:

[0010] 1. According to the present application, a composite material having an active component containing both copper element present in the valence state of Cu and copper element present in the valence state of CuO can be produced in situ, and the composite material has advantages such as good dispersibility of the active metal, a desired specific surface area, an aggregated pore size distribution, and high reaction activity, and is easy to prepare.

[0011] 2. According to the present application, a copper-carbon composite material with a controllable and stable Cu / Cu2O ratio can be obtained, which exhibits high selectivity for the production of methanol by hydrogenation of CO2.

[0012] 3. According to the present application, a precursor such as petroleum coke and a copper-containing compound are first pretreated in the presence of an organic solvent, which effectively enhances the contact between the copper-containing compound and the precursor through the infiltration swelling effect of the polar organic solvent, promotes the uniform dispersion of the copper-containing compound on the precursor, and accelerates the subsequent activation reaction of the precursor. Pretreatment with an organic solvent can be beneficial for the simultaneous production of Cu and CuO.

[0013] 4. According to the present application, the active component copper is introduced in situ during the activation process of the precursor, where diffusion paths into the lamellae and amorphous defects of the precursor graphite crystallites are created through pore formation by the activator, and the copper active component penetrates into the precursor's porous carbon pore channels together with the molten activator to form a highly dispersed structure. Furthermore, the use of a low activation temperature in the present application leads to the desired specific surface area and pore distribution, which is advantageous for the simultaneous production of the active components Cu and CuO.

[0014] 5. According to the present application, when a copper-carbon composite material is used in a catalyst for producing methanol by hydrogenating carbon dioxide, the porous carbon-based material used as the support provides abundant specific surface area and pore channels, acting as a structural promoter for highly dispersed support of the active components; meanwhile, the graphite microcrystalline layer of the porous carbon-based material also provides channels for electron transfer in the active centers and acts as a good conductor. This allows the catalytic activity of the Cu and CuO active centers to be better exerted, improving the reaction efficiency of methanol production by hydrogenating carbon dioxide. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is an XRD pattern of the copper-carbon composite material obtained in Example 1 of the present application. [Figure 2] FIG. 2 is a TEM image of the copper-carbon composite material obtained in Example 1 of the present application. [Figure 3] FIG. 3 is a pore distribution diagram of the copper-carbon composite material obtained in Example 1 of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present application will be described in detail below with reference to embodiments thereof, but it should be noted that the scope of the present application is not limited by those embodiments but is defined by the appended claims.

[0017] All publications, patent applications, patents and other documents cited in this specification are incorporated by reference in their entirety.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as those generally understood by those skilled in the art.In the event of any discrepancy, the contents described in this specification, including definitions, shall prevail.

[0018] In this specification, when a material, substance, method, step, apparatus, component, or the like is described as "commonly known to those skilled in the art," "prior art," or the like, it should be understood that the material, substance, method, step, apparatus, component, or the like includes not only those conventionally used in the relevant technical field at the time of filing this application, but also those that are no longer in general use but that become generally known in the relevant technical field to be suitable for a similar purpose.

[0019] Throughout the context of this specification and the claims, unless expressly stated otherwise, the term "comprise" or variations thereof, such as "comprises" or "comprising", shall be understood as including the elements or components expressly mentioned without excluding other elements or components.

[0020] In the context of this application, all numerical values ​​of parameters (e.g., amounts or conditions) shall be understood to be modified in all instances by the term "about," regardless of whether the term "about" is actually present before the numerical value.

[0021] In the context of this application, petroleum coke refers to solid coke produced by coking heavy oil in a coker.

[0022] In the context of this application, graphite precursor refers to any carbonaceous material that can be processed to produce graphite or to obtain a lamellar structure similar to graphite.

[0023] In the context of this application, activated carbon precursor refers to any carbonaceous material that can be treated to produce activated carbon or to obtain a pore structure similar to activated carbon.

[0024] In the context of this application, the specific surface area is measured according to the nitrogen physical adsorption method using an ASAP 2460 Physisorption Apparatus from Micromeritics Instrument Corporation under test conditions including: subjecting the sample to vacuum treatment at 200°C for 5 hours and carrying out the test at liquid nitrogen temperature (-196°C). The adsorption / desorption isotherms are obtained by static measurements, the specific surface area of ​​the catalyst is calculated according to the BET (Brunauer-Emmett-Teller) equation, and the pore size distribution is calculated according to the NLDFT method.

[0025] In the context of this application, the copper content in the composite material is obtained by measuring the metal content using a Thermal Scientific-IRIS Intrepid IIXSP Inductively Coupled Plasma Atomic Emission Spectrometer and calculating according to the formula: Copper content (%) = mass of copper / mass of composite material * 100%.

[0026] In the context of this application, the particle size of the active ingredient in the composite material is calculated from the XRD results using the Scherrer equation.

[0027] In the context of this application, the mass ratio of CuO / Cu in the composite is determined and calculated using a combination of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (XAES), using a Thermo Fisher Scientific (USA) Multilab 2000 X-ray photoelectron spectroscopy. The electron binding energy (BE) value is calibrated for sample charging effects using C 1s = 284.6 eV as an internal standard, and the surface atomic concentration ratio is calculated based on the peak area and calibrated with the atomic sensitivity factor.

[0028] In the context of this application, the evolution state of the active ingredient is characterized by transmission electron microscopy (TEM) under test conditions including: (i) sample preparation: grinding the composite material into powder, taking a small amount of sample, adding absolute ethyl alcohol therein, dispersing the sample by ultrasound, and finally dropping the dispersion onto a copper mesh and volatilizing the ethyl alcohol until dry for later use; and (ii) observing the sample under transmission electron microscopy.

[0029] In the context of this application, copper dispersion is measured by CO chemisorption under test conditions, including measurement using a Micromeritics Instrument Corporation Autochem 2910 Chemisorption Apparatus and detection using a thermal conductivity cell detector (TCD). The detailed procedures include: (i) catalyst pre-reduction: Approximately 0.1 g of the composite material is loaded into a U-shaped quartz reactor and first reduced with H at 350 °C for 1 hour, then purged with He gas at 360 °C for 1 hour, and then cooled to 50 °C; (ii) CO pulse adsorption: After the baseline is stabilized, a CO pulse adsorption experiment is performed using 5% CO / He as the adsorbate until the adsorption is saturated; and (iii) CO desorption: A temperature-programmed desorption experiment is performed under a He atmosphere at a heating rate of 10 °C / min up to 900 °C. The adsorption amount is then calculated based on the peak area. Copper dispersion = CO adsorption amount (g) / copper content in the composite (g) * 100%.

[0030] In the context of the present application, carbon content is measured according to the elemental analysis method under test conditions that include: performing an experiment in a Vario MICRO elemental analyzer by subjecting a sample to high temperature combustion oxidation, and separating the resulting gases to measure the carbon content.

[0031] In the context of this application, unless otherwise specified, all percentages, parts, ratios, etc. are expressed by weight and all pressures given are gauge pressures.

[0032] In the context of this application, any two or more embodiments of this application can be arbitrarily combined, and the resulting technical solutions form part of the initial disclosure of this application and are included in the scope of this application.

[0033] According to one embodiment of the present application, there is provided a copper-carbon composite, which is particularly suitable for use as a catalyst, and therefore may be referred to herein simply as a catalyst.

[0034] According to one embodiment of the present application, the copper-carbon composite material comprises an active component and a carrier.

[0035] According to one embodiment of the present application, the active component comprises a combination of Cu and Cu 2 O. The active component may also comprise additional components to adjust the catalytic properties or to meet the requirements of the present application.

[0036] According to one embodiment of the present application, the support is a porous carbonaceous material. Preferably, the porous carbonaceous material is a solid carbon-based material having a carbon content of more than 80% by weight, preferably derived from at least one selected from petroleum coke, needle coke, pitch, biomass char and coal, more preferably derived from petroleum coke.

[0037] According to one embodiment of the present application, the content of said combination, calculated based on the mass of Cu element, is 1 to 50% by weight, preferably 5 to 35% by weight, relative to 100% by weight of said composite material.

[0038] According to one embodiment of the present application, the composite material has an R1 value of 0.4 to 2:1, preferably 0.5 to 1.5:1, where R1 is the height ratio between the Cu2O peak and the Cu peak in the XRD pattern of the composite material. According to the present application, the composite material has a higher percentage of Cu2O compared to existing catalysts. If the R1 value of the copper-carbon composite is lower or higher than the above value, it will be less effective in catalyzing the hydrogenation of CO2 to produce methanol.

[0039] According to a preferred embodiment of the present application, the copper-carbon composite has an R value of 0.05-0.4:1, preferably 0.05-0.3:1, where the R value is the Cu content obtained by differentiating and imitating peaks based on XPS spectrum and Auger electron spectroscopy (XAES) of the composite. + peak and Cu 0 The R2 value is the area ratio between the peaks of the copper-carbon composite and the copper-carbon composite. According to a preferred embodiment, if the R2 value of the copper-carbon composite is higher than the above value, the catalyst will have poor storage stability and will be easily oxidized to copper oxide. On the other hand, if the R2 value is lower than the above value and the R1 value is also low, the composite will be less effective in catalyzing the hydrogenation of CO2 to produce methanol.

[0040] According to one embodiment of the present application, the copper-carbon composite material exhibits a substantially unchanged R1 value of 0.4 to 2:1, preferably 0.5 to 1.5:1, and a substantially unchanged R2 value of 0.05 to 0.4:1, preferably 0.05 to 0.3:1, when measured after being kept in an air atmosphere at 25°C for 48 hours. These measurement results indicate that the copper-carbon composite material of the present application has very strong storage stability, and the active ingredient can be maintained substantially unchanged for a long period of time.

[0041] According to one embodiment of the present application, at least a portion (and preferably substantially all) of the active component is embedded in the microcrystallite layer and amorphous defects of the graphite of the porous carbonaceous material.

[0042] According to one embodiment of the present application, the dispersion of copper is between 5% and 20%, preferably between 10% and 20%.

[0043] According to one embodiment of the present invention, the particle size of the active ingredient is between 3 nm and 20 nm, preferably between 5 nm and 15 nm.

[0044] According to one embodiment of the present application, the pore volume of pores having a pore diameter of 0.8 nm to 2 nm in the copper-carbon composite material is 30% to 50%, preferably 30% to 45% of the total pore volume.

[0045] According to one embodiment of the present application, the specific surface area of ​​the copper-carbon composite material is 100 to 600 m 2 / g, preferably 150 to 500m 2 / g.

[0046] According to one embodiment of the present application, there is also provided a method for producing a copper-carbon composite material.

[0047] According to one embodiment of the present application, the method comprises the following steps: contacting a carbonaceous material, a copper-containing compound, and an organic solvent under heat treatment conditions to obtain a pre-composite material (referred to as material A); The material A is brought into contact with an alkaline activator to carry out an activation reaction, thereby obtaining the copper-carbon composite material.

[0048] According to one embodiment of the present application, the carbonaceous material is a solid carbon-based material having a carbon content of more than 80 wt. % and is at least one selected from the group consisting of graphite precursors and activated carbon precursors. Preferably, the carbonaceous material is at least one selected from the group consisting of petroleum coke, needle coke, pitch, biomass char, and coal, more preferably petroleum coke.

[0049] According to one embodiment of the present application, the method further comprises washing and drying the resultant after the activation reaction to obtain a copper-carbon composite material.

[0050] According to one embodiment of the present application, the washing is usually water washing, where water washing means washing with water and filtering until the filtrate has a neutral pH.

[0051] According to one embodiment of the present application, the drying may be air drying or vacuum drying, preferably vacuum drying.

[0052] According to one embodiment of the present application, the drying temperature is 50° C. to 250° C., preferably 60° C. to 150° C. The drying time is 2 hours to 24 hours, preferably 5 hours to 16 hours.

[0053] According to one embodiment of the present application, the copper-containing compound is one or more selected from the group consisting of inorganic copper salts, organic copper salts, copper-containing oxides, and copper-containing hydroxides, specifically one or more selected from the group consisting of copper nitrate, basic copper carbonate, copper sulfate, copper chloride, copper formate, copper acetate, copper hydroxide, and copper oxide, and preferably one or more selected from the group consisting of copper chloride, copper nitrate, basic copper carbonate, copper sulfate, copper formate, and copper acetate.

[0054] According to one embodiment of the present application, the organic solvent is one or more selected from the group consisting of a pyrrolidone derivative, N,N-dimethylformamide, methanol, ethanol, tetrahydrofuran, and carbon disulfide, preferably a pyrrolidone derivative, more preferably at least one selected from N-methylpyrrolidone and N-ethylpyrrolidone, and particularly preferably N-methylpyrrolidone.

[0055] According to one embodiment of the present application, in step (1), a carbonaceous material, a copper-containing compound, and an organic solvent are uniformly mixed, subjected to heat treatment, and then dried to obtain material A.

[0056] According to one embodiment of the present application, the drying conditions include a drying temperature of 60°C to 350°C, preferably 80°C to 300°C; and a drying time of 0.5 hours to 24 hours, preferably 1 hour to 18 hours.

[0057] . According to one embodiment of the present application, drying may be carried out by any one of existing drying methods, specifically by one or more of oven drying, vacuum drying, and rotary evaporation drying, and preferably by vacuum drying or rotary evaporation drying.

[0058] According to one embodiment of the present application, the operating conditions of the heat treatment include a treatment temperature of 60°C to 400°C, preferably 80°C to 350°C, a treatment time of 0.1 hours to 24 hours, preferably 1 hour to 16 hours, and a treatment pressure (gauge pressure) of 0 MPa to 15 MPa, preferably 1 MPa to 10 MPa, more preferably 2 MPa to 8 MPa.

[0059] According to one embodiment of the present application, the heat treatment is carried out without introducing or adding liquid or vapor water, which means that, apart from the moisture itself that may be contained in each of the raw materials (i.e., the carbonaceous material, the copper-containing compound, and the organic solvent), no liquid or vapor water is intentionally introduced or added during the heat treatment.

[0060] According to one embodiment of the present application, the mass ratio of the carbonaceous material, the copper-containing compound, and the organic solvent is 1:0.01-1.2:1-100, preferably 1:0.1-0.8:10-50, and the copper-containing compound is calculated based on the mass of Cu element.

[0061] According to one embodiment of the present application, the alkaline activator is one or more selected from the group consisting of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide and calcium hydroxide, preferably potassium hydroxide.

[0062] According to one embodiment of the present application, the mass ratio of material A to the alkaline activator is 1:0.2-12, preferably 1:0.5-6.

[0063] According to one embodiment of the present application, the operating conditions for the activation reaction include one or more of a nitrogen atmosphere and / or an inert atmosphere, preferably a nitrogen atmosphere; an activation temperature of 300°C to 600°C, preferably 400°C to 550°C; and an activation time of 0.1 hours to 10 hours, preferably 0.5 hours to 8 hours. The alkaline activator is typically present in a molten state during the activation reaction. In this specification, "molten state" means that the alkaline activator is present as a liquid, but the temperature is not necessarily the melting temperature of the alkaline activator.

[0064] According to one embodiment of the present application, the inert gas is one or more selected from the group of helium, argon and neon.

[0065] According to one embodiment of the present application, the activation reaction is carried out without the introduction or addition of liquid or vapor water, which means that, apart from the moisture itself that may be contained in the respective starting materials (i.e., material A and the alkaline activator), no liquid or vapor water is intentionally introduced or added during the activation reaction.

[0066] According to one embodiment of the present application, there is also provided the use of a copper-carbon composite material according to the present application or a copper-carbon composite material obtained according to the method of the present application in the production of methanol by hydrogenation of carbon dioxide.

[0067] According to one embodiment of the present application, there is also provided the use of a copper-carbon composite material according to the present application or a copper-carbon composite material obtained according to the method of the present application in the adsorptive separation of CO.

[0068] According to one embodiment of the present application, there is also provided the use of a copper-carbon composite material according to the present application or a copper-carbon composite material obtained by a method according to the present application in the production of lower hydrocarbons by hydrogenation of carbon dioxide.

[0069] According to one embodiment of the present application, there is also provided the use of a copper-carbon composite material according to the present application or a copper-carbon composite material obtained by a method according to the present application in the photocatalytic conversion of carbon dioxide.

[0070] According to one embodiment of the present application, there is also provided the use of a copper-carbon composite material according to the present application or a copper-carbon composite material obtained by a method according to the present application in the electrocatalytic conversion of carbon dioxide.

[0071] According to the present application, the operating conditions for these applications are not particularly limited and may be those known in the art. [Example]

[0072] The present application will be described in more detail below with reference to examples, but the present application is not limited to these examples.

[0073] The activity of the composite material in the reaction to produce methanol by hydrogenation of carbon dioxide was evaluated in a fixed-bed reactor under the following conditions: a certain amount of catalyst was loaded into the reaction tube and heated to the reaction temperature under a nitrogen atmosphere. The nitrogen atmosphere was then switched to a reaction gas (carbon dioxide to hydrogen volume ratio 1:3, mixed with a certain amount of nitrogen as an internal standard), the gas space velocity was 3000 mL / (g·h), the reaction temperature was 250 °C, and the reaction pressure was 4 MPa. After the reaction stabilized, online analysis by gas chromatography was performed using an Agilent 8860 gas chromatograph equipped with a TCD detector.

[0074]

number

[0075]

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[0076] Example 1 Petroleum coke crushed to a particle size of 20–300 mesh, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.26:50 and treated at 5 MPa and 100°C for 8 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 10 hours. The resulting product A1 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:1.5 and activated at 500°C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 100°C for 5 hours to obtain composite material C-1. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0077] When observing the TEM image of composite material C-1, it can be seen that the active component is embedded in the microcrystalline layers and amorphous defects of the graphite of the support material.

[0078] Composite material C-1 was kept in air at 25°C for 48 hours, and then the R1 and R2 values ​​were measured, but no substantial changes were observed.

[0079] Example 2 Petroleum coke crushed to a particle size of 20–300 mesh, copper chloride, and N-ethylpyrrolidone were mixed uniformly in a mass ratio of 1:0.28:20 and treated at 2 MPa and 100°C for 3 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 180°C for 6 hours. The resulting product A2 was mixed uniformly with potassium hydroxide in a mass ratio of 1:1 and activated at 500°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 4 hours to obtain composite material C-2. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0080] Example 3 Petroleum coke crushed to a particle size of 20–300 mesh, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.42:40 and treated at 4 MPa and 200°C for 3 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 8 hours. The resulting product A3 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:1.5 and activated at 490°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 6 hours to obtain composite material C-3. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0081] Example 4 Petroleum coke crushed to a particle size of 20–300 mesh, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.13:30 and treated at 5 MPa and 150°C for 10 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 200°C for 6 hours. The resulting product A4 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:2 and activated at 450°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 100°C for 8 hours to obtain composite material C-4. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0082] Example 5 Petroleum coke crushed to 20-300 mesh particle sizes, copper nitrate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.68:30 and treated at 7 MPa and 110°C for 6 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 6 hours. The resulting product A5 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:0.8 and activated at 500°C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 7 hours to obtain composite material C-5. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0083] Example 6 Petroleum coke crushed to 20-300 mesh particle sizes, copper chloride, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.56:15 and treated at 2 MPa and 100°C for 10 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 200°C for 5 hours. The resulting product A6 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:1 and activated at 450°C for 6 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 130°C for 5 hours to obtain composite material C-6. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0084] Example 7 Petroleum coke crushed to 20-300 mesh particle sizes, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.49:40 and treated at 10 MPa and 100°C for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 8 hours. The resulting product A7 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:1.5 and activated at 500°C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 6 hours to obtain composite material C-7. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0085] Example 8 Petroleum coke, copper chloride, and N-methylpyrrolidone, crushed to a particle size of 20–300 mesh, were mixed uniformly in a mass ratio of 1:0.15:20 and treated at 3 MPa and 100°C for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 180°C for 4 hours. The resulting product A8 was mixed uniformly with potassium hydroxide in a mass ratio of 1:2 and activated at 525°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 110°C for 6 hours to obtain composite material C-8. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0086] Example 9 Petroleum coke crushed to a particle size of 20–300 mesh, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.19:45 and treated at 6 MPa and 250°C for 4 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 4 hours. The resulting product A9 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:2 and activated at 500°C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 100°C for 8 hours to obtain composite material C-9. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0087] Example 10 Petroleum coke crushed to 20-300 mesh particle sizes, copper nitrate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.42:40 and treated at 5 MPa and 350°C for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 180°C for 4 hours. The resulting product A10 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:3 and activated at 450°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 6 hours to obtain composite material C-10. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0088] Example 11 Petroleum coke crushed to a particle size of 20–300 mesh, copper chloride, and N,N-dimethylformamide were mixed uniformly in a mass ratio of 1:0.15:18 and treated at 2 MPa and 90°C for 3 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 140°C for 8 hours. The resulting product A11 was mixed uniformly with potassium hydroxide in a mass ratio of 1:2 and activated at 500°C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 110°C for 6 hours to obtain composite material C-11. The physical properties of the sample are shown in Table 1, and the evaluation results are shown in Table 2.

[0089] Example 12 Coal crushed to 20-300 mesh particles, copper nitrate, and N-ethylpyrrolidone were mixed uniformly in a mass ratio of 1:0.33:40 and treated at 3 MPa and 120°C for 4 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 6 hours. The resulting product A12 was mixed uniformly with potassium hydroxide in a mass ratio of 1:1.5 and activated at 450°C for 5 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 12 hours to obtain composite material C-12. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0090] Example 13 Petroleum coke crushed to a particle size of 20–300 mesh, copper nitrate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.36:40 and treated at 130°C under atmospheric pressure for 8 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 180°C for 5 hours. The resulting product A13 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:3 and activated at 475°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 110°C for 18 hours to obtain composite material C-13. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0091] Example 14 Petroleum coke crushed to 20-300 mesh particle sizes, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.09:9 and treated at 1 MPa and 100°C for 5 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 120°C for 10 hours. The resulting product A14 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:1.5 and activated at 500°C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 100°C for 18 hours to obtain composite material C-14. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0092] Example 15 Petroleum coke crushed to a particle size of 20–300 mesh, basic copper carbonate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.13:15 and treated at 2 MPa and 100°C for 3 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 130°C for 8 hours. The resulting product A15 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:7 and activated at 450°C for 6 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 130°C for 10 hours to obtain composite material C-15. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0093] Comparative Example 1 Specific surface area 421m 2 Activated carbon (1 / g) and copper chloride (1:0.5 by mass) were uniformly mixed and calcined at 550°C for 6 hours in a nitrogen atmosphere, followed by cooling to room temperature. The resulting product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum oven at 100°C for 6 hours to obtain composite material D-1. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0094] Comparative Example 2 Petroleum coke crushed to a particle size of 20–300 mesh, copper nitrate, and N-methylpyrrolidone were homogeneously mixed in a mass ratio of 1:0.42:40 and heated at 350°C under atmospheric pressure for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 180°C for 4 hours. The resulting product B2 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:3 and activated at 450°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 6 hours to obtain composite material D-2. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0095] Comparative Example 3 Petroleum coke crushed to a particle size of 20-300 mesh, basic copper carbonate, and potassium hydroxide were uniformly mixed in a mass ratio of 1:0.33:1 and activated at 500°C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum oven at 100°C for 5 hours to obtain composite material D-3. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0096] Comparative Example 4 Petroleum coke and copper nitrate, crushed to 20-300 mesh particle sizes, were mixed uniformly in a mass ratio of 1:0.42:40 and treated at 5 MPa and 350°C for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 180°C for 4 hours. The resulting product B4 was mixed uniformly with potassium hydroxide in a mass ratio of 1:3 and activated at 450°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 6 hours to obtain composite material D-4. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0097] Comparative Example 5 Petroleum coke and copper nitrate, crushed to 20-300 mesh particle sizes, were uniformly mixed in a mass ratio of 1:0.42 and heated at 350°C under atmospheric pressure for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven, where it was dried at 180°C for 4 hours. The resulting product B5 was uniformly mixed with potassium hydroxide in a mass ratio of 1:3 and activated at 450°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 6 hours to obtain composite material D-5. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0098] Comparative Example 6 1.32 g of polyethyleneimine was weighed out, 100 mL of ultrapure water was added, and the mixture was stirred until completely dissolved. Next, 1.97 g of copper nitrate was added to the mixture, followed by stirring until homogeneous. Next, 2 g of petroleum coke activated carbon was weighed out, stirred until homogeneous, and then placed in an autoclave. The autoclave was sealed and subjected to a hydrothermal reaction at 220°C for 3 hours. After the autoclave was allowed to cool to room temperature, the solid product was washed several times with deionized water and vacuum dried at 60°C to obtain composite material D-6.

[0099] Comparative Example 7 100 g of petroleum coke, crushed to a particle size of 20-300 mesh, was weighed and crushed into powder. Then, 46.83 g of sodium tetrachlorocarbonate and 300 g of potassium bicarbonate were mixed uniformly. The mixture was placed in a microwave furnace operating at a microwave frequency of 2450 MHz and heated to 900 °C at a microwave power of 0.3 kW under a nitrogen atmosphere for 20 minutes. After activation, the temperature was reduced to 300 °C under a nitrogen atmosphere, and a 5% (volume fraction) O2 / Ar mixed gas was introduced for 30 minutes. An appropriate amount of a 20 wt% glucose aqueous solution was weighed, added to the sample obtained above, and stirred in a water bath at 90 °C for 20 minutes. The obtained sample was crushed to powder, weighed, and mixed with deionized water in a mass ratio of 1:15. After thorough stirring, the solid-liquid separation was carried out until the pH of the filtrate became neutral. The obtained solid sample was placed in a vacuum drying oven and vacuum dried at 150°C for 6 hours to obtain composite material D-7.

[0100] Comparative Example 8 Petroleum coke crushed to 20-300 mesh particle size, copper nitrate, and water were homogeneously mixed in a mass ratio of 1:0.21:18 and treated at 2 MPa and 90°C for 3 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 6 hours. The resulting product B8 was homogeneously mixed with potassium hydroxide in a mass ratio of 1:2 and activated at 500°C for 6 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 110°C for 15 hours to obtain composite material D-8. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0101] Comparative Example 9 Graphite crushed to 20-300 mesh particles, copper nitrate, and N-methylpyrrolidone were mixed uniformly in a mass ratio of 1:0.42:40 and treated at 5 MPa and 350°C for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 6 hours. The resulting product B9 was mixed uniformly with potassium hydroxide in a mass ratio of 1:3 and activated at 500°C for 10 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was then dried in a vacuum drying oven at 120°C for 15 hours to obtain composite material D-9. The sample properties are shown in Table 1, and the evaluation results are shown in Table 2.

[0102] Comparative Example 10 Petroleum coke crushed to a particle size of 20–300 mesh, copper chloride, and N-methylpyrrolidone were uniformly mixed in a mass ratio of 1:0.21:20 and treated at 3 MPa and 100°C for 2 hours, then cooled to room temperature. A sample was collected and placed in a vacuum drying oven and dried at 150°C for 6 hours. The resulting product, B10, was placed in a tubular furnace with steam and activated at 525°C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the activated product was filtered and washed with water until the filtrate reached a neutral pH. The solid product was dried in a vacuum drying oven at 140°C for 8 hours to obtain composite material D-10. The physical properties of the sample are shown in Table 1, and the evaluation results are shown in Table 2.

[0103] [Table 1]

[0104] [Table 2]

Claims

1. A copper-carbon composite material comprising an active component and a carrier, wherein the active component is Cu and Cu ２ and O, wherein the support is a porous carbonaceous material, and the combination is present in an amount of 1 to 50 wt %, preferably 5 to 35 wt %, calculated by mass based on Cu element, relative to 100 wt % of the composite material, and the composite material has an R1 value of 0.4 to 2:1, preferably 0.5 to 1.5:1, wherein the R1 value is a value obtained by measuring the R1 value of Cu in an XRD pattern of the composite material. ２ The height ratio between the O peak and the Cu peak of the copper-carbon composite.

2. 2. The copper-carbon composite material according to claim 1, having an R value of 0.05 to 0.4:1, preferably 0.05 to 0.3:1, wherein the R value is obtained by decomposing and mimicking peaks based on XPS spectrum and Auger electron spectroscopy (XAES) of the composite material. ＋ and Cu ０ The area ratio between the peaks of the copper-carbon composite.

3. 2. The copper-carbon composite material according to claim 1, wherein the copper-carbon composite material exhibits an R1 value of 0.4 to 2:1, preferably 0.5 to 1.5:1, and an R2 value of 0.05 to 0.4:1, preferably 0.05 to 0.3:1, when measured after being kept in an air atmosphere at 25°C for 48 hours.

4. 2. The copper-carbon composite material of claim 1, wherein at least a portion (preferably substantially all) of the active component is embedded in the graphite microcrystalline layers and amorphous defects of the porous carbonaceous material, and / or the dispersion of copper is 5% to 20%, preferably 10% to 20%.

5. The copper-carbon composite material according to claim 1, wherein the active component has a particle size of 3 nm to 20 nm, preferably 5 nm to 15 nm.

6. 2. The copper-carbon composite material of claim 1, wherein the porous carbonaceous material is a solid carbon-based material having a carbon content of more than 80% by weight, preferably derived from at least one of petroleum coke, needle coke, pitch, biomass char and coal, more preferably derived from petroleum coke.

7. 2. The copper-carbon composite material according to claim 1, wherein the pore volume of pores having a pore diameter of 0.8 nm to 2 nm accounts for 30% to 50%, preferably 30% to 45%, of the total pore volume.

8. 100 to 600 m ２ / g, preferably 150 to 500m ２ 2. The copper-carbon composite material according to claim 1, having a specific surface area of ​​1000 W / g.

9. A method for producing a copper-carbon composite material, comprising the steps of: (1) contacting a carbonaceous material, a copper-containing compound, and an organic solvent under heat treatment conditions to obtain a pre-composite material (referred to as material A); (2) contacting the material A with an alkaline activator to carry out an activation reaction, thereby obtaining the copper-carbon composite material; Here, the carbonaceous material is a solid carbon-based material having a carbon content of more than 80% by weight, and is at least one selected from the group consisting of graphite precursors and activated carbon precursors.

10. 10. The method for producing a copper-carbon composite material according to claim 9, further comprising washing and drying the copper-carbon composite material after the activation reaction is completed to obtain the copper-carbon composite material.

11. The method for producing a copper-carbon composite material according to claim 10, wherein the drying temperature is from 50°C to 250°C, preferably from 60°C to 150°C.

12. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the copper-containing compound is one or more selected from the group consisting of inorganic copper salts, organic copper salts, copper-containing oxides, and copper-containing hydroxides, specifically one or more selected from the group consisting of copper nitrate, basic copper carbonate, copper sulfate, copper chloride, copper formate, copper acetate, copper hydroxide, and copper oxide, and preferably one or more selected from the group consisting of copper chloride, copper nitrate, basic copper carbonate, copper sulfate, copper formate, and copper acetate.

13. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the organic solvent is one or more selected from the group consisting of a pyrrolidone derivative, N,N-dimethylformamide, methanol, ethanol, tetrahydrofuran, and carbon disulfide, preferably a pyrrolidone derivative, more preferably at least one selected from the group consisting of N-methylpyrrolidone and N-ethylpyrrolidone, and particularly preferably N-methylpyrrolidone.

14. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the carbonaceous material is at least one selected from the group consisting of petroleum coke, needle coke, pitch, biomass char and coal, more preferably petroleum coke.

15. 10. The method for producing a copper-carbon composite material according to claim 9, wherein in step (1), the carbonaceous material, the copper-containing compound, and the organic solvent are uniformly mixed, subjected to a heat treatment, and then dried to obtain material A.

16. 16. The method for producing a copper-carbon composite material according to claim 15, wherein the drying conditions include a drying temperature of 60°C to 350°C, preferably 80°C to 300°C, and a drying time of 0.5 hours to 24 hours, preferably 1 hour to 18 hours.

17. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the operating conditions of the heat treatment include a treatment temperature of 60°C to 400°C, preferably 80°C to 350°C, a treatment time of 0.1 hours to 24 hours, preferably 1 hour to 16 hours, and a treatment pressure (gauge pressure) of 0 MPa to 15 MPa, preferably 1 MPa to 10 MPa, and more preferably 2 MPa to 8 MPa.

18. 10. The method for producing a copper-carbon composite material according to claim 9, wherein said heat treatment is carried out without the introduction or addition of liquid or vapor water.

19. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the mass ratio of the carbonaceous material, the copper-containing compound, and the organic solvent is 1:0.01-1.2:1-100, preferably 1:0.1-0.8:10-50, wherein the amount of the copper-containing compound is calculated based on the mass of Cu element.

20. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the alkaline activator is one or more selected from the group consisting of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, and calcium hydroxide, preferably potassium hydroxide.

21. The method for producing a copper-carbon composite material according to claim 9, wherein the mass ratio of material A to alkaline activator is 1:0.2-12, preferably 1:0.5-6.

22. 10. The method for producing a copper-carbon composite material according to claim 9, wherein the operating conditions of the activation reaction include: the alkaline activator being in a molten state; one or more of a nitrogen atmosphere and / or an inert atmosphere, preferably a nitrogen atmosphere; the activation temperature being 300°C to 600°C, preferably 400°C to 550°C; and the activation time being 0.1 hours to 10 hours, preferably 0.5 hours to 8 hours.

23. The method for producing a copper-carbon composite material according to claim 9, wherein the activation reaction is carried out without introducing or adding liquid or vapor water.

24. 10. Use of the copper-carbon composite material according to claim 1 or the copper-carbon composite material obtained by the method according to claim 9 in the production of methanol by hydrogenation of carbon dioxide.

25. Use of the copper-carbon composite material according to claim 1 or the copper-carbon composite material obtained by the method according to claim 9 in the adsorptive separation of CO.

26. 10. Use of the copper-carbon composite material according to claim 1 or the copper-carbon composite material obtained by the method according to claim 9 in the production of lower hydrocarbons by hydrogenation of carbon dioxide.

27. Use of the copper-carbon composite material according to claim 1 or obtained by the method according to claim 9 in the photocatalytic conversion of carbon dioxide.

28. Use of the copper-carbon composite material according to claim 1 or obtained by the method according to claim 9 in the electrocatalytic conversion of carbon dioxide.

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