Alkenyl-carbon-copper oxide functional composites and methods of making the same

Abstract

The application provides an ene-carbon-cuprous oxide functional composite material and a preparation method thereof. The ene-carbon-cuprous oxide functional composite material or the ene-carbon-cuprous oxide functional composite material prepared by using the patent method comprises an ene-carbon material matrix and cuprous oxide particles grown on the ene-carbon material matrix, the ene-carbon material matrix has pores, and the cuprous oxide nanoparticles are semi-embedded and grown on the ene-carbon matrix, and the interface is in close contact, so that the excess aggregated electrons are quickly transported and led out, and the problems of valence state change and structure damage caused by the rise of local electron density are effectively solved. + The problems of valence state change and structure damage caused by the rise of local electron density are effectively solved.

Description

Technical Field

[0001] This invention relates to the field of olefin-carbon functional composite material preparation technology, specifically to an olefin-carbon material with semi-embedded cuprous oxide nanoparticles and its preparation method. Background Technology

[0002] As human society has developed to its current state, the excessive use of fossil fuels and the rampant emission of greenhouse gases have inevitably led to increasingly severe global warming and energy shortages. Today, with heightened awareness of the energy crisis and environmental protection, humanity has begun extensive research and exploration into resource recycling, intelligent manufacturing, and energy conservation and emission reduction.

[0003] Among them, high-commercial-value C is produced by electrocatalytic reduction of greenhouse gas carbon dioxide as a raw material. 2+ This work is of great significance for achieving a neutral carbon cycle and alleviating the energy and environmental crisis. In the electrocatalytic reduction of carbon dioxide, the catalyst plays a decisive role. Among the many electrocatalysts, the copper-based catalyst cuprous oxide (Cu₂O) has been a focus of research due to its ability to moderately bind key intermediates and convert them into long-chain hydrocarbons and multi-carbon oxides.

[0004] Using cuprous oxide (Cu₂O) as a catalyst, its {100} crystal facet exhibits high C / C coupling activity and high selectivity for ethylene (C₂H₄). In practical electrocatalytic reduction applications, although Cu₂O shows high selectivity for C… 2+ The product achieved the ideal Faraday efficiency, but due to the high negative potential present in the electrocatalytic reduction of carbon dioxide, it is prone to degradation in Cu. + The surrounding region is enriched with a large number of electrons, and the electron density increases, leading to a metastable monovalent Cu. + When reduced to elemental copper, its structure is destroyed, making it difficult to maintain its catalytic activity and selective stability. Furthermore, the catalyst's dispersibility during the catalytic process and its recyclability in later applications are also issues that need to be considered and addressed.

[0005] Of the published cases, case CN110508279A reported a cuprous oxide-embedded graphene ultrafine composite sphere, its preparation method, and its application. However, the cuprous oxide prepared by it is in the form of spherical particles, lacking the {100} crystal facet with high CC coupling activity. Moreover, the composite material is in an aggregated state. Whether in the application of photocatalytic degradation of the organic dye methyl orange mentioned in the case or in other catalytic applications, the aggregation of particles will lead to a reduction in the active contact area between the catalyst and the catalytic target, resulting in low catalytic efficiency. Furthermore, case CN114853051A reports a cuprous oxide@copper oxide-graphene nanocomposite material and its preparation and application. It involves directly mixing cuprous oxide and graphene oxide under alkaline conditions, followed by filtration and drying. However, this direct mixing method leads to the oxidation of the cuprous oxide raw material to form copper oxide. Moreover, the final product produced by the direct mixing method has a severe interfacial steric hindrance effect, which is not conducive to the transport and separation of electron-hole pairs during the catalytic process, resulting in performance degradation. In addition, the final product has a graphene-coated microstructure, and the active reaction surface of cuprous oxide cannot be fully exposed, making it unsuitable for the electrochemical catalytic carbon dioxide reduction reaction mentioned in this case.

[0006] Numerous SCI-indexed publications have reported on the application of cuprous oxide nanomaterials in the electrocatalytic carbon dioxide reduction reaction. These publications often employ methods such as non-metallic doping modification, surface-loaded silica modification, and noble metal doping modification to improve and regulate performance. For details, please refer to the following SCI-indexed publication: "Tailoring the Catalytic Microenvironment of Cu2O with SiO2 to Enhance C..." 2+ Product Selectivity in CO2Electroreduction", "Stabilizing Cu2O for enhancing selectivity of CO2electroreduction to C2H4 with the modification of Pd nanoparticles", "FacetDopant Regulation of Cu2O Boosts Electrocatalytic CO2 Reduction to Formate".

[0007] Graphene, a honeycomb-shaped two-dimensional material composed of carbon atoms bonded in an sp2 hybridization manner, possesses excellent electrical, thermal, and mechanical properties. Along with graphite, carbon nanotubes, and fullerenes, it is a typical representative of the olefin family and plays a superior role in various application fields. Summary of the Invention

[0008] Regarding the presence of cuprous ions (Cu) mentioned in the appeal... + To address issues such as valence state changes, structural damage, dispersion, and recyclability, the primary objective of this invention is to provide a functional composite material of olefinic carbon and cuprous oxide, characterized in that it comprises an olefinic carbon matrix and cuprous oxide particles grown on the olefinic carbon matrix, wherein the olefinic carbon matrix has pores.

[0009] Preferably, the graphene-carbon material matrix is ​​at least one of graphene, graphite fiber, and graphene fiber, and the graphene can be any one or more of bubble CVD graphene powder, reduced redox graphene, and graphene prepared by mechanical ball milling.

[0010] Preferably, the cuprous oxide is in the form of cubic particles, and the cuprous oxide cubic particles are semi-embedded on the olefinic carbon material.

[0011] Preferably, the average particle size of the cubic cuprous oxide particles is ≤200nm.

[0012] The second objective of this invention is to provide a method for preparing the above-mentioned olefinic carbon-cuprous oxide functional composite material, specifically comprising the following steps:

[0013] (1) Weigh a certain mass of olefin carbon material, copper-containing raw material and potassium hydroxide and mix them;

[0014] (2) The mixed materials are placed in a quartz tube furnace for heating and reaction;

[0015] (3) After the reaction is complete and the powder is cooled to room temperature, wash and dry it to obtain the target product.

[0016] Preferably, in step (1), the mass ratio of the olefinic carbon material to the copper-containing raw material is 10:1-3, and the mass ratio of the olefinic carbon material to potassium hydroxide is 1:3-5.

[0017] Preferably, the mixing in step (1) specifically involves mixing the olefinic material, copper-containing raw material, and potassium hydroxide using a 50% aqueous ethanol solution.

[0018] Preferably, the heating reaction in step (2) is as follows: the mixed powder is pushed into the heating reaction zone of the tube furnace, the mechanical pump is turned on to draw a vacuum, the heating curve is set, the temperature is first raised to 90°C and held for 30 minutes to remove the moisture in the powder, and then the temperature is raised to 750-900°C and held for 60 minutes. 200 sccm of inert gas is passed through the furnace for protection throughout the process.

[0019] Preferably, the cleaning in step (3) specifically involves stirring and cleaning it with a 0.1-0.8 mol / L acid solution for 5-20 minutes, followed by cleaning with deionized water until neutral.

[0020] Preferably, the amount of acid solution used is 200-400 times the mass of the olefinic material.

[0021] Compared with the prior art, the olefinic carbon-cuprous oxide functional composite material provided by the present invention / the olefinic carbon-cuprous oxide functional composite material prepared by the above method has the following technical advantages:

[0022] Cuprous oxide particles are uniformly dispersed and semi-embedded on the surface of graphene, graphite fiber and other carbon materials, which effectively solves the problems of uneven dispersion and easy agglomeration of nanoparticles, insufficient exposure of active surfaces and difficulty in recycling and reuse.

[0023] Using graphene, graphite fiber, and other carbonaceous materials as substrates, cuprous oxide nanoparticles are semi-embedded and grown on them with tight interfacial contact, enabling rapid transport and extraction of excess aggregated electrons. This effectively solves the problem of Cu(II) ions in the electrocatalytic reduction process. + Problems related to changes in valence state and structural damage caused by an increase in local electron density.

[0024] The cuprous oxide particles semi-embedded on the olefinic carbon material have a cubic structure, and the exposed surfaces belong to the {100} crystal plane group with high CC coupling activity, which ensures the high ethylene C2H4 selectivity of the material. Attached Figure Description

[0025] Appendix Figure 1 SEM image of the final product obtained in Example 1

[0026] Appendix Figure 2 SEM image of the final product obtained in Example 2

[0027] Appendix Figure 3 SEM image of the final product obtained in Example 3

[0028] Appendix Figure 4 SEM image of the final product obtained in Comparative Example 1

[0029] Appendix Figure 5 SEM image of the final product obtained in Comparative Example 2

[0030] Appendix Figure 6 SEM image of the final product obtained in Comparative Example 3

[0031] Appendix Figure 7 SEM image of the final product obtained in Comparative Example 4

[0032] Appendix Figure 8SEM image of the final product obtained in Comparative Example 5 Implementation

[0033] The technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0034] In an embodiment of the present invention, a functional composite material of olefinic carbon-cuprous oxide is provided, characterized in that it comprises an olefinic carbon material matrix and cuprous oxide particles grown on the olefinic carbon material matrix, wherein the olefinic carbon material matrix has pores. The presence of pores in the olefinic carbon material matrix can effectively act as an electron "trap," enabling the effective capture and rapid transport of electrons during electrocatalytic reduction, thus preventing the cuprous oxide ions (Cu) from being trapped. + Excessive local electron density leads to changes in catalyst valence state and structural damage, resulting in catalyst failure. The specific principle is as follows: the formation of pores signifies the absence of carbon atoms, creating numerous dangling bonds. As a common surface state, these bonds deplete carriers and pin the Fermi level around the pores, generating a spherical depletion region. This depletion region drives electrons inward and attracts holes to the surface, effectively capturing electrons. For electrons and holes to recombine, they must overcome a potential barrier, thus achieving effective separation, extending carrier lifetime, and improving catalytic efficiency. Simultaneously, the ultra-high carrier mobility resulting from the free movement of electrons on the delocalized large π bonds in graphene, along with the ultrafast confined transport of the one-dimensional graphite fiber structure, allows for rapid and timely transport of captured electrons.

[0035] In some specific embodiments, the graphene-carbon material is at least one of graphene, graphite fiber, and graphene fiber. The graphene can be any one or more of bubble CVD graphene powder, reduced redox graphene, and graphene prepared by mechanical ball milling. The reason for choosing the above materials as the matrix is ​​that they have excellent electrical conductivity and can realize the rapid transport and extraction of excess accumulated electrons.

[0036] In some specific embodiments, the cuprous oxide is in the form of cubic particles, which are semi-embedded in the olefinic material. Cubic cuprous oxide particles exhibit higher CC coupling activity compared to {100} crystal faces of other shapes.

[0037] In some specific embodiments, the average particle size of the cubic cuprous oxide particles is ≤200 nm. The smaller the average particle size of the cuprous oxide particles, the smaller the active contact area with the target catalyst, and the better its catalytic activity.

[0038] In an embodiment of the present invention, a method for preparing the above-mentioned olefinic carbon-cuprous oxide functional composite material is provided, the specific steps of which are as follows:

[0039] (1) Weigh a certain mass of olefin carbon material, copper-containing raw material and potassium hydroxide and mix them;

[0040] (2) The mixed materials are placed in a quartz tube furnace for heating and reaction;

[0041] (3) After the reaction is complete and the powder is cooled to room temperature, wash and dry it to obtain the target product.

[0042] In this process, cubic cuprous oxide particles can be grown. The principle is as follows: During the powder raw material mixing stage, the alkaline environment provided by the dissolved potassium hydroxide causes the copper-containing raw material to generate copper hydroxide Cu(OH)2. During the heating process, it gradually transforms into copper oxide. At high temperature, copper oxide undergoes a carbothermic reduction reaction with carbon, reducing it to copper and simultaneously thermally etching the carbon material, creating nanopores. Copper then adheres to these nanopores. Simultaneously, potassium hydroxide also undergoes a carbothermic reaction with carbon at high temperature, etching the carbon material. These two reactions consume a portion of the potassium hydroxide, while the remaining potassium hydroxide and potassium produced by the carbothermic reaction are used to further etch the carbon material. During the cleaning stage after the reaction, the copper is dissolved in the cleaning solution. Subsequently, the copper attached to the pores of the olefinic carbon material is oxidized by the components in the cleaning solution and dissolved in the solution to generate copper ion-containing substances. The unoxidized parts act as small crystal nuclei for later nucleation and growth. Due to the high reactivity of the nanopore defects on the olefinic carbon material, the copper ions in the solution will preferentially accumulate at this point to reach saturation and attach to the small crystal nuclei. After the drying process, the copper ions are thermally reduced to cuprous ions and begin to grow in situ around the small crystal nuclei. Driven by the principle of minimum free energy of the system, it grows along the direction perpendicular to the high-energy crystal plane {111}, so the final cuprous oxide has a cubic structure.

[0043] In this process, the principle by which cubic cuprous oxide particles can achieve semi-embedded growth is as follows: During the powder raw material mixing stage, the alkaline environment provided by the dissolution of potassium hydroxide will cause the copper-containing raw material to generate copper hydroxide Cu(OH)2. During the heating process, it will gradually transform into copper oxide. At high temperature, copper oxide will undergo a carbothermic reduction reaction with carbon to generate copper. During this process, the olefinic carbon material in contact with copper oxide will be etched with nanopores (it should be distinguished here from the large-diameter pores on the olefinic carbon material. The generation of nanopores is to achieve the semi-embedded growth of cuprous oxide, while the generation of large-diameter pores is to achieve electron capture and transport). Meanwhile, it is simultaneously reduced to copper and distributed at the nanopores. The nanopores generated by thermal etching can be understood as the absence of carbon atoms in graphene sheets and graphite fiber skeletons. As a defect, the exposed edge structure and dangling bonds give it high reactivity. During the cleaning process after the reaction, the nucleation and growth of cuprous ions will preferentially begin at these nanopore defects. Because the thermal etching ability of copper oxide and carbon is limited in the early stage, and the diameter of the graphene-carbon material is on the μm level, once the carbothermal reaction begins, the copper oxide is reduced to copper and loses its etching effect. Therefore, the cuprous oxide nanoparticles generated later will be semi-embedded and grown on the graphene-carbon material.

[0044] In some specific embodiments, the copper-containing raw material can be selected as any one or more of metallic copper powder or copper salt, and the specific selection is not limited.

[0045] In some specific embodiments, the mass ratio of the olefinic carbon material to the copper-containing raw material is 10:1-3. This ratio ensures that cuprous oxide has a suitable growth density on the olefinic carbon material substrate. If the copper content is too high, the growth density of cuprous oxide will increase, which will easily lead to particle interference and fusion, thereby reducing the catalytic activity of the product.

[0046] In some specific embodiments, the mass ratio of the olefinic carbon material to potassium hydroxide is 1:3-5, where potassium hydroxide is used as both an etching agent and an activator. If the potassium hydroxide content is too high, it can easily completely etch the olefinic carbon material matrix; if the content is too low, its etching and activation effects are limited, and it is impossible to etch pore features into the olefinic carbon substrate.

[0047] In some specific embodiments, the mixing of the olefin carbon material, the copper-containing raw material, and potassium hydroxide is carried out in a 50% aqueous ethanol solution. The olefin carbon material and the copper-containing raw material have better dispersibility in the ethanol solution, while the 50% aqueous solution can ensure the dissolution of potassium hydroxide. In this step, the mixed powder is stirred until it becomes a paste, thereby achieving uniform adhesion of the copper-containing raw material on the olefin carbon material matrix.

[0048] In some specific embodiments, the heating reaction in step (2) is as follows: the mixed powder is pushed into the heating reaction zone of the tube furnace, the mechanical pump is turned on to evacuate the vacuum, the heating curve is set, the temperature is first raised to 90°C and held for 30 minutes to remove the moisture in the powder, and then the temperature is raised to 750-900°C and held for 60 minutes, with 200 sccm of inert gas provided for protection throughout the process. Potassium hydroxide will undergo a carbothermic reaction with the olefin carbon material at high temperature, etching holes on the surface of the olefin carbon material. The reaction equation is as follows:

[0049] 6KOH + 2C → 2K↑ + 3H2↑ + 2K2CO3

[0050] K₂CO₃ + C → K₂O + 2CO↑

[0051] K₂O + C → 2K↑ + CO↑

[0052] In some specific embodiments, the cleaning in step (3) specifically involves stirring and cleaning with a 0.1-0.8 mol / L acid solution for 5-20 minutes, followed by cleaning with deionized water until neutral. If the cleaning time is too short, the copper in the nanopores of the carbon material cannot undergo proper oxidation reaction with the cleaning solution due to the short contact time between the cleaning solution and the carbon material. The concentration of copper ions in the solution is too low, which cannot sustain the growth of a large number of in-situ nucleation particles, resulting in poor growth of cuprous oxide cubic particles. If the cleaning time is too long, all the copper in the nanopores will dissolve into the cleaning solution and be removed, resulting in the inability of cuprous oxide nanoparticles to grow.

[0053] In some specific embodiments, the amount of acid solution used is 200-400 times the mass of the olefinic material.

[0054] The following specific embodiments further illustrate the content of the present invention, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field.

[0055] Example 1

[0056] Step (1): Weigh 0.2g of graphene fiber, 0.02g of copper powder and 0.8g of potassium hydroxide into a plastic beaker, add an appropriate amount of 50% ethanol aqueous solution and stir until a paste is formed.

[0057] Step (2): Place the paste mixed in step (1) into a corundum crucible and put it into the reaction zone of a quartz tube furnace. Close the furnace opening and turn on the vacuum pump. Heat the furnace to 90°C and hold for 30 minutes. Then heat the furnace to 850°C and hold for 60 minutes. Argon gas of 200 sccm is introduced throughout the process for protection.

[0058] Step (3): Take out the powder that has cooled to room temperature after the reaction and place it in a beaker. Stir and wash it with 60 ml of 0.5 mol / L hydrochloric acid solution for 12 min. Then wash it with deionized water until the pH is neutral. After filtration, dry it at 85℃ to obtain the final sample.

[0059] We performed morphological characterization on the final obtained samples, from the attached... Figure 1 The SEM characterization results clearly show the significant cubic characteristics of the cubic cuprous oxide nanoparticles. The exposed surfaces belong to the {100} crystal plane family with high CC coupling activity. The average size of the nanoparticles is 200 nm. It can be seen that the cubic cuprous oxide particles are uniformly dispersed and grown in a semi-embedded manner on the surface of graphene fibers. This growth mode ensures the uniform dispersion of cuprous oxide nanoparticles, the tightness of the bonding with the matrix interface, the activity and stability of the electrocatalytic reduction process, and the recyclability of the catalyst. Finally, the pores on the graphene fiber surface can also be observed. This is due to a series of activation reactions between potassium hydroxide and graphene materials at high temperatures, etching out this characteristic structure. The presence of these pores can effectively act as an electron "trap." These "traps" generate numerous dangling bonds, which, as a common surface state, deplete carriers and pin Fermi levels around the pores, creating a spherical depletion region. The existence of this depletion region drives electrons to move inward and attracts holes to move towards the surface, thereby achieving effective electron capture. This enables the effective capture and rapid transport of electrons during electrocatalytic reduction, avoiding the formation of cuprous ions (Cu). + Excessive local electron density leads to changes in the valence state and structural damage of the catalyst, resulting in its failure.

[0060] Example 2

[0061] Example 2 differs from Example 1 only in that the raw material, graphene fiber, is replaced with graphene; the remaining steps are the same. The SEM characterization image of the final product is attached. Figure 2 As shown, it can also be seen that it is uniformly dispersed and semi-embedded on the surface of the graphene sheet. Similarly, there are also pore structures formed by etching caused by potassium hydroxide activation. In addition, since the graphene sheet is easy to re-accumulate due to van der Waals forces, this novel sandwich structure is generated as shown in the figure.

[0062] Example 3

[0063] Example 3 differs from Example 2 in that the raw material copper powder is replaced with copper chloride; all other steps remain the same. The SEM image of the final product is shown in the attached image. Figure 3 As shown, cuprous oxide nanoparticles are uniformly dispersed and semi-embedded on the graphene sheets, exhibiting the same activated etched pore characteristics.

[0064] Comparative Example 1

[0065] Comparative Example 1 differed from Example 1 only in that the amount of copper powder used in step 1 was changed to 0.08 g, while the remaining steps were the same. The SEM characterization image of the final product is attached. Figure 4 As shown, due to the increase in copper raw materials, the growth density of cuprous oxide on graphene fibers increases, the dispersion uniformity decreases, and particle interference and fusion occur, resulting in a decrease in the catalytic activity of the final product.

[0066] Comparative Example 2

[0067] Comparative Example 2 changed the amount of potassium hydroxide used in Example 1 to 0.4 g, while the remaining steps were the same as in Example 1. The SEM characterization image of the final product is attached. Figure 5 As shown, although the cuprous oxide cubic particles are semi-embedded on the surface of the graphene fiber, the activation effect is limited due to the insufficient amount of potassium hydroxide, and no pore features appear on the surface of the graphene fiber.

[0068] Comparative Example 3

[0069] Comparative Example 3 was prepared using a traditional wet chemical method. Step (1): 0.2g of graphene fiber, 0.02g of copper chloride, and 0.8g of potassium hydroxide were weighed into a plastic beaker, and 60ml of 50% ethanol aqueous solution was added. The mixture was heated and stirred in a 60℃ water bath for 45min. Step (2): After stirring, the mixture was dried at 85℃. After drying, it was washed with 60ml of 0.5mol / L hydrochloric acid solution for 12min, and then washed with deionized water until the pH was neutral. After filtration, it was dried at 85℃. The SEM characterization image of the final product is shown below. Figure 6 As shown, no obvious semi-embedded growth of cuprous oxide nanoparticles was observed on the graphene fibers, nor were any pore features observed on the graphene fibers. This indicates that the heating reaction is one of the necessary conditions for etching out pore features, and also one of the conditions for the embedded growth of cuprous oxide cubic particles.

[0070] Comparative Example 4

[0071] The main difference between Comparative Example 4 and Example 1 is that Comparative Example 4 was washed with 60 ml of 0.5 mol / L hydrochloric acid solution for 25 min with stirring. The SEM characterization image of the final product is attached. Figure 7 As shown, only a few cuprous oxide nanoparticles were observed to grow semi-embedded. Most of the copper in the nanopores dissolved into the cleaning solution and was removed, preventing the cuprous oxide nanoparticles from growing.

[0072] Comparative Example 5

[0073] The main difference between Comparative Example 5 and Example 1 is that the hydrochloric acid cleaning step was not performed. The SEM characterization image of the final product is shown in the attached figure. Figure 8As shown, no semi-embedded growth of cuprous oxide nanoparticles was observed, indicating that the acid washing process is an essential step for the growth of cuprous oxide particles.

[0074] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only for the purpose of helping to understand the method and core ideas of the present invention. The above descriptions are only preferred embodiments of the present invention. It should be noted that due to the limitations of textual expression, while there are objectively infinite specific structures, those skilled in the art can make several improvements, modifications, or changes without departing from the principles of the present invention, and can also combine the above technical features in an appropriate manner. These improvements, modifications, changes, or combinations, or the direct application of the inventive concept and technical solution to other situations without modification, should all be considered within the scope of protection of the present invention.

Claims

1. A functional composite material of olefinic carbon-cuprous oxide, characterized in that, The composite material comprises an olefinic carbon material matrix and cuprous oxide particles grown on the olefinic carbon material matrix, wherein the olefinic carbon material matrix has pores; the olefinic carbon-cuprous oxide functional composite material is prepared by the following method: (1) Weigh a certain mass of olefin carbon material, copper-containing raw material and potassium hydroxide and mix them. The mass ratio of the olefin carbon material to the copper-containing raw material is 10:1-3 and the mass ratio of the olefin carbon material to potassium hydroxide is 1:3-5. (2) The mixed material is placed in a quartz tube furnace for heating reaction. The heating reaction is specifically as follows: the mixed powder is pushed into the heating reaction zone of the tube furnace, the mechanical pump is turned on to draw a vacuum, the heating curve is set, the temperature is first raised to 90°C and held for 30 minutes to remove the moisture in the powder, and then the temperature is raised to 750-900°C and held for 60 minutes. 200 sccm of inert gas is passed through the furnace for protection throughout the process. (3) After the reaction is completed and the powder is cooled to room temperature, it is washed and dried to obtain the target product. The washing is carried out by stirring and washing with 0.1-0.8 mol / L acid solution for 5-20 min, followed by washing with deionized water until neutral.

2. A functional composite material of olefinic carbon-cuprous oxide as described in claim 1, characterized in that, The graphene-carbon material matrix is ​​at least one of graphene and graphene fiber, and the graphene is any one or more of bubble CVD graphene powder, reduced redox graphene, and graphene prepared by mechanical ball milling.

3. A functional composite material of olefinic carbon-cuprous oxide as described in claim 1, characterized in that, The cuprous oxide is in the form of cubic particles, which are semi-embedded in the carbon material.

4. A functional composite material of olefinic carbon-cuprous oxide as described in claim 3, characterized in that, The average particle size of the cubic cuprous oxide particles is ≤200nm.

5. A functional composite material of olefinic carbon-cuprous oxide as described in claim 1, characterized in that, The mixing in step (1) specifically involves mixing the olefinic material, copper-containing raw material, and potassium hydroxide using a 50% ethanol aqueous solution.

6. A functional composite material of olefinic carbon-cuprous oxide as described in claim 1, characterized in that, The amount of acid solution used is 200-400 times the mass of the olefinic carbon material.

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