Fullerene-modified cobalt-based transition metal oxide nanocomposites, methods of making and applications thereof

Abstract

This invention belongs to the field of electrocatalytic materials technology, specifically relating to fullerene-modified cobalt-based transition metal oxide nanocomposites, their preparation methods, and applications. The fullerene-modified cobalt-based nanocomposites prepared by combining fullerenes with cobalt-based materials not only significantly improve the catalytic activity and selectivity of the chloride evolution reaction (CER), but also effectively inhibit material corrosion and deactivation under strong oxidizing environments. Their performance is significantly superior to traditional cobalt-based materials and cobalt-based materials modified with carbon black or graphene. This breakthrough provides a novel solution to address the inherent defects of cobalt-based catalysts, demonstrating significant application prospects in highly corrosive electrochemical reactions such as CER. It can be used for efficient electrochlorination treatment of recalcitrant organic pollutants in various water bodies, including groundwater, surface water, and industrial wastewater.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic materials technology. More specifically, it relates to fullerene-modified cobalt-based transition metal oxide nanocomposites, their preparation methods, and applications. Background Technology

[0002] Chlorine (Cl2) is one of the key basic chemical raw materials in modern industry, widely used in polyvinyl chloride synthesis, pulp bleaching, drinking water disinfection, and fine chemical manufacturing. Currently, industrial chlorine production heavily relies on the chlor-alkali electrolysis process, which consumes approximately 2% of global electricity generation, with the electrolysis stage accounting for as much as 60% of the energy consumption—making it a typical high-energy-consuming chemical process. Therefore, improving the energy conversion efficiency of the chlorine evolution reaction (CER) has become a core issue for achieving energy conservation and emission reduction in the chlor-alkali industry and promoting the low-carbon transformation of the chemical industry.

[0003] In the traditional chlor-alkali industry, the mainstream catalyst for the chlorine evolution reaction (CER) is ruthenium-iridium-based mixed metal oxides (RuIr-MMOs). While these catalysts can maintain a certain level of catalytic activity in harsh environments with high potential and high chloride ion concentrations, their high raw material costs are due to the scarcity of precious metal resources. Furthermore, long-term use is prone to the dissolution and loss of precious metals, leading to a decline in catalytic performance and further restricting the economic and environmental benefits of the process. Therefore, there is an urgent need to develop non-precious metal-based CER electrocatalysts based on abundant Earth elements.

[0004] Cobalt-based oxides are considered promising candidates for non-precious metal chlorine evolution reaction catalysts due to their advantages such as low cost, high elemental abundance, and tunable electronic structure. However, existing cobalt-based oxide catalysts still have shortcomings: First, the intrinsic electronic structure of the cobalt active center is difficult to adapt to the energy barrier requirements of the chlorine evolution reaction, resulting in insufficient catalytic activity and easy occurrence of oxygen evolution side reactions, reducing the selectivity of chlorine products; second, in high-potential and highly corrosive electrolysis environments, cobalt-based oxides are prone to oxidation, dissolution, and structural collapse, making it difficult to meet the stability requirements for long-term industrial operation.

[0005] Therefore, developing cobalt-based catalysts that combine excellent catalytic activity, high selectivity, and long-term stability has become an urgent research need. Summary of the Invention

[0006] This invention addresses the common problems of low catalytic activity, poor selectivity, and insufficient cycle stability in existing cobalt-based chlorine evolution catalysts, and aims to provide a fullerene-modified cobalt-based nanocomposite material and its preparation method.

[0007] The primary objective of this invention is to provide a method for preparing fullerene-modified cobalt-based nanocomposites.

[0008] A second objective of this invention is to provide a fullerene-modified cobalt-based nanocomposite material obtained by the aforementioned preparation method.

[0009] A third objective of this invention is to provide the application of the fullerene-modified cobalt-based nanocomposite material in the preparation of electrode catalytic materials.

[0010] The fourth objective of this invention is to provide an electrode catalytic material.

[0011] A fifth objective of this invention is to provide the application of the fullerene-modified cobalt-based nanocomposite material or the electrode catalytic material in chlorination reaction and / or electrochlorination degradation.

[0012] The above-mentioned objective of this invention is achieved through the following technical solution:

[0013] This invention provides a method for preparing fullerene-modified cobalt-based nanocomposites, comprising the following steps: S1: Mix the metal salt and organic ligand in a solvent, react thoroughly, and then perform post-treatment to obtain a cobalt-based metal-organic ligand precursor. S2: The cobalt-based metal-organic ligand precursor obtained in S1 is modified with fullerene to obtain fullerene-modified cobalt-based metal-organic ligand nanomaterials. S3: The fullerene-modified cobalt-based metal-organic ligand nanomaterials obtained in S2 are pyrolyzed at 200~500 °C to obtain the fullerene-modified cobalt-based nanocomposite material. In step S1, the metal component in the metal salt includes at least cobalt.

[0014] This invention creatively discovers that the composite structure constructed from fullerenes and cobalt-based oxide materials not only significantly enhances the catalytic activity and reaction selectivity of CER (Chemical Evolution of Chlorine) but also effectively suppresses corrosion deactivation under strong oxidizing environments. Compared to traditional cobalt-based materials, its catalytic performance and stability are significantly improved, even surpassing cobalt-based materials modified with other carbon nanomaterials (such as carbon black and graphene). This groundbreaking discovery provides a novel solution to address the inherent defects of cobalt-based catalysts and shows significant application potential in highly corrosive electrochemical reactions such as the chlorine evolution reaction (CER).

[0015] Preferably, in step S1, the molar ratio of the metal salt to the organic ligand is 1:(0.2~20), more preferably 1:(0.4~16).

[0016] Preferably, in step S1, the ratio of the metal salt to the solvent is 1 mmol: (0.5~80) mL, more preferably 1 mmol: (0.8~70) mL.

[0017] Preferably, in step S1, the metal component in the metal salt further includes a doped metal, which is selected from at least one of nickel, iron, manganese, copper, zinc, tungsten, chromium, molybdenum, lanthanum, cerium, europium, indium, gallium, titanium, tin, and bismuth.

[0018] More preferably, the doped metal includes at least one of chromium, tungsten, titanium, zinc, manganese, and lanthanum.

[0019] Preferably, the molar ratio of the metal component cobalt to the doped metal in the metal salt is (1~60):1, more preferably (1~49):1.

[0020] Preferably, in step S1, the metal salt is selected from at least one of nitrates, acetates, chlorides, carbonates, and sulfates.

[0021] More preferably, in step S1, the metal salt is selected from at least one of nitrates, acetates, chlorides, and sulfates.

[0022] Preferably, in step S1, the organic ligand is selected from at least one of carboxylic acid compounds, alcohol compounds, and imidazole compounds.

[0023] More preferably, the carboxylic acid compound is selected from benzene carboxylic acids and / or ethylenediaminetetraacetic acid.

[0024] Optionally, the benzene carboxylic acid is selected from at least one of isophthalic acid, phthalic acid, terephthalic acid, 2-aminoterephthalic acid, 5-aminoisophthalic acid, 2,5-dihydroxyterephthalic acid, trimesin, triphenylcarboxylic acid, trimesin, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-2,4,4'-tricarboxylic acid, 3,3'-biphenylcarboxylic acid, and 2,4'-biphenylcarboxylic acid.

[0025] More preferably, the alcohol compound is selected from polyol compounds, specifically at least one of ethylene glycol, propylene glycol, hexanediol, pentanediol, glycerol, 1,4-butanediol, and 1,2,4-butanetriol.

[0026] More preferably, the imidazole compound is selected from 2 Methylimidazole, 2,4 At least one of dimethylimidazole, 2-ethylimidazole, N-benzoylimidazole, and benzimidazole.

[0027] More preferably, the organic ligand is selected from 2,5-dihydroxyterephthalic acid, 2,4-dihydroxyterephthalic acid, etc. At least one of dimethylimidazole, ethylenediaminetetraacetic acid, ethylene glycol, 2,6-naphthalenedicarboxylic acid, and trimellitic acid.

[0028] Preferably, in step S1, the solvent is selected from water, monohydric alcohols, polyhydric alcohols, ketones, ethers, halogenated hydrocarbons, amides, sulfoxides, nitriles, and pyridines.

[0029] More preferably, the monohydric alcohol compound is selected from at least one of methanol, ethanol, isopropanol, butanol, benzyl alcohol, and cycloethanol.

[0030] More preferably, the polyol compound is selected from at least one of ethylene glycol, propylene glycol, hexanediol, pentanediol, glycerol, 1,4-butanediol, and 1,2,4-butanetriol.

[0031] More preferably, the ketone compound includes acetone.

[0032] More preferably, the ether compound is selected from at least one of diethyl ether, tetrahydrofuran, and 1,4-dioxane.

[0033] More preferably, the halocarbon compound is selected from at least one of dichloromethane, chloroform, and tetrachloroethane.

[0034] More preferably, the amide compound includes N,N-dimethylformamide.

[0035] More preferably, the sulfoxide compound includes dimethyl sulfoxide.

[0036] More preferably, the nitrile compound includes acetonitrile.

[0037] More preferably, the pyridine compound includes pyridine.

[0038] More preferably, in step S1, the solvent is selected from at least one of water, N,N-dimethylformamide, ethanol, ethylene glycol, and isopropanol.

[0039] Furthermore, when the organic ligand is selected from polyol compounds, it simultaneously acts as both an organic ligand and a solvent.

[0040] Preferably, in step S1, the reaction temperature is 50~250 ℃, more preferably 80~180 ℃.

[0041] Preferably, in step S1, the reaction time is 3 to 60 h, more preferably 5 to 48 h.

[0042] Preferably, in step S1, the post-processing includes washing and drying.

[0043] Optionally, the washing process involves washing the cobalt-based metal-organic ligand precursor 2 to 5 times with at least one of methanol, ethanol, and acetone, specifically washing the cobalt-based metal-organic ligand precursor 3 times with ethanol.

[0044] Optionally, the drying process is carried out at 40-80°C for 8-16 hours, specifically at 60°C for 12 hours.

[0045] Optionally, in step S2, the fullerene can be obtained commercially.

[0046] Preferably, in step S2, the fullerene is selected from C 20+2k , where k is an integer ≥ 0.

[0047] More preferably, k is an integer of 20 ≤ k ≤ 32.

[0048] Optionally, in step S2, the fullerene is selected from C 60 C 70 C 76 C 80 C 84 At least one of them.

[0049] Preferably, in step S2, the modification specifically includes the following steps: The cobalt-based metal-organic ligand precursor material obtained in step S1 was placed in a solution containing fullerene and stirred to allow for full reaction. After post-treatment, fullerene-modified cobalt-based metal-organic ligand nanomaterials were obtained.

[0050] Preferably, in step S2, the solvent of the fullerene-containing solution is selected from aromatic solvents and / or non-aromatic solvents.

[0051] More preferably, the aromatic solvent is selected from at least one of benzene, toluene, m-xylene, chlorobenzene, and 1,2-dichlorobenzene.

[0052] More preferably, the non-aromatic solvent is selected from at least one of carbon disulfide and carbon tetrachloride.

[0053] Preferably, in the specific steps of the above modification, the temperature for the full reaction is 25~150 ℃, more preferably 50~115 ℃.

[0054] Preferably, in the specific steps of the above modification, the time for the full reaction is 4 to 150 hours, more preferably 6 to 120 hours.

[0055] Preferably, in the specific steps of the above modification, the concentration of the fullerene solution is 0.5~100 mmol / L, more preferably 1~60 mmol / L.

[0056] Preferably, in the specific steps of the above modification, the post-processing includes centrifugation and drying.

[0057] Optionally, in the specific steps of the above modification, the drying is performed at 40~80 ℃ for 8~16 h, specifically at 60 ℃ for 12 h.

[0058] Preferably, in step S3, the pyrolysis is carried out in an air atmosphere.

[0059] Preferably, in step S3, the pyrolysis temperature is 200~450 ℃.

[0060] Furthermore, in step S3, the heating rate of the pyrolysis is 1~20 ℃ / min, more preferably 2~10 ℃ / min.

[0061] Preferably, in step S3, the air flow rate of the air atmosphere is 1~200 mL / min, more preferably 5~70 mL / min.

[0062] The present invention also provides a fullerene-modified cobalt-based nanocomposite material prepared by the preparation method described above.

[0063] The present invention also provides the application of the fullerene-modified cobalt-based nanocomposite material in the preparation of electrode catalytic materials.

[0064] The present invention also provides an electrode catalytic material, comprising the fullerene-modified cobalt-based nanocomposite material.

[0065] Furthermore, the electrode catalytic material also includes a substrate, on which the fullerene-modified cobalt-based nanocomposite material is loaded.

[0066] Furthermore, the material of the substrate includes electrodes.

[0067] Furthermore, the electrode comprises a glassy carbon electrode.

[0068] As an alternative implementation, the fullerene-modified cobalt-based nanocomposite material is loaded onto a substrate by drop-addition or coating.

[0069] Further, as an optional implementation, the electrode catalytic material is prepared by the following steps: dispersing the fullerene-modified cobalt-based nanocomposite material in a solvent to obtain a dispersion; adding the obtained dispersion dropwise onto a substrate and drying it to obtain the electrode catalytic material.

[0070] Optionally, the dispersion is selected from at least one of perfluorosulfonic acid resin, ethanol, and water, specifically a mixed solution composed of perfluorosulfonic acid resin, ethanol, and water.

[0071] The present invention also provides the application of the fullerene-modified cobalt-based nanocomposite material or the electrode catalytic material in chlorination reaction and / or electrochlorination degradation.

[0072] Furthermore, the chlorine evolution reaction refers to the reaction of chloride ions (Cl-) during electrolysis. - The reaction in which the anode is oxidized to produce chlorine gas (Cl2).

[0073] Furthermore, the source of the chloride ions includes solutions containing chloride ions.

[0074] Furthermore, the chloride-containing solution includes at least one of sodium chloride solution, potassium chloride solution, and seawater.

[0075] Furthermore, electrochlorination degradation utilizes an electrochemical reaction. Through the electrolysis of a chloride-containing solution, a chlorine evolution reaction occurs at the anode to generate Cl2. Cl2 further generates highly active chlorine-based oxidants (such as Cl2, HClO, and ClO). - (etc.), thereby oxidizing and decomposing organic matter in the water (including but not limited to chlorinated organic matter).

[0076] Optionally, the organic matter is an organic pollutant; the organic pollutant includes organic matter containing halogen functional groups (CX, where X is any one of fluorine, chlorine, bromine, and iodine), organic matter containing hydroxyl functional groups (-OH), organic matter containing nitrogen functional groups, and organic matter containing unsaturated bonds.

[0077] Further optionally, the functional groups in the nitrogen-containing organic compound include nitro (-NO2), amino (-NH2), and amide (-CONH2).

[0078] Further optionally, the unsaturated bonds in the organic compound containing unsaturated bonds include carbon-carbon double bonds (C=C), carbon-carbon triple bonds (C≡C), carbon-nitrogen double bonds (C=N), and carbon-oxygen double bonds (C=O).

[0079] Specifically, the organic pollutant may optionally include at least one of 4-chlorophenol and 2,4,6-trichlorophenol.

[0080] The present invention has the following beneficial effects: This invention achieves a significant leap forward in the overall performance of catalysts through the innovative combination of fullerenes and cobalt-based materials. In the electrocatalytic chlorination reaction (CER), this material not only exhibits significantly superior catalytic activity and reaction selectivity compared to traditional cobalt-based materials and carbon black or graphene-modified cobalt-based materials, but also effectively inhibits corrosion and deactivation under strong oxidizing conditions, greatly extending its service life. This breakthrough successfully overcomes the shortcomings of traditional cobalt-based catalysts, such as insufficient activity, poor selectivity, and poor stability, providing a new solution for developing highly efficient and durable CER electrocatalytic materials. These materials can be used in the chlor-alkali industry and for the efficient electrochlorination treatment of recalcitrant organic pollutants in various water bodies, including groundwater, surface water, and industrial wastewater. Attached Figure Description

[0081] Figure 1 The Co3O4@C prepared in Example 1 80 SEM image of the nanocomposite material.

[0082] Figure 2 The CoCrO prepared in Example 2 x @C 70 SEM image of the nanocomposite material.

[0083] Figure 3 CoWO prepared in Example 3 x @C 84 SEM image of the nanocomposite material.

[0084] Figure 4 The CoZnTiO prepared in Example 4 x @C 60 SEM image of the nanocomposite material.

[0085] Figure 5 CoMnLaO prepared in Example 5 x @C 76 SEM image of the nanocomposite material.

[0086] Figure 6 CoCeSnO prepared in Example 6 x @C 70 SEM image of the nanocomposite material.

[0087] Figure 7 The LSV diagrams are of the electrocatalytic CERs of the nanomaterials obtained in Example 1 and Comparative Examples 1, 2, and 3.

[0088] Figure 8 The stability test results of the nanomaterials electrocatalyzing CER obtained in Example 1 and Comparative Examples 1, 2, and 3 are shown.

[0089] Figure 9The LSV diagrams show the electrocatalytic CERs of the nanomaterials obtained in Example 2 and Comparative Example 4.

[0090] Figure 10 The LSV diagrams are of the electrocatalytic CERs of the nanomaterials obtained in Example 3 and Comparative Example 5.

[0091] Figure 11 The LSV diagrams are for the electrocatalytic CER of the nanomaterials obtained in Example 4 and Comparative Example 6.

[0092] Figure 12 The LSV diagrams are for the electrocatalytic CER of the nanomaterials obtained in Example 5 and Comparative Example 7.

[0093] Figure 13 The LSV diagrams are for the electrocatalytic CER of the nanomaterials obtained in Example 6 and Comparative Example 8.

[0094] Figure 14 The graph shows the performance of the nanomaterials obtained in Example 5 and Comparative Example 7 in the electrochlorination degradation of 4-chlorophenol.

[0095] Figure 15 The graph shows the performance of the nanomaterials obtained in Example 6 and Comparative Example 8 in the electrochlorination degradation of 2,4,6-trichlorophenol. Detailed Implementation

[0096] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0097] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0098] The reagents used in this invention are sourced from the following sources: Fullerenes: Maclean, C 84 Item No. F708411; C 70 Item No. F699196; C 60 Product number F698216; C 76 Product number: F708409; Carbon black: Suzhou Shengernuo Technology Co., Ltd., item number 2026011501; Graphene: Aladdin, item number G477237.

[0099] Example 1 Co3O4@C 80 Nanocomposite materials The Co3O4@C 80 The preparation method of nanocomposite materials includes the following steps: (1) 1.746 g (6 mmol) of cobalt nitrate (Co(NO3)2) 0.475 g (2.4 mmol) of 2,5-dihydroxyterephthalic acid (DHTA) was dissolved in a well-mixed N,N-dimethylformamide-ethanol-water (volume ratio 1:1:1, total volume 60 mL). The mixture was stirred thoroughly on a stirrer for 1 h (stirrer speed 500 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 100 °C for 24 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt-hydroxyterephthalic acid precursor (Co-DHTA).

[0100] (2) Immerse the Co-DHTA precursor obtained in step (1) in a 1 mmol / L solution of carbon disulfide. 80 (CAS: 133947-15-6) The solution was stirred at 50 °C for 120 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. This solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain Co-DHTA@C. 80 Nanomaterials.

[0101] (3) Take the Co-DHTA@C obtained in step (2) 80 The nanocomposite powder was placed in a muffle furnace, and under an air atmosphere with an air flow rate controlled at 5 mL / min, the temperature was increased from room temperature to 350 °C at a heating rate of 5 °C / min. The mixture was then heat-treated at 350 °C for 1 h, followed by natural cooling to obtain Co3O4@C. 80 Nanocomposite materials.

[0102] Material characterization: The obtained Co3O4@C was examined using a scanning electron microscope (SEM). 80 The morphology of the nanocomposite material was characterized, and the results are as follows: Figure 1 As shown, the morphology of the obtained material is that of flower-shaped microspheres.

[0103] Example 2 CoCrO x @C 70 Nanocomposite materials The CoCrO x @C 70 (x is an integer in the range of 2 to 6, varying with the valence state of the metal, the same below) The preparation method of nanocomposite materials includes the following steps: (1) 4.982 g (20 mmol) of cobalt acetate (Co(CH3COO)2) 4H2O), 4.583 g (20 mmol) chromium acetate (Cr(CH3COO)3) and 1.538 g (16 mmol) 2,4 Dimethylimidazole (DMIM) was dissolved in 50 mL of ethanol and stirred thoroughly on a stirrer for 2 h (stirrer speed 500 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 80 °C for 48 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt chromium-methylimidazole precursor (CoCr-DMIM).

[0104] (2) Immerse the CoCr-DMIM precursor obtained in step (1) in 40 mmol / L HCl with chlorobenzene as solvent. 70 The solution was stirred at 115 °C for 6 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. This solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain CoCr-DMIM@C. 70 Nanomaterials.

[0105] (3) The CoCr-DMIM@C obtained in step (2) 70 The nanocomposite powder was placed in a muffle furnace, and under an air atmosphere with an air flow rate controlled at 15 mL / min, the temperature was increased from room temperature to 400 °C at a heating rate of 2 °C / min. The mixture was then heat-treated at 400 °C for 2 h, followed by natural cooling after the process to obtain CoCrO. x @C 70 Nanocomposite materials.

[0106] Material characterization: Scanning electron microscopy was used to study CoCrO x @C 70 The morphology of the nanocomposite material was characterized, and the results are as follows: Figure 2 As shown, the morphology of the obtained material is that of hollow porous microspheres.

[0107] Example 3 CoWO x @C 84 Nanocomposite materials The CoWO x @C 84 The preparation method of nanocomposite materials includes the following steps: (1) 4.663 g (19.6 mmol) cobalt chloride (CoCl2·6H2O), 0.159 g (0.4 mmol) tungsten chloride (WCl6) and 5.728 g (19.6 mmol) ethylenediaminetetraacetic acid (EDTA) were dissolved in 30 mL of ultrapure water and stirred thoroughly on a stirrer for 2 h (stirrer speed 600 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction. The reaction was carried out at 120 ℃ for 36 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 ℃ for 12 h to obtain the cobalt-tungsten-ethylenediaminetetraacetic acid precursor (CoW-EDTA).

[0108] (2) Immerse the CoW-EDTA precursor obtained in step (1) in a 10 mmol / L solution with toluene as the solvent. 84 The solution was stirred at 80 °C for 72 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. This solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain CoW-EDTA@C 84 Nanomaterials.

[0109] (3) Take the CoW-EDTA@C obtained in step (2) 84 The nanocomposite powder was placed in a muffle furnace, and under an air atmosphere with an air flow rate controlled at 30 mL / min, the temperature was increased from room temperature to 300 °C at a heating rate of 10 °C / min. The mixture was then heat-treated at 300 °C for 4 h, followed by natural cooling to obtain CoWO. x @C 84 Nanocomposite materials.

[0110] Material characterization: The obtained CoWO was analyzed using a scanning electron microscope. x @C 84 The morphology of the nanocomposite material was characterized, and the results are as follows: Figure 3 As shown, the morphology of the obtained material is that of nanosheets.

[0111] Example 4 CoZnTiO x @C 60 Nanocomposite materials The CoZnTiO x @C 60 The preparation method of nanocomposite materials includes the following steps: (1) 27.538 g (98 mmol) of cobalt sulfate (CoSO4) 7H2O), 0.240 g (1 mmol) titanium sulfate (Ti(SO4)2), 0.280 g (1 mmol) zinc sulfate (ZnSO4) Cobalt zinc titanium-ethylene glycol (CoZnTi-EG) was dissolved in 87.4 mL (1.568 mol) of ethylene glycol (EG) and stirred thoroughly on a stirrer for 3 h (stirrer speed 600 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 150 °C for 5 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt zinc titanium-ethylene glycol precursor (CoZnTi-EG).

[0112] (2) Immerse the CoZnTi-EG precursor obtained in step (1) in a 20 mmol / L solution with carbon tetrachloride as the solvent. 60 The solution was stirred at 60 °C for 48 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. This solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain CoZnTi-EG@C 60 Nanomaterials.

[0113] (3) Take the CoZnTi-EG@C obtained in step (2) 60 The nanocomposite powder was placed in a muffle furnace, and under an air atmosphere with an air flow rate controlled at 70 mL / min, the temperature was increased from room temperature to 250 °C at a heating rate of 3 °C / min. The mixture was then heat-treated at 250 °C for 2 h, followed by natural cooling after the process to obtain CoZnTiO2. x @C 60 Nanocomposite materials.

[0114] Material characterization: The obtained CoZnTiO was analyzed using a scanning electron microscope. x @C 60 The morphology of the nanocomposite material was characterized, and the results are as follows: Figure 4 As shown, the morphology of the obtained material is that of nanosheets composed of nanoparticles.

[0115] Example 5 CoMnLaO x @C 76 Nanocomposite materials The CoMnLaO x @C 76 The preparation method of nanocomposite materials includes the following steps: (1) 0.76 g (3.2 mmol) of cobalt chloride (CoCl2) 6H2O), 0.0792 g (0.4 mmol) manganese chloride (MnCl2) 4H2O), 0.149 g (0.4 mmol) lanthanum chloride LaCl3 7H2O and 1.384 g (6.4 mmol) of 2,6-naphthalenedicarboxylic acid (NDA) were dissolved in 30 mL of N,N-dimethylformamide and stirred thoroughly on a stirrer for 0.5 h (stirrer speed 600 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 180 °C for 8 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt manganese lanthanum-naphthalenedicarboxylic acid precursor (CoMnLa-NDA).

[0116] (2) Immerse the CoMnLa-NDA precursor obtained in step (1) in a 60 mmol / L solution with 1,2-dichlorobenzene as the solvent. 76 The solution was stirred at 100 °C for 24 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. This solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain CoMnLa-NDA@C. 76 Nanomaterials.

[0117] (3) Take the CoMnLa-NDA@C obtained in step (2) 76 The nanocomposite powder was placed in a muffle furnace and heated from room temperature to 450 °C at a rate of 2 °C / min under an air atmosphere with an air flow rate controlled at 30 mL / min. The mixture was then heat-treated at 450 °C for 1 h, followed by natural cooling to obtain CoMnLaO. x @C 76 Nanocomposite materials.

[0118] Material characterization: The obtained CoMnLaO was analyzed using scanning electron microscopy. x @C 76 The morphology of the nanocomposite material was characterized, and the results are as follows: Figure 5 As shown, the morphology of the obtained material is leaf-shaped.

[0119] Example 6 CoCeSnO x @C 70 Nanocomposite materials The CoCeSnO x @C 70 The preparation method of nanocomposite materials includes the following steps: (1) 0.0524 g (0.18 mmol) cobalt nitrate (Co(NO3)2·6H2O), 0.0087 g (0.02 mmol) cerium nitrate (Ce(NO3)3·6H2O), 0.007 g (0.02 mmol) tin chloride (SnCl4·5H2O) and 0.151 g (0.72 mmol) trimellitic acid (TMA) were dissolved in 15 mL of isopropanol and stirred thoroughly on a stirrer for 3 h (stirrer speed was 300 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction. The reaction was carried out at 120 ℃ for 10 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 ℃ for 12 h to obtain the cobalt-cerium-tin-triptyl phthalic acid precursor (CoCeSn-TMA).

[0120] (2) Immerse the CoCeSn-TMA precursor obtained in step (1) in a 20 mmol / L solution with benzene as the solvent. 70 The solution was stirred at 65 °C for 96 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. This solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain CoCeSn-TMA@C 70 Nanomaterials.

[0121] (3) Take the CoCeSn-TMA@C obtained in step (2) 70 The nanocomposite powder was placed in a muffle furnace and heated from room temperature to 200 °C at a rate of 8 °C / min under an air atmosphere with an air flow rate controlled at 10 mL / min. The mixture was then heat-treated at 200 °C for 6 h, followed by natural cooling to obtain CoCeSnO. x @C 70 Nanocomposite materials.

[0122] Material characterization: The obtained CoCeSnO was analyzed using a scanning electron microscope. x @C 70 The morphology of the nanocomposite material was characterized, and the results are as follows: Figure 6 As shown, the morphology of the obtained material is that of nanoparticles.

[0123] Comparative Example 1: Co3O4 Nanomaterials The preparation method of the Co3O4 nanomaterials differs from that in Example 1 in that the fullerene C process was not performed. 80 The modifications are the same as in Example 1, and the other steps are the same, specifically including the following steps: (1) 1.746 g (6 mmol) of cobalt nitrate (Co(NO3)2) 0.475 g (2.4 mmol) of 2,5-dihydroxyterephthalic acid (DHTA) was dissolved in a well-mixed N,N-dimethylformamide-ethanol-water (volume ratio 1:1:1, 60 mL) solvent. The mixture was stirred thoroughly on a stirrer for 1 h (stirrer speed 500 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 100 °C for 24 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt-hydroxyterephthalic acid precursor (Co-DHTA).

[0124] (2) Place the Co-DHTA precursor powder obtained in step (1) in a muffle furnace. Under an air atmosphere, the air flow rate is controlled at 5 mL / min. The temperature is increased from room temperature to 350 ℃ at a heating rate of 5 ℃ / min. Heat treatment is carried out at 350 ℃ for 1 h. After the program is completed, the material is naturally cooled to obtain Co3O4 nanomaterial.

[0125] Comparative Example 2: Co3O4@Carbon black nanomaterials The preparation method of the Co3O4@Carbon black nanomaterial differs from that in Example 1 in that fullerene C is used. 80 The modification was replaced with an equal mass of carbon black, and the other steps were the same as in Example 1, specifically including the following steps: (1) 1.746 g (6 mmol) of cobalt nitrate (Co(NO3)2) 0.475 g (2.4 mmol) of 2,5-dihydroxyterephthalic acid (DHTA) was dissolved in a well-mixed N,N-dimethylformamide-ethanol-water (volume ratio 1:1:1, total volume 60 mL). The mixture was stirred thoroughly on a stirrer for 1 h (stirrer speed 500 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 100 °C for 24 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt-hydroxyterephthalic acid precursor (Co-DHTA).

[0126] (2) Immerse the Co-DHTA precursor obtained in step (1) in a 0.96 g / L carbon black solution with carbon disulfide as the solvent (the mass concentration of carbon black in this solution is the same as that in the carbon disulfide solution in step S3 of Example 1). 80(The mass concentrations were equal), stirred at 50℃ for 120 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. The solid product was then dried in a forced-air drying oven at 60 ℃ for 12 h to obtain Co-DHTA@Carbon black nanomaterials.

[0127] (3) Place the Co-DHTA@Carbon black nanocomposite powder obtained in step (2) in a muffle furnace. Under an air atmosphere, the air flow rate is controlled at 5 mL / min. The temperature is increased from room temperature to 350 ℃ at a heating rate of 5 ℃ / min. Heat treatment is carried out at 350 ℃ for 1 h. After the program is completed, it is naturally cooled to obtain Co3O4@Carbon black nanocomposite.

[0128] Comparative Example 3: Co3O4@Graphene Nanomaterials The preparation method of the Co3O4@Graphene nanomaterial differs from that in Example 1 in that the fullerene C is used. 80 The modification was replaced with an equal mass of graphene modification, and the other steps were the same as in Example 1, specifically including the following steps: (1) 1.746 g (6 mmol) of cobalt nitrate (Co(NO3)2) 0.475 g (2.4 mmol) of 2,5-dihydroxyterephthalic acid (DHTA) was dissolved in a well-mixed N,N-dimethylformamide-ethanol-water (volume ratio 1:1:1, total volume 60 mL). The mixture was stirred thoroughly on a stirrer for 1 h (stirrer speed 500 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 100 °C for 24 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt-hydroxyterephthalic acid precursor (Co-DHTA).

[0129] (2) Immerse the Co-DHTA precursor obtained in step (1) in a 0.96 g / L graphene solution using carbon disulfide as the solvent (the mass concentration of graphene in this solution is the same as that in the carbon disulfide solution in step S3 of Example 1). 80 (The mass concentrations were equal), stirred at 50 °C for 120 h, then centrifuged, the supernatant was discarded, and the solid product was obtained. The solid product was then dried in a forced-air drying oven at 60 °C for 12 h to obtain Co-DHTA@Graphene nanomaterials.

[0130] (3) Place the Co-DHTA@Graphene nanocomposite powder obtained in step (2) in a muffle furnace. Under an air atmosphere, the air flow rate is controlled at 5 mL / min. The temperature is increased from room temperature to 350 ℃ at a heating rate of 5 ℃ / min. Heat treatment is carried out at 350 ℃ for 1 h. After the program is completed, it is naturally cooled to obtain Co3O4@Graphene nanocomposite.

[0131] Comparative Example 4 CoCrO x Nanomaterials The CoCrO x The preparation method of the nanomaterials differs from that in Example 2 in that the fullerene C process was not performed. 70 The modifications are the same as in Example 2, and the other steps are the same, specifically including the following steps: (1) 4.982 g (20 mmol) of cobalt acetate (Co(CH3COO)2) 4H2O), 4.583 g (20 mmol) chromium acetate (Cr(CH3COO)3) and 1.538 g (16 mmol) 2,4 Dimethylimidazole (DMIM) was dissolved in 50 mL of ethanol and stirred thoroughly on a stirrer for 2 h (stirrer speed 500 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 80 °C for 48 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt chromium-methylimidazole precursor (CoCr-DMIM).

[0132] (2) The CoCr-DMIM precursor obtained in step (1) was placed in a muffle furnace. Under an air atmosphere, the air flow rate was controlled at 15 mL / min, and the temperature was increased from room temperature to 400 ℃ at a heating rate of 2 ℃ / min. The temperature was then subjected to heat treatment at 400 ℃ for 2 h. After the process was completed, the mixture was allowed to cool naturally to obtain CoCrO. x Nanomaterials.

[0133] Comparative Example 5 CoWO x Nanomaterials The CoWO x The preparation method of the nanomaterials differs from that in Example 3 in that the fullerene C process was not performed. 84 The modifications are the same as in Example 3, and the other steps are the same, specifically including the following steps: (1) 4.663 g (19.6 mmol) cobalt chloride (CoCl2·6H2O), 0.159 g (0.4 mmol) tungsten chloride (WCl6) and 5.728 g (19.6 mmol) ethylenediaminetetraacetic acid (EDTA) were dissolved in 30 mL of ultrapure water and stirred thoroughly on a stirrer for 2 h (stirrer speed 600 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction. The reaction was carried out at 120 ℃ for 36 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 ℃ for 12 h to obtain the cobalt-tungsten-ethylenediaminetetraacetic acid precursor (CoW-EDTA).

[0134] (2) The CoW-EDTA precursor obtained in step S1 was placed in a muffle furnace. Under an air atmosphere, the air flow rate was controlled at 30 mL / min, and the temperature was increased from room temperature to 300 ℃ at a heating rate of 10 ℃ / min. The temperature was then subjected to heat treatment at 300 ℃ for 4 h. After the process was completed, the mixture was allowed to cool naturally to obtain CoWO. x Nanomaterials.

[0135] Comparative Example 6: CoZnTiO x Nanomaterials The CoZnTiO x The preparation method of the nanomaterials differs from that in Example 4 in that the fullerene C process was not performed. 60 The modifications are the same as in Example 4, and the other steps are the same, specifically including the following steps: (1) 27.538 g (98 mmol) of cobalt sulfate (CoSO4) 7H2O), 0.240 g (1 mmol) titanium sulfate (Ti(SO4)2), 0.280 g (1 mmol) zinc sulfate (ZnSO4) Cobalt zinc titanium-ethylene glycol (CoZnTi-EG) was dissolved in 87.4 mL (1.568 mol) of ethylene glycol (EG) and stirred thoroughly on a stirrer for 3 h (stirrer speed 600 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 150 °C for 5 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt zinc titanium-ethylene glycol precursor (CoZnTi-EG).

[0136] (2) The CoZnTi-EG precursor obtained in step (1) was placed in a muffle furnace. Under an air atmosphere, the air flow rate was controlled at 70 mL / min, and the temperature was increased from room temperature to 250 ℃ at a heating rate of 3 ℃ / min. The temperature was then subjected to heat treatment at 250 ℃ for 2 h. After the process was completed, the temperature was allowed to cool naturally to obtain CoZnTiO. x Nanomaterials.

[0137] Comparative Example 7 CoMnLaO x Nanomaterials The CoMnLaO x The preparation method of the nanomaterials differs from that in Example 5 in that the fullerene C process was not performed. 76 The modifications are the same as in Example 5, and the other steps are the same, specifically including the following steps: (1) 0.76 g (3.2 mmol) of cobalt chloride (CoCl2) 6H2O), 0.0792 g (0.4 mmol) manganese chloride (MnCl2) 4H2O), 0.149 g (0.4 mmol) LaCl3 7H2O and 1.384 g (6.4 mmol) of 2,6-naphthalenedicarboxylic acid (NDA) were dissolved in 30 mL of N,N-dimethylformamide and stirred thoroughly on a stirrer for 0.5 h (stirrer speed 600 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction at 180 °C for 8 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt manganese lanthanum-naphthalenedicarboxylic acid precursor (CoMnLa-NDA).

[0138] (2) The CoMnLa-NDA precursor obtained in step (1) was placed in a muffle furnace. Under an air atmosphere, the air flow rate was controlled at 30 mL / min, and the temperature was increased from room temperature to 450 ℃ at a heating rate of 2 ℃ / min. The temperature was then subjected to heat treatment at 450 ℃ for 1 h. After the process was completed, the product was allowed to cool naturally to obtain CoMnLaO. x Nanomaterials.

[0139] Comparative Example 8 CoCeSnO x Nanomaterials The CoCeSnO x The preparation method of the nanomaterials differs from that in Example 6 in that the fullerene C process was not performed. 70 The modifications are the same as in Example 6, and the other steps are the same, specifically including the following steps: (1) 0.0524 g (0.18 mmol) cobalt nitrate (Co(NO3)2·6H2O), 0.0087 g (0.02 mmol) cerium nitrate (Ce(NO3)3·6H2O), 0.007 g (0.02 mmol) tin chloride (SnCl4·5H2O) and 0.151 g (0.72 mmol) trimellitic acid (TMA) were dissolved in 15 mL of isopropanol and stirred thoroughly on a stirrer for 3 h (stirrer speed was 300 rpm) to obtain a mixed solution. The solution was then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a forced-air drying oven for coordination complexation reaction. The reaction was carried out at 120 °C for 10 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the cobalt-cerium-tin-triptyl phthalic acid precursor (CoCeSn-TMA).

[0140] (2) The CoCeSn-TMA precursor obtained in step (1) was placed in a muffle furnace. Under an air atmosphere, the air flow rate was controlled at 10 mL / min, and the temperature was increased from room temperature to 200 ℃ at a heating rate of 8 ℃ / min. The temperature was then subjected to heat treatment at 200 ℃ for 6 h. After the process was completed, the mixture was allowed to cool naturally to obtain CoCeSnO. x Nanomaterials.

[0141] Application Example 1: Performance Testing of the Electrocatalytic Chlorine Evolution Reaction (CER) Electrochemical tests were performed using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. The performance indicators for the electrocatalytic material were: voltage (E) required to achieve the current density, Cl2 selectivity, and stability.

[0142] Using a catalyst-modified glassy carbon electrode (3 mm in diameter) as the working electrode and a Pt sheet (2 × 2 cm) as the working electrode... 2 The electrode used is a counter electrode, and a saturated calomel electrode (SCE, immersed in a saturated KCl solution) is used as the reference electrode. 1 M NaCl is the chlorine evolution electrolyte, and 1 M Na₂SO₄ is the neutral oxygen evolution electrolyte. According to formula E... (RHE) =E (SCE) +0.244+0.0591 x pH, the potential value E (RHE) By E (SCE)The working electrode was prepared as follows: 3 mg of fullerene or the solid catalyst obtained in the examples or comparative examples was dispersed in a mixed solution of 240 μL water, 240 μL ethanol, and 20 μL 5 wt% perfluorosulfonic acid resin (Nafion). The mixture was then sonicated for approximately 30 min to obtain a homogeneous catalyst dispersion. Subsequently, 3 μL of the catalyst dispersion was dropwise added to a glassy carbon electrode, and the electrode was dried overnight at room temperature. Before each electrochemical data acquisition, the solution resistance (R0) of all materials was measured at the open-circuit potential. s The catalyst was activated by multiple CV scans within the voltage range of 0.5–1.8 V vs. SCE. After the CV scan results stabilized, the LSV curve was tested at 0.5–1.8 V vs. SCE, and 95% IR compensation was applied to the LSV curve. Furthermore, the CER performance of the material was tested over a certain period using chronopotentiometric (CP) method, and the product was quantitatively analyzed by ultraviolet-visual spectrophotometry (UV-vis). The specific test procedure was as follows: After the CP test, 1 mL of the reaction solution was pipetted into 9 mL of deionized water for dilution. 0.5 mL of buffer solution and 0.5 mL of N,N-diethyl-p-phenylenediamine oxalate (DPD) were added to the solution. After standing at room temperature for 20 s, the solution was tested using a UV-visual spectrophotometer. The characteristic peak was located at 510 nm. The Cl2 content in the solution was obtained by comparing with the prepared NaClO standard curve, and the Cl2 selectivity was calculated. Finally, the CP was recorded at a constant current (50 mA / cm²). 2 The stability of electrocatalytic materials is evaluated by the change of voltage over time.

[0143] This application example relates to Example 1 (Co3O4@C 80 The CER performance of Comparative Example 1 (Co3O4), Comparative Example 2 (Co3O4@Carbonblack), and Comparative Example 3 (Co3O4@Graphene) was tested. LSV results are available in [link to LSV results]. Figure 7 And at 50 mA / cm 2 A CP test was performed for 180 s. After sampling, the Cl2 concentration was obtained by UV-vis analysis, and the Cl2 selectivity was calculated. Finally, at 50 mA / cm²... 2 The stability of the electrocatalytic material was evaluated using CP testing, and the results are shown below. Figure 8 .Depend on Figure 7 It is evident that, regarding CER performance, Co3O4@C 80 With C 80 Compared to Co3O4, Co3O4@Carbon black, and Co3O4@Graphene, it achieves the same current density of 50 mA / cm². 2 Voltage (E)50 is smaller, E 50 vs. RHE are Co3O4@C 80 (1.779 V) < Co3O4@Graphene (1.805 V) < Co3O4@Carbon black (1.820 V) < Co3O4 (1.841 V), while C 80 has no catalytic activity, indicating that the nanocomposite prepared in the embodiment of the present invention has better CER performance. To further prove the high selectivity of the Co3O4@C 80 material for CER, it was placed in a 1 M Na2SO4 electrolyte without Cl - for testing. As Figure 7 shown, its response current is negligible, indicating that the material hardly undergoes OER within the test potential range. After introducing 1 M NaCl, its current density increases significantly. This comparison result proves that Co3O4@C 80 has excellent CER selectivity and can effectively inhibit the competitive OER side reaction.

[0144] According to UV-vis test, at a current density of 50 mA / cm², the Cl2 selectivity of Example 1 (Co3O4@C 80 ) is as high as 98%, significantly better than that of Comparative Example 1 (Co3O4, 80%), Comparative Example 2 (Co3O4@Carbon black, 87%) and Comparative Example 3 (Co3O4@Graphene, 89%). In addition, under the constant current condition of 50 mA / cm 2 the long-term stability test shows that (the results are shown in Figure 8 ) the performance of Example 1 (Co3O4@C 80 ) can be stably maintained for at least 80 hours, while the stable times of Comparative Example 1 (Co3O4), Comparative Example 2 (Co3O4@Carbon black) and Comparative Example 3 (Co3O4@Graphene) are 20 hours, 40 hours and 50 hours respectively. Thus, the stability of Example 1 is significantly better than all the above comparative examples. The above experimental results show that compared with Co3O4 unmodified or modified with other carbon nanomaterials, the Co3O4@C 80 nanocomposite prepared by modifying with fullerene C 80 not only exhibits better activity, higher Cl2 selectivity in CER, but also exhibits longer catalytic stability.

[0145] Performance test of electrocatalytic chlorine evolution reaction (CER) in Application Example 2 This application example tests the performance of Example 2 (CoCrO x @C 70) and Comparative Example 4 (CoCrO) x The CER performance of the ) was tested, and the LSV results are shown in [link to LSV test]. Figure 9 And at 50 mA / cm 2 A CP test was performed for 180 s. After sampling, the concentration of Cl2 was obtained by UV-vis and the selectivity of Cl2 was calculated. The specific test conditions are the same as in Application Example 1.

[0146] Reference Figure 9 It can be seen that, for CER performance, CoCrO x @C 70 With CoCrO x In comparison, to achieve the same current density of 50 mA / cm 2 Voltage (E) 50 Smaller, E 50 vs. RHE are CoCrO x @C 70 (1.786 V) <CoCrO x (1.814 V). According to UV-vis testing, at a current density of 50 mA / cm², CoCrO x @C 70 The Cl2 selectivity is as high as 97%, which is significantly better than CoCrO. x (82%). Based on the above performance results, it can be seen that the material obtained in Example 2 (CoCrO) x @C 70 The CER performance of the material obtained in Example 4 (CoCrO) is superior to that of the material obtained in Comparative Example 4. x ).

[0147] Application Example 3: Performance Testing of the Electrocatalytic Chlorine Evolution Reaction (CER) This application example is for Example 3 (CoWO) x @C 84 ) and Comparative Example 5 (CoWO x The CER performance of the ) was tested, and the LSV results are shown in [link to LSV test]. Figure 10 And at 50 mA / cm 2 A CP test was performed for 180 s. After sampling, the concentration of Cl2 was obtained by UV-vis and the selectivity of Cl2 was calculated. The specific test conditions are the same as in Application Example 1.

[0148] Reference Figure 10 It can be seen that, regarding CER performance, CoWO x @C 84 With CoWO x In comparison, to achieve the same current density of 50 mA / cm 2 Voltage (E) 50 Smaller, E 50vs. RHE are CoWO x @C 84 (1.798 V) <CoWO x (1.837 V). According to UV-vis testing, at a current density of 50 mA / cm², CoWO x @C 84 The Cl2 selectivity is as high as 95%, which is significantly better than CoWO. x (78%). Based on the above performance results, it can be seen that the material obtained in Example 3 (CoWO) x @C 84 The CER performance of the material obtained in Example 5 is superior to that of the material obtained in Comparative Example 5 (CoWO). x ).

[0149] Application Example 4: Performance Testing of the Electrocatalytic Chlorine Evolution Reaction (CER) This application example applies to Example 4 (CoZnTiO) x @C 60 ) and Comparative Example 6 (CoZnTiO) x The CER performance of the ) was tested, and the LSV results are shown in [link to LSV test]. Figure 11 And at 50 mA / cm 2 A CP test was performed for 180 s. After sampling, the concentration of Cl2 was obtained by UV-vis and the selectivity of Cl2 was calculated. The specific test conditions are the same as in Application Example 1.

[0150] Reference Figure 11 It can be seen that, for CER performance, CoZnTiO x @C 60 With CoZnTiO x In comparison, to achieve the same current density of 50 mA / cm 2 Voltage (E) 50 Smaller, E 50 vs. RHE are CoZnTiO x @C 60 (1.792 V) <CoZnTiO x (1.843V). According to UV-vis testing, at a current density of 50 mA / cm², CoZnTiO x @C 60 The Cl2 selectivity is as high as 96%, which is significantly better than CoZnTiO. x (81%). Based on the above performance results, it can be seen that the material obtained in Example 4 (CoZnTiO) x @C 60 The CER performance of the material obtained in Example 6 (CoZnTiO) is superior to that of the material obtained in Comparative Example 6. x ).

[0151] Application Example 5: Performance Testing of Electrocatalytic Chlorine Evolution (CER) This application example applies to Example 5 (CoMnLaO) x @C 76 ) and Comparative Example 7 (CoMnLaO x The CER performance of the ) was tested, and the LSV results are shown in [link to LSV test]. Figure 12 And at 50 mA / cm 2 A CP test was performed for 180 s. After sampling, the concentration of Cl2 was obtained by UV-vis and the selectivity of Cl2 was calculated. The specific test conditions are the same as in Application Example 1.

[0152] Reference Figure 12 It can be seen that, for CER performance, CoMnLaO x @C 76 With CoMnLaO x In comparison, to achieve the same current density of 50 mA / cm 2 Voltage (E) 50 Smaller, E 50 vs. RHE are CoMnLaO x @C 76 (1.785 V) <CoMnLaO x (1.811V). According to UV-vis testing, at a current density of 50 mA / cm², CoMnLaO x @C 76 The Cl2 selectivity is as high as 97%, which is significantly better than CoMnLaO. x (86%). Based on the above performance results, it can be seen that the material obtained in Example 5 (CoMnLaO) x @C 76 The CER performance of the material obtained in Example 7 (CoMnLaO) is superior to that of the material obtained in Comparative Example 7. x ).

[0153] Application Example 6: Performance Testing of the Electrocatalytic Chlorine Evolution Reaction (CER) This application example applies to Example 6 (CoCeSnO) x @C 70 ) and Comparative Example 8 (CoCeSnO) x The CER performance of the ) was tested, and the LSV results are shown in [link to LSV test]. Figure 13 And at 50 mA / cm 2 A CP test was performed for 180 s. After sampling, the concentration of Cl2 was obtained by UV-vis and the selectivity of Cl2 was calculated. For specific test results, refer to Application Example 1.

[0154] Reference Figure 13 It can be seen that, for CER performance, CoCeSnOx @C 70 With CoCeSnO x In comparison, to achieve the same current density of 50 mA / cm 2 Voltage (E) 50 Smaller, E 50 vs. RHE are CoCeSnO x @C 70 (1.789 V) <CoCeSnO x (1.821V). According to UV-vis testing, at a current density of 50 mA / cm², CoCeSnO x @C 70 The Cl2 selectivity is as high as 97%, which is significantly better than CoCeSnO. x (84%). Based on the above performance results, it can be seen that the material obtained in Example 6 (CoCeSnO) x @C 70 The CER performance of the material obtained in Example 8 (CoCeSnO) is superior to that of the material obtained in Comparative Example 8. x ).

[0155] Application Example 7: Performance Test of Electrochlorination Degradation of 4-Chlorophenol Using 4-chlorophenol as a substrate, this application example applies to Example 5 (CoMnLaO) x @C 76 ) and Comparative Example 7 (CoMnLaO x The performance of the electrochlorination process for degrading 4-chlorophenol with active chlorine was tested. The initial concentration of 4-chlorophenol in the system was 50 mg / L. The specific steps are as follows: Using a catalyst-modified glassy carbon electrode (3 mm in diameter) as the working electrode, a Pt sheet (2 × 2 cm) was used. 2 The electrode used is a counter electrode, and a saturated calomel electrode (SCE, immersed in saturated KCl solution) is used as the reference electrode. The electrolyte contains 50 mg / L 4-chlorophenol and 1 M NaCl. An application rate of 20 mA / cm² is applied. 2 The reaction was started with a constant current. At regular intervals, 1 mL of the reaction suspension was taken, and 1 mL of methanol was immediately added to quench the active chlorine and terminate the reaction. The solution was then filtered through a 0.22 μm filter before analysis. The concentration of 4-chlorophenol in the solution was analyzed by high-performance liquid chromatography (HPLC).

[0156] Reference Figure 14 It can be seen that CoMnLaO x @C 76 A 99% degradation rate of 4-chlorophenol was achieved within 45 minutes, significantly superior to CoMnLaO. x (60% within 1 hour). Based on the above performance results, it can be seen that the material obtained in Example 5 (CoMnLaO)x @C 76 The electrochlorination of active chlorine to degrade 4-chlorophenol exhibits better performance than the material obtained in Comparative Example 7 (CoMnLaO). x ) Application Example 8: Performance Test of Electrochlorination Degradation of 2,4,6-Trichlorophenol Using 2,4,6-trichlorophenol as a substrate, this application example applies to Example 6 (CoCeSnO) x @C 70 ) and Comparative Example 8 (CoCeSnO) x The performance of the electrochlorination process for degrading 2,4,6-trichlorophenol using active chlorine was tested. The initial concentration of 2,4,6-trichlorophenol in the system was 50 mg / L. The specific steps are as follows: Using a catalyst-modified glassy carbon electrode (3 mm in diameter) as the working electrode, a Pt sheet (2 × 2 cm) was used. 2 The electrode used is a counter electrode, and a saturated calomel electrode (SCE, immersed in saturated KCl solution) is used as the reference electrode. The electrolyte contains 50 mg / L 2,4,6-trichlorophenol and 1 M NaCl. An application rate of 20 mA / cm² is applied. 2 The reaction was started with a constant current. At regular intervals, 1 mL of the reaction suspension was taken, and 1 mL of methanol was immediately added to quench the active chlorine and terminate the reaction. The solution was then filtered through a 0.22 μm filter before analysis. The concentration of 2,4,6-trichlorophenol in the solution was analyzed by high-performance liquid chromatography (HPLC).

[0157] Reference Figure 15 It can be seen that CoCeSnO x @C 70 A 98% degradation rate of 2,4,6-trichlorophenol was achieved within 1 hour, significantly superior to CoCeSnO. x (45% within 1 hour). Based on the above performance results, it can be seen that the material obtained in Example 6 (CoCeSnO) x @C 70 The electrochlorination of active chlorine to degrade 2,4,6-trichlorophenol showed better performance than the material obtained in Comparative Example 8 (CoCeSnO). x ).

[0158] In summary, this invention, through the combination of fullerenes and cobalt-based materials, prepares a fullerene-modified cobalt-based nanocomposite material. This material not only significantly enhances the catalytic activity and reaction selectivity of CER (Conversion of Chlorine) but also effectively suppresses corrosion deactivation under strong oxidizing environments. Compared to traditional cobalt-based materials, its catalytic performance and stability are significantly improved, even surpassing those of cobalt-based materials modified with similar carbon nanomaterials (carbon black, graphene). This groundbreaking discovery provides a novel solution to address the inherent defects of cobalt-based catalysts, demonstrating significant application prospects in highly corrosive electrochemical reactions such as CER. It is suitable for the efficient electrochlorination treatment of recalcitrant organic pollutants in various water bodies, including groundwater, surface water, and industrial wastewater.

[0159] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a fullerene-modified cobalt-based nanocomposite material, characterized in that, Includes the following steps: S1: Mix the metal salt and organic ligand in a solvent, react thoroughly, and then perform post-treatment to obtain a cobalt-based metal-organic ligand precursor. S2: The cobalt-based metal-organic ligand precursor obtained in S1 is modified with fullerene to obtain fullerene-modified cobalt-based metal-organic ligand nanomaterials. S3: The fullerene-modified cobalt-based metal-organic ligand nanomaterials obtained in S2 are pyrolyzed at 200~500 °C to obtain the fullerene-modified cobalt-based nanocomposite material. In step S1, the metal component in the metal salt includes at least cobalt.

2. The method as described in claim 1, characterized in that, The fullerene is selected from C 20+2k , where k is an integer ≥ 0.

3. The method as described in claim 2, characterized in that, k is an integer where 20 ≤ k ≤ 32.

4. The method as described in claim 1, characterized in that, In step S2, the modification specifically includes the following steps: The cobalt-based metal-organic ligand precursor material obtained in step S1 was placed in a solution containing fullerene and stirred to allow for full reaction. After post-treatment, fullerene-modified cobalt-based metal-organic ligand nanomaterials were obtained.

5. The method as described in claim 1, characterized in that, The metal component in the metal salt also includes a doped metal, which is selected from at least one of nickel, iron, manganese, copper, zinc, tungsten, chromium, molybdenum, lanthanum, cerium, europium, indium, gallium, titanium, tin, and bismuth.

6. The method as described in claim 1, characterized in that, The organic ligand is selected from at least one of carboxylic acid compounds, alcohol compounds, and imidazole compounds.

7. The fullerene-modified cobalt-based nanocomposite material prepared by the preparation method according to any one of claims 1 to 6.

8. The application of the fullerene-modified cobalt-based nanocomposite material according to claim 7 in the preparation of electrode catalytic materials.

9. An electrode catalytic material, characterized in that, Including the fullerene-modified cobalt-based nanocomposite material as described in claim 7.

10. The application of the fullerene-modified cobalt-based nanocomposite material of claim 7 or the electrode catalytic material of claim 9 in chlorination reaction and / or electrochlorination degradation.

Images