Fullerene-modified transition metal hydroxide nanomaterial array and preparation method and application thereof

Abstract

The application belongs to the technical field of organic electro-oxidation electrode materials, and particularly relates to a fullerene-modified transition metal hydroxide nano-array material and a preparation method and application thereof. The application utilizes a solvent thermal reaction to in-situ grow the transition metal hydroxide nano-array on a current collector, then realizes surface amino modification by means of grafting of a silane coupling agent with amino groups, and finally obtains the surface fullerene-modified transition metal hydroxide nano-array material through an addition reaction of amino groups and a carbon-carbon double bond of fullerene. The strong electron-withdrawing capacity of fullerene is conducive to optimizing the surface electronic structure of the material, thereby improving the intrinsic catalytic activity. Meanwhile, fullerene can also promote the adsorption and enrichment of organic substrates on the surface of the material through conjugated π bonds and hydrophobic interactions, thereby improving the mass transfer efficiency. Benefiting from the above-mentioned improvement mechanisms, the obtained nano-array material has the advantages of high electro-catalytic activity and fast mass transfer efficiency, and can be widely applied to a series of organic electro-oxidation reactions.

Description

Technical Field

[0001] This invention relates to the field of organic electro-oxidation electrode materials. More specifically, it relates to a fullerene-modified transition metal hydroxide nanoarray material, its preparation method, and its applications. Background Technology

[0002] Against the backdrop of increasingly severe energy crises and environmental problems, and the imperative to achieve the "dual carbon" target, the development of efficient, economical, safe, and sustainable synthetic methods is becoming increasingly important for research in the field of organic synthesis. Organic electro-oxidation utilizes "greener" electrons to replace traditional chemical oxidants, converting organic substrates such as alcohols, aldehydes, ketones, and amines into high-value-added organic products through electro-oxidation. This overcomes the shortcomings of traditional organic chemical processes, such as severe environmental pollution, low product purity, and harsh reaction conditions, and has excellent development potential and application prospects. In the field of organic electro-oxidation, noble metal-based catalysts (such as Pt, Pd, Au, etc.) have attracted much attention due to their superior catalytic performance. For example, Si et al. prepared a PdAg alloy (PdAg / NF) material grown on nickel foam and used it for the electrocatalytic oxidation of ethylene glycol to prepare glycolic acid in a coupled hydrogen evolution process, while efficiently obtaining glycolic acid and high-purity hydrogen (Di Si, Bingyan Xiong, Lisong Chen, Jianlin Shi. Highly selective and efficient electrocatalytic synthesis of glycolic acid incoupling with hydrogen evolution[J]. Chem Catalysis, 2021.). Although it has a high Faraday efficiency, the high cost and scarcity of the noble metals used limit its large-scale application in actual production. Therefore, developing highly active, stable, and low-cost organic electro-oxidation catalysts based on abundant non-noble metal elements has important application value.

[0003] Currently, transition metal-based catalysts such as Co and Ni are widely used in the field of organic electro-oxidation, but the performance of most of these materials still cannot compare with that of noble metal-based materials. The main limiting factors are insufficient catalytic activity due to unfavorable electronic structures and slow mass transfer kinetics caused by the low diffusion coefficient of organic substrates in electrolyte solutions. Therefore, developing transition metal-based catalytic materials with high catalytic activity and fast mass transfer efficiency based on design strategies that regulate the electronic structure of materials and improve mass transfer efficiency will be beneficial for the further promotion of organic electro-oxidation technology. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the existing non-precious metal-based organic electro-oxidation materials, such as poor catalytic activity and low mass transfer efficiency, and to provide a fullerene-modified transition metal hydroxide nanoarray material with good catalytic activity and excellent mass transfer efficiency.

[0005] The purpose of this invention is to provide a method for preparing fullerene-modified transition metal hydroxide nanoarray materials.

[0006] Another object of the present invention is to provide the application of the fullerene-modified transition metal hydroxide nanoarray material in organic electro-oxidation reactions.

[0007] The above-mentioned objective of this invention is achieved through the following technical solution:

[0008] This invention provides a method for preparing fullerene-modified transition metal hydroxide nanoarray materials, comprising the following steps:

[0009] S1. Preparation of transition metal hydroxide nanoarrays;

[0010] S2. The transition metal hydroxide nanoarray obtained in step S1 is placed in a silane coupling agent solution containing amino groups for grafting modification and post-treatment to obtain a transition metal hydroxide nanoarray material with amino-modified surface.

[0011] S3. The amino-modified transition metal hydroxide nanoarray material obtained in step S2 is placed in a solvent containing fullerene for fullerene modification and post-treatment to obtain fullerene-modified transition metal hydroxide nanoarray material.

[0012] This invention achieves surface amino modification by grafting a transition metal hydroxide nanoarray with an amino-containing silane coupling agent, and further obtains a surface fullerene-modified transition metal hydroxide nanoarray material through the addition reaction of amino and fullerene carbon-carbon double bonds.

[0013] The fullerene-modified transition metal hydroxide nanoarray material of this invention exhibits good catalytic activity and excellent mass transfer efficiency. On the one hand, the fullerenes modified on the surface of the nanoarray material have strong electron-withdrawing capabilities, which helps to optimize the electronic structure of the material surface and thus improve catalytic activity; on the other hand, fullerenes can promote the adsorption and enrichment of organic substrates on the surface of the catalytic material through conjugated π bonds and hydrophobic interactions, thereby improving mass transfer efficiency.

[0014] The preparation method described in this invention is economical, fast, and can be mass-produced, which will help promote the application of the obtained nanoarray materials in the field of organic electro-oxidation.

[0015] Preferably, in step S1, the specific steps for preparing the transition metal hydroxide nanoarray are as follows: placing the current collector in a mixed solution containing transition metal salt and precipitant, performing a solvothermal reaction, and then performing post-treatment to obtain the transition metal hydroxide nanoarray.

[0016] In this invention, a current collector is placed in a mixed solution containing a transition metal salt and a precipitant, and after mixing, a solvothermal reaction is carried out to obtain a transition metal hydroxide nanoarray grown in situ on the current collector.

[0017] Preferably, in steps S1 to S3, the post-processing is washing and drying.

[0018] Preferably, in step S1, the transition metal in the transition metal salt is selected from at least one of Ni, Fe, Co, Cu, Zn, Mn, Mo, V, Ce, W, Ti, Zr, Cr, Sc, and Y. Ni, Fe, Co, Cu, Zn, and Mn are common transition metals with catalytic activity in the field of organic electro-oxidation, while Mo, V, Ce, W, Ti, Zr, Cr, Sc, and Y are some conventional dopants. Appropriate doping is beneficial to improving the activity of the catalytic material.

[0019] More preferably, in step S1, the transition metal in the transition metal salt is a primary transition metal, or a primary transition metal and a doped transition metal; the primary transition metal is selected from at least one of Ni, Fe, Co, Cu, Zn, and Mn; the doped transition metal is selected from at least one of Mo, V, Ce, W, Ti, Zr, Cr, Sc, and Y.

[0020] Furthermore, in step S1, when the transition metal in the transition metal salt is a primary transition metal and a doped transition metal, the molar ratio of the doped transition metal to the primary transition metal is 1:(1-100); specifically, it can be 1:1, 1:9, 1:19, 1:49, 1:69, 1:89, 1:99, 1:100, etc., or any range formed by the above ratios, such as 1:(1-9), 1:(1-19), 1:(1-99), etc., and the present invention is not limited thereto.

[0021] Preferably, in step S1, the transition metal salt is selected from one or more of nitrates, acetates, sulfates, carbonates, and chlorides.

[0022] Preferably, in step S1, the concentration of the transition metal salt in the mixed solution is 1–10000 mM. More preferably, the concentration of the transition metal salt in the mixed solution is 10–5000 mM, specifically 10 mM, 100 mM, 500 mM, 1000 mM, 3000 mM, 5000 mM, etc., or any range formed by the above values, such as 10–100 mM, 10–500 mM, 10–3000 mM, etc., and the present invention is not limited thereto.

[0023] Preferably, in step S1, the precipitant is selected from at least one of potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, hexamethylenetetramine, urea, and sodium oxalate.

[0024] Preferably, in step S1, the molar ratio of the transition metal salt to the precipitant is 1:(1-20). More preferably, the molar ratio of the transition metal salt to the precipitant is 1:(1-16); specifically, it can be 1:1, 1:2, 1:4, 1:8, or 1:16.

[0025] Further, in step S1, the current collector is a metal current collector, carbon cloth, or carbon paper. Preferably, the metal current collector is a metal foam, metal foil, metal plate, or metal mesh, and the metal of the metal current collector is Fe, Co, Ni, Cu, Zn, Al, Ti, or stainless steel.

[0026] Further, in step S1, the temperature of the solvothermal reaction is 50–250°C. Preferably, the temperature of the solvothermal reaction is 60–200°C; specifically, it can be 60°C, 80°C, 100°C, 120°C, 150°C, 180°C, or 200°C.

[0027] Preferably, in step S1, the solvothermal reaction time is 1 to 96 hours. Specifically, the solvothermal reaction time is 1 hour, 2 hours, 5 hours, 8 hours, 12 hours, 24 hours, 48 ​​hours, or 96 hours.

[0028] Further, in step S2, the amino-containing silane coupling agent is selected from at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminoethylaminomethyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminohexylaminomethyltrimethoxysilane, methylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, aminoethylaminopropylmethyldimethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, methylaminopropylmethyldiethoxysilane, and methylaminomethylmethyldiethoxysilane.

[0029] Preferably, the amino-containing silane coupling agent is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminoethylaminomethyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, or aminohexylaminomethyltrimethoxysilane.

[0030] Preferably, in step S2, the solvent used in the amino-containing silane coupling agent solution is selected from one or more of water, methanol, ethanol, isopropanol, ethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, 1,6-hexanediol, pentanediol, glycerol, toluene, acetonitrile, acetone, methyl acetate, and ethyl acetate.

[0031] Preferably, in step S2, the specific operation of the grafting modification is a stirring reaction.

[0032] Preferably, in step S2, the grafting modification temperature is 25–150°C. More preferably, the grafting modification temperature is 30–80°C, specifically 30°C, 40°C, 50°C, 60°C, 70°C, or 80°C.

[0033] Preferably, in step S2, the grafting modification time is 0.5 to 48 hours, and more preferably, the grafting modification time is 2 to 24 hours, specifically 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 18 hours, or 24 hours.

[0034] Preferably, in step S2, the volume percentage of the silane coupling agent in the amino-containing silane coupling agent solution is 0.01% to 30%. More preferably, it can be 0.1% to 10%, specifically 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 5%, or 10%.

[0035] Preferably, in step S3, the fullerene is selected from C 20 C 60 C 70 C 72 C 76 C 80 C 84 C 96 At least one of the following. Preferably, the fullerene is C10. 60 C 70 C 76 C 80 C 84 .

[0036] Preferably, in step S3, the fullerene-containing solvent is selected from one or more of the aromatic solvents toluene, chlorobenzene, 1,2-dichlorobenzene, and m-xylene, or the non-aromatic solvents carbon disulfide and carbon tetrachloride.

[0037] Preferably, the fullerene modification is carried out by a stirring reaction.

[0038] Preferably, in step S3, the fullerene modification temperature is 20–150°C. More preferably, the fullerene modification temperature is 40–120°C, specifically 40°C, 50°C, 60°C, 80°C, 100°C, or 120°C.

[0039] Preferably, in step S3, the fullerene modification time is 1 to 240 hours. More preferably, the fullerene modification time is 6 to 120 hours, specifically 6 hours, 12 hours, 24 hours, 48 ​​hours, 72 hours, 96 hours, or 120 hours.

[0040] Preferably, in step S3, the molar concentration of the fullerene in the solvent is 0.1 to 100 mmol / L, more preferably, it can be 1.0 to 50 mmol / L, specifically 1.0 mmol / L, 5.0 mmol / L, 10 mmol / L, 20 mmol / L, or 50 mmol / L.

[0041] Meanwhile, the present invention also protects the fullerene-modified transition metal hydroxide nanoarray material prepared by the preparation method.

[0042] Furthermore, this invention protects the application of the fullerene-modified transition metal hydroxide nanoarray material in organic electro-oxidation reactions.

[0043] Preferably, the organic electro-oxidation is an organic electro-oxidation reaction of organic alcohols, aldehydes, ketones, amines, etc.

[0044] The fullerene-modified transition metal hydroxide nanoarray material prepared by this invention has excellent catalytic activity, can catalyze organic electro-oxidation reactions, and improve their Faraday efficiency.

[0045] The present invention has the following beneficial effects:

[0046] This invention grafts a transition metal hydroxide nanoarray with an amino-containing silane coupling agent to imbue the material surface with amino groups. Finally, through the addition reaction of the surface amino groups with the carbon-carbon double bonds of fullerenes, a fullerene-modified transition metal hydroxide nanoarray material is obtained. The preparation method of this invention is economical, simple, rapid, and capable of large-scale mass production. Furthermore, the material prepared by this invention benefits from the fullerene modification, which optimizes its surface electronic structure and further enhances its catalytic activity. Simultaneously, the fullerene modification facilitates the adsorption and enrichment of organic substrates on the catalytic material surface, thereby improving mass transfer efficiency. Based on the above enhancement mechanism, the obtained fullerene-modified transition metal hydroxide nanoarray material exhibits excellent electrocatalytic performance for a series of organic electro-oxidation reactions. Attached Figure Description

[0047] Figure 1 The TM / Ni(OH)2-C prepared in Example 1 84 SEM image of nanoarray material.

[0048] Figure 2 The NF / CoCe-OH-C prepared in Example 2 60 SEM image of nanoarray material.

[0049] Figure 3 The IF / CuY-OH-C prepared in Example 3 76 SEM image of nanoarray material.

[0050] Figure 4 The SS / FeMnCr-OH-C prepared in Example 4 80 SEM image of nanoarray material.

[0051] Figure 5 The CC / NiZnV-OH-C prepared in Example 5 70 SEM image of nanoarray material.

[0052] Figure 6 The AlF / NiCoSc-OH-C prepared in Example 6 60 SEM image of nanoarray material.

[0053] Figure 7 The LSV diagrams show the electrocatalytic cyclohexanol oxidation reaction of the nanoarray materials in Example 1 and Comparative Examples 1, 2, and 3.

[0054] Figure 8 The LSV diagrams show the electrocatalytic oxidation of ethylene glycol using nanoarray materials in Example 2 and Comparative Example 4.

[0055] Figure 9 The LSV diagrams show the electrocatalytic oxidation of benzylamine using nano-array materials in Example 3 and Comparative Example 5.

[0056] Figure 10 The LSV diagrams show the electrocatalytic oxidation of 5-hydroxymethylfurfural using nano-array materials in Example 4 and Comparative Example 6.

[0057] Figure 11 The LSV diagrams show the electrocatalytic oxidation of benzyl alcohol using nanoarray materials in Example 5 and Comparative Example 7.

[0058] Figure 12 The LSV diagrams show the electrocatalytic oxidation of cyclohexanone using nanoarray materials in Example 6 and Comparative Example 8. Detailed Implementation

[0059] 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.

[0060] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0061] Example 1 TM / Ni(OH)2-C 84 Nanoarray materials

[0062] The TM / Ni(OH)2-C 84 The preparation method of nanoarray materials includes the following steps:

[0063] S1. Dissolve 1.244 g (5 mmol) nickel acetate tetrahydrate (NiC4H6O4·4H2O) and 2.804 g (20 mmol) hexamethylenetetramine (HMTA) in 50 mL of ultrapure water. Stir the mixture thoroughly for 1 h (stirrer speed 500 rpm) until a homogeneous solution is obtained. Then, immerse two 2×4 cm pretreated titanium mesh (TM) in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 120 °C for 12 h. After the reaction is completed, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, respectively, and dry it in a forced-air drying oven at 60 °C for 12 h to obtain Ni(OH)2 nanoarray material loaded on the TM current collector.

[0064] S2. Immerse the Ni(OH)2 nanoarray material loaded with the TM current collector obtained in step S1 into 2% 3-aminopropyltriethoxysilane (C9H) solvent using methanol. 23 In a NO3Si solution, the mixture was stirred at 30°C for 24 hours. After grafting modification, it was washed three times with anhydrous ethanol and dried in a forced-air drying oven at 60°C for 6 hours to obtain Ni(OH)2@C9H supported on the TM current collector. 23 NO3Si nanoarray materials;

[0065] S3. Load the Ni(OH)2@C9H onto the TM current collector obtained in step S2. 23 NO3Si nanoarray material was immersed in 1 mmol / L solution of toluene. 84 The solution was stirred at 80°C for 48 hours, then washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60°C for 12 hours to obtain Ni(OH)2-C supported on the TM current collector. 84 Nanoarray materials.

[0066] Material characterization:

[0067] The obtained product was characterized by SEM to obtain the material morphology. Figure 1 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the TM current collector.

[0068] Example 2NF / CoCe-OH-C 60 Nanoarray materials

[0069] The NF / CoCe-OH-C 60 The preparation method of nanoarray materials includes the following steps:

[0070] S1. Dissolve 43.655g (150mmol) cobalt nitrate hexahydrate (Co(NO3)2·6H2O), 65.133g (150mmol) cerium nitrate hexahydrate (Ce(NO3)3·6H2O) and 144.144g (2.4mol) urea (CH4N2O) in 100mL of ultrapure water. Stir the mixture thoroughly for 3h (650rpm) until a homogeneous solution is obtained. Then, immerse three 4×5cm pretreated nickel foam (NF) sheets in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 180℃ for 8h. After the reaction, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, and dry it in a forced-air drying oven at 60℃ for 24h to obtain CoCe-OH nanoarray material loaded on NF current collector.

[0071] S2. Immerse the CoCe-OH nanoarray material loaded with the NF current collector obtained in step S1 into 0.5% aminoethylaminomethyltriethoxysilane (C9H) solvent with isopropanol as the solvent. 24 In an N2O3Si solution, the mixture was stirred at 60°C for 8 hours. After grafting modification, it was washed three times with anhydrous ethanol and dried in a forced-air drying oven at 60°C for 12 hours to obtain CoCe-OH@C9H loaded on the NF current collector. 24 N2O3Si nanoarray materials;

[0072] S3. Load the CoCe-OH@C9H onto the NF current collector obtained in step S2. 24 N2O3Si nanoarray material was immersed in a 10 mmol / L solution of m-xylene. 60 The solution was stirred at 100℃ for 24 h, then washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60℃ for 24 h to obtain CoCe-OH-C supported on the NF current collector. 60 Nanoarray materials.

[0073] Material characterization:

[0074] The obtained product was characterized by SEM to obtain the material morphology. Figure 2As can be seen from the figure, there is a uniformly distributed nanosheet structure on the NF current collector.

[0075] Example 3 IF / CuY-OH-C 76 Nanoarray materials

[0076] The IF / CuY-OH-C 76 The preparation method of nanoarray materials includes the following steps:

[0077] S1. Dissolve 3.3414 g (19.6 mmol) copper chloride dihydrate (CuCl2·2H2O), 0.1213 g (0.4 mmol) yttrium chloride hexahydrate (YCl3·6H2O) and 1.402 g (20 mmol) ammonia water (NH3·H2O) (25%-28% wt) in 40 mL of ultrapure water. Stir the solution thoroughly for 0.5 h (stirrer speed 500 rpm) until a homogeneous mixture is obtained. Then, immerse two 2×3 cm pretreated iron foam (IF) sheets in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 200 °C for 1 h. After the reaction, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, and dry it in a forced-air drying oven at 60 °C for 12 h to obtain CuY-OH nanoarray material loaded on the IF current collector.

[0078] S2. Immerse the CuY-OH nanoarray material loaded with the IF current collector obtained in step S1 into 10% aminohexylaminomethyltrimethoxysilane (C) solvent with glycerol as the solvent. 10 H 26 In an N2O3Si solution, the mixture was stirred at 80°C for 2 hours. After grafting modification, it was washed three times with anhydrous ethanol and dried in a forced-air drying oven at 60°C for 12 hours to obtain CuY-OH@C supported on an IF current collector. 10 H 26 N2O3Si nanoarray materials;

[0079] S3. Load CuY-OH@C onto the IF current collector obtained in step S2. 10 H 26 N2O3Si nanoarray material was immersed in 1 mmol / L solution of benzene as solvent. 76 The solution was stirred at 60°C for 72 hours, then washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60°C for 12 hours to obtain CuY-OH-C supported on the IF current collector. 76 Nanoarray materials.

[0080] Material characterization:

[0081] The obtained product was characterized by SEM to obtain the material morphology. Figure 3As can be seen from the figure, there are uniformly distributed nanosheet structures on the IF current collector.

[0082] Example 4 SS / FeMnCr-OH-C 80 Nanoarray materials

[0083] The SS / FeMnCr-OH-C 80 The preparation method of nanoarray materials includes the following steps:

[0084] S1. 4.866 g (18 mmol) ferric chloride hexahydrate (FeCl3·6H2O), 0.198 g (1 mmol) manganese chloride tetrahydrate (MnCl2·4H2O), 0.266 g (1 mmol) chromium chloride hexahydrate (CrCl3·6H2O) and 2.804 g (20 mmol) hexamethylenetetramine (HMTA) were dissolved in 20 mL of ultrapure water and stirred thoroughly on a stirrer for 2 h (stirrer speed 600 rpm) until a homogeneous mixed solution was obtained. Then, two 1×3 cm pretreated stainless steel (SS) sheets were immersed in the solution, transferred to a high-pressure reactor, sealed, and placed in a forced-air drying oven for solvothermal reaction at 100 °C for 48 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60 °C for 6 h to obtain FeMnCr-OH nanoarray material loaded on SS current collector.

[0085] S2. The FeMnCr-OH nanoarray material loaded with the SS current collector obtained in step S1 is immersed in 1% diethylenetriaminepropyltrimethoxysilane (C) solvent with acetone as the solvent. 10 H 27 In an N3O3Si) solution, the mixture was stirred at 40℃ for 18 h, then grafted and modified, washed three times with anhydrous ethanol, and dried in a forced-air drying oven at 60℃ for 6 h to obtain FeMnCr-OH@C supported on an SS current collector. 10 H 27 N3O3Si nanoarray materials;

[0086] S3. Load FeMnCr-OH@C onto the SS current collector obtained in step S2. 10 H 27 N3O3Si nanoarray material was immersed in a 20 mmol / L solution of carbon disulfide. 80 The solution was stirred at 40°C for 120 h, then washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60°C for 12 h to obtain FeMnCr-OH-C supported on the SS current collector. 80 Nanoarray materials.

[0087] Material characterization:

[0088] The obtained product was characterized by SEM to obtain the material morphology. Figure 4 As can be seen from the figure, there are uniformly distributed nanosheet structures on the SS current collector.

[0089] Example 5CC / NiZnV-OH-C 70 Nanoarray materials

[0090] The CC / NiZnV-OH-C 70 The preparation method of nanoarray materials includes the following steps:

[0091] S1. 15.166 g (98 mmol) of nickel sulfate (NiSO4), 0.179 g (1 mmol) of zinc sulfate (ZnSO4·H2O), 0.163 g (1 mmol) of vanadium oxysulfate hydrate (VOSO4·xH2O) and 48.048 g (800 mmol) of urea (CH4N2O) were dissolved in 1000 mL of ultrapure water and stirred thoroughly on a stirrer for 4 h (stirrer speed was 550 rpm) until a homogeneous mixed solution was obtained. Then, 4 pieces of 5×6 cm pretreated carbon cloth (CC) were immersed in the solution, transferred to a high-pressure reactor, sealed and placed in a forced-air drying oven for solvothermal reaction at 150 °C for 24 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed 3 times with ultrapure water and anhydrous ethanol respectively, and dried in a forced-air drying oven at 60 °C for 24 h to obtain NiZnV-OH nanoarray material loaded on CC current collector.

[0092] S2. Immerse the NiZnV-OH nanoarray material loaded with CC current collector obtained in step S1 into 0.1% methylaminopropyltrimethoxysilane (C7H) solvent using ethanol. 19 In a NO3Si solution, the mixture was stirred at 70°C for 4 hours. After grafting modification, it was washed three times with anhydrous ethanol and dried in a forced-air drying oven at 60°C for 12 hours to obtain NiZnV-OH@C7H supported on a CC current collector. 19 NO3Si nanoarray materials;

[0093] S3. Load the NiZnV-OH@C7H onto the CC current collector obtained in step S2. 19 NO3Si nanoarray material was immersed in 50 mmol / L solution with 1,2-dichlorobenzene as solvent. 70 The solution was stirred at 120℃ for 6 hours, then washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60℃ for 24 hours to obtain NiZnV-OH-C supported on the CC current collector. 70 Nanoarray materials.

[0094] Material characterization:

[0095] The obtained product was characterized by SEM to obtain the material morphology. Figure 5 As can be seen from the figure, there are uniformly distributed nanosheet structures on the CC current collector.

[0096] Example 6 AlF / NiCoSc-OH-C 60 Nanoarray materials

[0097] The AlF / NiCoSc-OH-C 60 The preparation method of nanoarray materials includes the following steps:

[0098] S1. Dissolve 0.093 g (0.32 mmol) nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 0.012 g (0.04 mmol) cobalt nitrate hexahydrate (Co(NO3)2·6H2O), 0.014 g (0.04 mmol) scandium nitrate hexahydrate (Sc(NO3)3·6H2O) and 0.359 g (6.4 mmol) potassium hydroxide (KOH) in 40 mL of ultrapure water and stir thoroughly on a stirrer for 1 h. (Stirring speed is 450 rpm) After obtaining a homogeneous mixed solution, immerse two 1×3 cm pretreated aluminum foils (AlF), transfer them to a high-pressure reactor, seal them and place them in a forced-air drying oven for solvothermal reaction at 60℃ for 96 h. After the reaction is completed, allow it to cool naturally. The cooled material is washed three times with ultrapure water and anhydrous ethanol respectively, and dried in a forced-air drying oven at 60℃ for 12 h to obtain NiCoSc-OH nanoarray material loaded on AlF current collector;

[0099] S2. Immerse the NiCoSc-OH nanoarray material loaded on the AlF current collector obtained in step S1 into 0.2% aminoethylaminopropyltrimethoxysilane (C8H) solvent. 22 In an AlF current collector, NiCoSc-OH@C8H3O3 was prepared by stirring at 50°C for 10 h, followed by grafting modification and washing three times with anhydrous ethanol. The resulting product was then dried in a forced-air drying oven at 60°C for 6 h to obtain NiCoSc-OH@C8H3O3 supported on an AlF current collector. 22 N2O3Si nanoarray materials;

[0100] S3. Load the NiCoSc-OH@C8H onto the AlF current collector obtained in step S2. 22 N2O3Si nanoarray material was immersed in 5 mmol / L solution of toluene. 60 The solution was stirred at 50°C for 96 hours, then washed three times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60°C for 12 hours to obtain NiCoSc-OH-C supported on an AlF current collector. 60 Nanoarray materials.

[0101] Material characterization:

[0102] The obtained product was characterized by SEM to obtain the material morphology. Figure 6 As can be seen from the figure, there are uniformly distributed nanosheet structures on the AlF current collector.

[0103] Comparative Example 1™ / Ni(OH)2 Nanoarray Material

[0104] The preparation method of the TM / Ni(OH)2 nanoarray material includes the following steps:

[0105] S1. Dissolve 1.244 g (5 mmol) nickel acetate tetrahydrate (NiC4H6O4·4H2O) and 2.804 g (20 mmol) hexamethylenetetramine (HMTA) in 50 mL of ultrapure water. Stir the mixture thoroughly for 1 h (stirrer speed 500 rpm) until a homogeneous solution is obtained. Immerse two 2×4 cm pretreated titanium meshes (TM) in the solution, transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 120 °C for 12 h. After the reaction is completed, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, respectively, and dry it in a forced-air drying oven at 60 °C for 12 h to obtain Ni(OH)2 nanoarray material loaded on the TM current collector.

[0106] The difference between Comparative Example 1 and Example 1 is that the 3-aminopropyltriethoxysilane (C9H) reaction was not performed. 23 NO3Si) grafting and subsequent fullerene C 84 Modification.

[0107] Comparative Example 2TM / Ni(OH)2-Carbon Nanoarray Material

[0108] The preparation method of the TM / Ni(OH)2-Carbon nanoarray material includes the following steps:

[0109] S1. Dissolve 1.244 g (5 mmol) nickel acetate tetrahydrate (NiC4H6O4·4H2O) and 2.804 g (20 mmol) hexamethylenetetramine (HMTA) in 50 mL of ultrapure water. Stir the mixture thoroughly for 1 h (stirrer speed 500 rpm) until a homogeneous solution is obtained. Then, immerse two 2×4 cm pretreated titanium mesh (TM) in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 120 °C for 12 h. After the reaction is completed, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, respectively, and dry it in a forced-air drying oven at 60 °C for 12 h to obtain Ni(OH)2 nanoarray material loaded on the TM current collector.

[0110] S2. Immerse the Ni(OH)2 nanoarray material loaded with the TM current collector obtained in step S1 into 2% 3-aminopropyltriethoxysilane (C9H) solvent using methanol. 23 In a NO3Si solution, the mixture was stirred at 30°C for 24 hours. After grafting modification, it was washed three times with anhydrous ethanol and dried in a forced-air drying oven at 60°C for 6 hours to obtain Ni(OH)2@C9H supported on the TM current collector. 23 NO3Si nanoarray materials;

[0111] S3. Load the Ni(OH)2@C9H onto the TM current collector obtained in step S2. 23 NO3Si nanoarray material was immersed in a toluene solution containing 1.009 g / L carbon black (the mass concentration of carbon black in this solution is the same as that in the toluene solution in step S3 of Example 1). 84 (with equal mass concentration), stirred at 80℃ for 48h, then washed 3 times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60℃ for 12h to obtain Ni(OH)2-Carbon nanoarray material loaded on TM current collector.

[0112] Compared to Example 1, Comparative Example 2 differs in that it did not involve fullerene C. 84 Instead of surface modification, carbon black modification is performed.

[0113] Comparative Example 3TM / Ni(OH)2-Graphene Nanoarray Material

[0114] The preparation method of the TM / Ni(OH)2-Graphene nanoarray material includes the following steps:

[0115] S1. Dissolve 1.244 g (5 mmol) nickel acetate tetrahydrate (NiC4H6O4·4H2O) and 2.804 g (20 mmol) hexamethylenetetramine (HMTA) in 50 mL of ultrapure water. Stir the mixture thoroughly for 1 h (stirrer speed 500 rpm) until a homogeneous solution is obtained. Then, immerse two 2×4 cm pretreated titanium mesh (TM) in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 120 °C for 12 h. After the reaction is completed, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, respectively, and dry it in a forced-air drying oven at 60 °C for 12 h to obtain Ni(OH)2 nanoarray material loaded on the TM current collector.

[0116] S2. Immerse the Ni(OH)2 nanoarray material loaded with the TM current collector obtained in step S1 into 2% 3-aminopropyltriethoxysilane (C9H) solvent using methanol. 23In a NO3Si solution, the mixture was stirred at 30°C for 24 hours. After grafting modification, it was washed three times with anhydrous ethanol and dried in a forced-air drying oven at 60°C for 6 hours to obtain Ni(OH)2@C9H supported on the TM current collector. 23 NO3Si nanoarray materials;

[0117] S3. Load the Ni(OH)2@C9H onto the TM current collector obtained in step S2. 23 NO3Si nanoarray material was immersed in a toluene solution containing 1.009 g / L graphene (the mass concentration of graphene in this solution is the same as that in the toluene solution in step S3 of Example 1). 84 (with equal mass concentration), stirred at 80℃ for 48h, then washed 3 times with ultrapure water and anhydrous ethanol, and dried in a forced-air drying oven at 60℃ for 12h to obtain Ni(OH)2-Graphene nanoarray material loaded on TM current collector.

[0118] The difference between Comparative Example 3 and Example 1 is that the fullerene C-type reaction was not performed. 84 Instead of surface modification, the graphene is modified.

[0119] Comparative example 4NF / CoCe-OH nanoarray materials

[0120] The preparation method of the NF / CoCe-OH nanoarray material includes the following steps:

[0121] S1. Dissolve 43.655 g (150 mmol) cobalt nitrate hexahydrate (Co(NO3)2·6H2O), 65.133 g (150 mmol) cerium nitrate hexahydrate (Ce(NO3)3·6H2O), and 144.144 g (2.4 mol) urea (CH4N2O) in 100 mL of ultrapure water. Stir the solution thoroughly for 3 h (650 rpm) until a homogeneous mixture is obtained. Then, immerse three 4×5 cm pretreated nickel foam (NF) sheets in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 180 °C for 8 h. After the reaction, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, and dry it in a forced-air drying oven at 60 °C for 24 h to obtain the CoCe-OH nanoarray material loaded on the NF current collector.

[0122] The difference between Comparative Example 4 and Example 2 is that the aminoethylaminomethyltriethoxysilane (C9H) was not used. 24 Grafting of N2O3Si and subsequent fullerene C 60 Modification.

[0123] Comparative example: 5IF / CuY-OH nanoarray material

[0124] The preparation method of the IF / CuY-OH nanoarray material includes the following steps:

[0125] S1. Dissolve 3.3414 g (19.6 mmol) copper chloride dihydrate (CuCl2·2H2O), 0.1213 g (0.4 mmol) yttrium chloride hexahydrate (YCl3·6H2O) and 1.402 g (20 mmol) ammonia water (NH3·H2O) (25%-28% wt) in 40 mL of ultrapure water. Stir the solution thoroughly for 0.5 h (stirrer speed 500 rpm) until a homogeneous mixture is obtained. Then, immerse two 2×3 cm pretreated iron foam (IF) sheets in the solution. Transfer the solution to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 200 °C for 1 h. After the reaction, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, respectively, and dry it in a forced-air drying oven at 60 °C for 12 h to obtain CuY-OH nanoarray material loaded on the IF current collector.

[0126] Compared to Example 3, Comparative Example 5 differs in that it did not involve the reaction of aminohexylaminomethyltrimethoxysilane (C 10 H 26 Grafting of N2O3Si and subsequent fullerene C 76 Modification.

[0127] Comparative example: 6SS / FeMnCr-OH nanoarray material

[0128] The preparation method of the SS / FeMnCr-OH nanoarray material includes the following steps:

[0129] S1. 4.866 g (18 mmol) ferric chloride hexahydrate (FeCl3·6H2O), 0.198 g (1 mmol) manganese chloride tetrahydrate (MnCl2·4H2O), 0.266 g (1 mmol) chromium chloride hexahydrate (CrCl3·6H2O) and 2.804 g (20 mmol) hexamethylenetetramine (HMTA) were dissolved in 20 mL of ultrapure water and stirred thoroughly on a stirrer for 2 h (stirrer speed 600 rpm) until a homogeneous mixed solution was obtained. Then, two 1×3 cm pretreated stainless steel (SS) sheets were immersed in the solution, transferred to a high-pressure reactor, sealed, and placed in a forced-air drying oven for solvothermal reaction at 100 °C for 48 h. After the reaction was completed, the solution was allowed to cool naturally. The cooled material was washed three times with ultrapure water and three times with anhydrous ethanol, and then dried in a forced-air drying oven at 60 °C for 6 h to obtain FeMnCr-OH nanoarray material loaded on SS current collector.

[0130] Compared to Example 4, Comparative Example 6 differs in that it did not involve the reaction of diethylenetriaminepropyltrimethoxysilane (C10 H 27 Grafting of N3O3Si and subsequent fullerene C 80 Modification.

[0131] Comparative example: 7CC / NiZnV-OH nanoarray material

[0132] The preparation method of the CC / NiZnV-OH nanoarray material includes the following steps:

[0133] S1. Dissolve 15.166 g (98 mmol) nickel sulfate (NiSO4), 0.179 g (1 mmol) zinc sulfate (ZnSO4·H2O), 0.163 g (1 mmol) vanadium oxysulfate hydrate (VOSO4·xH2O), and 48.048 g (800 mmol) urea (CH4N2O) in 1000 mL of ultrapure water. Stir the solution thoroughly for 4 h (550 rpm) until a homogeneous mixture is obtained. Immerse four 5×6 cm pretreated carbon cloth (CC) sheets in the solution, transfer the mixture to a high-pressure reactor, seal it, and place it in a forced-air drying oven for a solvothermal reaction at 150 °C for 24 h. After the reaction, allow it to cool naturally. Wash the cooled material three times with ultrapure water and anhydrous ethanol, and dry it in a forced-air drying oven at 60 °C for 24 h to obtain NiZnV-OH nanoarray material loaded on CC current collector.

[0134] The difference between Comparative Example 7 and Example 5 is that the reaction with methylaminopropyltrimethoxysilane (C7H) was not performed. 19 NO3Si) grafting and subsequent fullerene C 70 Modification.

[0135] Comparative Example 8AlF / NiCoSc-OH Nanoarray Material

[0136] The preparation method of the AlF / NiCoSc-OH nanoarray material includes the following steps:

[0137] S1. Dissolve 0.093 g (0.32 mmol) nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 0.012 g (0.04 mmol) cobalt nitrate hexahydrate (Co(NO3)2·6H2O), 0.014 g (0.04 mmol) scandium nitrate hexahydrate (Sc(NO3)3·6H2O) and 0.359 g (6.4 mmol) potassium hydroxide (KOH) in 40 mL of ultrapure water and stir thoroughly on a stirrer for 1 h. (Stirring speed is 450 rpm) After obtaining a homogeneous mixed solution, immerse two 1×3 cm pretreated aluminum foils (AlF) in the solution, transfer them to a high-pressure reactor, seal them, and place them in a forced-air drying oven for solvothermal reaction at 60℃ for 96 h. After the reaction is completed, allow it to cool naturally. The cooled material is washed three times with ultrapure water and anhydrous ethanol, and then dried in a forced-air drying oven at 60℃ for 12 h to obtain NiCoSc-OH nanoarray material loaded on AlF current collector.

[0138] The difference between Comparative Example 8 and Example 6 is that the aminoethylaminopropyltrimethoxysilane (C8H) reaction was not performed. 22 Grafting of N2O3Si and subsequent fullerene C 60 Modification.

[0139] Application Example 1: Performance Testing of Cyclohexanol Electro-oxidation (CXLOR)

[0140] Electrochemical tests were performed using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. The main indicators for evaluating the activity of the nanoarray materials prepared in the examples or comparative examples were: the voltage (E) required to achieve the same current density, the formation rate of the target product, and the Faraday efficiency.

[0141] Three-electrode system: The nanoarray material prepared in the examples or comparative examples is used as the working electrode (1×1cm), the Pt sheet (2×2cm) is used as the counter electrode, and the Hg / HgO electrode (immersed in 1.0M KOH solution) is used as the reference electrode. The electrolyte used is potassium hydroxide solution containing cyclohexanol (1M KOH + 0.1M cyclohexanol).

[0142] Before each electrochemical data acquisition, the solution resistance (R0) of all materials was measured at the open-circuit potential. s) Values were scanned multiple times for CV curves until stable within the voltage range of 0.1 - 0.9 V vs. Hg / HgO, and then LSV tests were carried out within the voltage range of 0 - 1.0 V vs. Hg / HgO. The LSV curve was compensated with 95% IR. At the same time, according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916×pH, the potential value E(Hg / HgO) was converted to E(RHE). In addition, the CXLOR performance of the material was tested for 5 h by chronoamperometry (CA test), and the electrolyte after CA test was quantitatively analyzed by GC. Specific test procedure: After the CA test was completed, 2 mL of electrolyte was extracted with a syringe and injected into a certain amount of deionized water for dilution. Then a small amount of 1M HCl was added to adjust the pH value of the solution. Then dichloromethane was added for extraction. The organic phase was transferred to a sample bottle, and then a small amount of Na2SO4 was added for dehydration. 2 μL of the sample was injected into the injector. GC test parameters: The detector was an FID detector, the chromatographic column was a DB-5ms capillary column, and the carrier gas was N2. The inlet temperature was 250 °C, the FID detector temperature was 300 °C, the H2 flow rate was 30 mL / min, the air flow rate was 400 mL / min, and the tail blow N2 flow rate was 25 mL / min. Subsequently, GC-MS was used for qualitative analysis.

[0143] This application example tested the CXLOR performance of Example 1 (TM / Ni(OH)2-C 84 ), Comparative Example 1 (TM / Ni(OH)2), Comparative Example 2 (TM / Ni(OH)2-Carbon), and Comparative Example 3 (TM / Ni(OH)2-Graphene). The LSV results are shown in Figure 7 . From Figure 7 it can be seen that for the CXLOR performance, compared with TM / Ni(OH)2, TM / Ni(OH)2-Carbon, and TM / Ni(OH)2-Graphene, when reaching the same current density of 50 mA·cm 84 , the potential (E -2 ) is smaller. E 50 vs. RHE are TM / Ni(OH)2-C 50 (1.422 V) < TM / Ni(OH)2-Graphene (1.571 V) < TM / Ni(OH)2-Carbon (1.588 V) < TM / Ni(OH)2 (1.611 V), preliminarily indicating that the nanoarray material prepared in the embodiment of the present invention has better CXLOR performance 84 .

[0144] According to the GC test, Example 1 (TM / Ni(OH)2-C 84The rate of adipic acid formation at 1.45 V vs. RHE was 0.079 mmol / (h·cm). 2 The Faraday efficiency was 91.2%; the adipic acid formation rate of Comparative Example 1 (TM / Ni(OH)2) at 1.45V vs. RHE was 0.032 mmol / (h·cm). 2 The Faraday efficiency was 48.6%; the adipic acid formation rate of Comparative Example 2 (TM / Ni(OH)2-Carbon) at 1.45V vs. RHE was 0.046 mmol / (h·cm). 2 The Faraday efficiency was 52.8%; the adipic acid formation rate of Comparative Example 3 (TM / Ni(OH)2-Graphene) at 1.45 V vs. RHE was 0.055 mmol / (h·cm). 2 The Faraday efficiency is 59.4%. Based on the above performance results, it can be seen that Example 1 (TM / Ni(OH)2-C) 84 The CXLOR performance of the fullerene-modified nanoarray material is superior to that of Comparative Example 1 (TM / Ni(OH)2), Comparative Example 2 (TM / Ni(OH)2-Carbon), and Comparative Example 3 (TM / Ni(OH)2-Graphene). The differences in these experimental results indicate that only the fullerene-modified nanoarray material exhibits good catalytic organic electro-oxidation performance, with its Faradaic efficiency increasing by 72.72% compared to the carbon black-modified nanoarray material (Comparative Example 2) and by 53.54% compared to the graphene-modified nanoarray material (Comparative Example 3).

[0145] Application Example 2: Performance Testing of Ethylene Glycol Electro-oxidation (EGOR)

[0146] Electrochemical tests were performed using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. The main indicators for evaluating the activity of the nanoarray materials prepared in the examples or comparative examples were: the voltage (E) required to achieve the same current density, the formation rate of the target product, and the Faraday efficiency.

[0147] Three-electrode system: The nanoarray material prepared in the examples or comparative examples is used as the working electrode (1×1cm), the graphite rod is used as the counter electrode, and the Hg / HgO electrode (immersed in 1.0M KOH solution) is used as the reference electrode. The electrolyte used is potassium hydroxide solution containing ethylene glycol (1M KOH + 0.1M ethylene glycol).

[0148] Before each electrochemical data acquisition, the solution resistance (R0) of all materials was measured at the open-circuit potential. s) Values were scanned multiple times for CV curves until stable within the voltage range of 0.1 - 0.9V vs. Hg / HgO, and then LSV tests were carried out within the voltage range of 0.1 - 0.9V vs. Hg / HgO. The LSV curve was subjected to 95% IR compensation. Meanwhile, according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 × pH, the potential value E(Hg / HgO) was converted to E(RHE). In addition, the EGOR performance of the material was tested for 3h by chronoamperometry (CA test), and the electrolyte after CA test was quantitatively analyzed by HPLC. Specific test procedure: After the CA test was completed, 200 μL of the electrolyte was extracted with a syringe and injected into a certain amount of deionized water for dilution, and then a small amount of 0.5M H2SO4 was added to adjust the pH value of the solution. The solution was filtered through a 0.22 μm filter membrane and 20 μL of the sample was injected into the injector. HPLC test parameters: The detector was a UV detector, the chromatographic column was an organic acid column, the mobile phase was 8mM H2SO4, the wavelength was 210nm, the column temperature was 50°C, the flow rate was 0.6mL / min, and the detection time was 16min. Subsequently, qualitative analysis was carried out using HPLC-MS.

[0149] This application example tested the EGOR performance of Example 2 (NF / CoCe-OH-C 60 ) and Comparative Example 4 (NF / CoCe-OH). The LSV results are shown in Figure 8 . As can be seen from the figure, for the EGOR performance, compared with NF / CoCe-OH, NF / CoCe-OH-C 60 has a smaller potential (E -2 ) when reaching the same current density of 100 mA·cm 100 . E 100 vs. RHE are NF / CoCe-OH-C 60 (1.406V) < NF / CoCe-OH (1.452V), which preliminarily indicates that the nanoarray material prepared in the embodiment of the present invention has better EGOR performance.

[0150] According to the HPLC test, the formic acid production rate of Example 2 (NF / CoCe-OH-C 60 ) was 0.816 mmol / (h·cm 2 ) at 1.45V vs. RHE, and the Faraday efficiency was 95.1%; the formic acid production rate of Comparative Example 4 (NF / CoCe-OH) was 0.563 mmol / (h·cm 2 ) at 1.45V vs. RHE, and the Faraday efficiency was 61.2%. According to the above performance results, it can be seen that Example 2 (NF / CoCe-OH-C 60The EGOR performance of (NF / CoCe-OH) is better than that of Comparative Example 4.

[0151] Application Example 3: Performance Testing of the Electro-oxidation Reaction of Aniline (BANOR)

[0152] Electrochemical tests were performed using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. The main indicators for evaluating the activity of the nanoarray materials prepared in the examples or comparative examples were: the voltage (E) required to achieve the same current density, the formation rate of the target product, and the Faraday efficiency.

[0153] Three-electrode system: The nanoarray material prepared in the examples or comparative examples is used as the working electrode (1×1cm), the Pt sheet (2×2cm) is used as the counter electrode, and the Hg / HgO electrode (immersed in 1.0M KOH solution) is used as the reference electrode. The electrolyte used is potassium hydroxide solution containing benzylamine (1M KOH + 0.01M benzylamine).

[0154] Before each electrochemical data acquisition, the solution resistance (R0) of all materials was measured at the open-circuit potential. s The potential values ​​were repeatedly scanned within the voltage range of 0.2–0.8 V vs. Hg / HgO until stable. Then, the potential values ​​were tested within the voltage range of 0.1–1.0 V vs. Hg / HgO, and the LSV curves were compensated for with 95% IR. The potential value E(Hg / HgO) was converted to E(RHE) according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 × pH. Furthermore, the BANOR performance of the material was tested for 2 hours using the chronoamperometry (CA test), and the electrolyte after the CA test was quantitatively analyzed by HPLC. The specific test procedure was as follows: After the CA test, 200 μL of electrolyte was drawn with a syringe and diluted with a certain amount of deionized water. A small amount of 0.5 M H₂SO₄ was added to adjust the pH of the solution. The solution was filtered through a 0.22 μm filter membrane, and 20 μL of sample was injected into the syringe. HPLC test parameters: UV detector, C18 column, mobile phase: a mixture of methanol and 0.05M potassium dihydrogen phosphate (methanol:potassium dihydrogen phosphate = 70:30), wavelength: 250 nm, column temperature: 50℃, flow rate: 0.8 mL / min, detection time: 7 min. Qualitative analysis was subsequently performed using HPLC-MS.

[0155] This application example relates to Example 3 (IF / CuY-OH-C) 76 The BANOR performance of IF / CuY-OH and Comparative Example 4 (IF / CuY-OH) was tested. LSV results are available in [link to LSV results]. Figure 9. As can be seen from the figure, for the BANOR performance, IF / CuY-OH-C 76 Compared with IF / CuY-OH, when reaching the same current density of 10 mA·cm -2 , the potential (E 10 ) is smaller. The E 10 vs. RHE of IF / CuY-OH-C 76 (1.366 V) < IF / CuY-OH (1.406 V), preliminarily indicating that the nanoarray material prepared in the embodiment of the present invention has better BANOR performance.

[0156] According to HPLC tests, for Example 3 (IF / CuY-OH-C 76 ), the production rate of benzonitrile is 0.364 mmol / (h·cm ) at 1.45 V vs. RHE, and the Faraday efficiency is 90.2%; for Comparative Example 5 (IF / CuY-OH), the production rate of benzonitrile is 0.242 mmol / (h·cm 2 ) at 1.45 V vs. RHE, and the Faraday efficiency is 59.5%. According to the above performance results, it can be seen that the BANOR performance of Example 3 (IF / CuY-OH-C 2 ) is better than that of Comparative Example 5 (IF / CuY-OH). 76 ) is better than that of Comparative Example 5 (IF / CuY-OH).

[0157] Application Example 4 Performance test of 5-hydroxymethylfurfural electrooxidation reaction (HMFOR)

[0158] Electrochemical tests were carried out using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N), and a standard three-electrode system was used for measurement; the main indicators for evaluating the activity of the nanoarray materials prepared in the examples or comparative examples are: the voltage (E) required to reach the same current density, the production rate of the target product, and the Faraday efficiency.

[0159] Three-electrode system: The nanoarray material prepared in the example or comparative example was used as the working electrode (1×1 cm), a Pt sheet (2×2 cm) was used as the counter electrode, and a Hg / HgO electrode (immersed in 1.0 M KOH solution) was used as the reference electrode. The electrolyte used was a potassium hydroxide solution containing 5-hydroxymethylfurfural (1 M KOH + 0.01 M 5-hydroxymethylfurfural).

[0160] Before each electrochemical data acquisition, the solution resistance (R s) Values were scanned multiple times for CV curves to stability within the voltage range of 0.2 - 0.8 V vs. Hg / HgO, and then LSV tests were carried out within the voltage range of 0.1 - 1.0 V vs. Hg / HgO. The LSV curve was compensated by 95% IR. Meanwhile, according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 × pH, the potential value E(Hg / HgO) was converted to E(RHE). In addition, the HMFOR performance of the material was tested for 2 h by chronoamperometry (CA test), and the electrolyte after CA test was quantitatively analyzed by HPLC. Specific test procedure: After the CA test was completed, 200 μL of the electrolyte was extracted with a syringe and injected into a certain amount of deionized water for dilution, and then a small amount of 0.5 M H2SO4 was added to adjust the pH value of the solution. The solution was filtered through a 0.22 μm filter membrane and 20 μL of the sample was injected into the injector. HPLC test parameters: The detector was a UV detector, the chromatographic column was C18, the mobile phase was a mixed solution of methanol and 0.05 M potassium dihydrogen phosphate (methanol: potassium dihydrogen phosphate = 70:30), the wavelength was 250 nm, the column temperature was 50 °C, the flow rate was 0.8 mL / min, and the detection time was 7 min. Subsequently, qualitative analysis was carried out by HPLC-MS.

[0161] This application example tested the HMFOR performance of Example 4 (SS / FeMnCr-OH-C 80 ) and Comparative Example 6 (SS / FeMnCr-OH), and the LSV results are shown in Figure 10 . As can be seen from the figure, for the HMFOR performance, compared with SS / FeMnCr-OH, when reaching the same current density of 100 mA·cm 80 , the potential (E -2 ) is smaller, and E 100 3] vs. RHE are SS / FeMnCr-OH-C 100 (1.400 V) < SS / FeMnCr-OH (1.468 V), preliminarily indicating that the nanoarray material prepared in the embodiment of the present invention has better HMFOR performance. 80 (1.400V) < SS / FeMnCr-OH(1.468V), preliminarily indicating that the nanoarray material prepared in the embodiment of the present invention has better HMFOR performance.

[0162] According to the HPLC test, for Example 4 (SS / FeMnCr-OH-C 80 ), the production rate of furandicarboxylic acid (FDCA) at 1.45 V vs. RHE is 0.157 mmol / (h·cm 2 ), and the Faraday efficiency is 94.8%; for Comparative Example 6 (SS / FeMnCr-OH), the production rate of furandicarboxylic acid (FDCA) at 1.45 V vs. RHE is 0.095 mmol / (h·cm 2The Faraday efficiency is 62.3%. Based on the above performance results, it can be seen that Example 4 (SS / FeMnCr-OH-C) 80 The HMFOR performance of ) is better than that of Comparative Example 6 (SS / FeMnCr-OH).

[0163] Application Example 5: Performance Testing of Benzyl Alcohol Electro-oxidation (BAOR)

[0164] Electrochemical tests were performed using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. The main indicators for evaluating the activity of the nanoarray materials prepared in the examples or comparative examples were: the voltage (E) required to achieve the same current density, the formation rate of the target product, and the Faraday efficiency.

[0165] Three-electrode system: The nanoarray material prepared in the examples or comparative examples is used as the working electrode (1×1cm), the Pt sheet (2×2cm) is used as the counter electrode, and the Hg / HgO electrode (immersed in 1.0M KOH solution) is used as the reference electrode. The electrolyte used is a potassium hydroxide solution containing benzyl alcohol (1M KOH + 0.01M benzyl alcohol).

[0166] Before each electrochemical data acquisition, the solution resistance (R0) of all materials was measured at the open-circuit potential. s The potential values ​​were repeatedly scanned using CV curves within the voltage range of 0.1–0.9 V vs. Hg / HgO until stable. Then, LSV tests were performed within the voltage range of 0–1.0 V vs. Hg / HgO, and the LSV curves were compensated for with 95% IR. Simultaneously, the potential value E(Hg / HgO) was converted to E(RHE) according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 × pH. Furthermore, the BAOR performance of the material was tested for 1 hour using the chronoamperometry (CA test), and the electrolyte after the CA test was quantitatively analyzed by HPLC. The specific test procedure was as follows: After the CA test, 200 μL of electrolyte was drawn using a syringe and diluted with a certain amount of deionized water. A small amount of 0.5 M H₂SO₄ was added to adjust the pH of the solution. The solution was filtered through a 0.22 μm filter membrane, and 20 μL of sample was injected into the syringe. HPLC test parameters: UV detector, C18 column, mobile phase: a mixture of methanol and 0.05M potassium dihydrogen phosphate (methanol:potassium dihydrogen phosphate = 70:30), wavelength: 250 nm, column temperature: 50℃, flow rate: 0.8 mL / min, detection time: 7 min. Qualitative analysis was subsequently performed using HPLC-MS.

[0167] This application example relates to Example 5 (CC / NiZnV-OH-C) 70) and the BAOR performance of Comparative Example 7 (CC / NiZnV-OH) was tested. The LSV results are shown in Figure 11 . As can be seen from the figure, for the BAOR performance, CC / NiZnV-OH-C 70 nanorod array material has a smaller E 200 , and E 200 vs. RHE are CC / NiZnV-OH-C 70 (1.556 V) < CC / NiZnV-OH (1.624 V), preliminarily indicating that the nanorod array material prepared in the embodiment of the present invention has better BAOR performance.

[0168] According to HPLC testing, for Example 5 (SS / FeMnCr-OH-C 80 ), the production rate of benzoic acid is 0.562 mmol / (h·cm 2 ) at 1.45 V vs. RHE, and the Faraday efficiency is 90.7%; for Comparative Example 7 (CC / NiZnV-OH), the production rate of benzoic acid is 0.325 mmol / (h·cm 2 ) at 1.45 V vs. RHE, and the Faraday efficiency is 58.6%. According to the above performance results, it can be seen that the HMFOR performance of Example 5 (CC / NiZnV-OH-C 70 ) is better than that of Comparative Example 7 (CC / NiZnV-OH).

[0169] Performance test of cyclohexanone electrooxidation reaction (CYCOR) in Application Example 6

[0170] Electrochemical tests were carried out using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N), and measurements were made using a standard three-electrode system; the main indicators for evaluating the activity of the nanorod array materials prepared in the examples or comparative examples were: the voltage (E) required to reach the same current density, the production rate of the target product, and the Faraday efficiency.

[0171] Three-electrode system: The nanorod array materials prepared in the examples or comparative examples were used as the working electrode (1×1 cm), a Pt sheet (2×2 cm) was used as the counter electrode, and a Hg / HgO electrode (immersed in 1.0 M KOH solution) was used as the reference electrode. The electrolyte used was a potassium hydroxide solution containing cyclohexanone (1 M KOH + 0.1 M cyclohexanone).

[0172] Before each electrochemical data acquisition, the solution resistance (R s) Values were repeatedly scanned for CV curves until stable within the voltage range of 0.1 - 0.9 V vs. Hg / HgO. Then, LSV tests were carried out within the voltage range of 0 - 1.0 V vs. Hg / HgO, and 95% IR compensation was performed on the LSV curve. Meanwhile, according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 × pH, the potential value E(Hg / HgO) was converted to E(RHE). In addition, the CYCOR performance of the material was tested for 4 h by chronoamperometry (CA test), and the electrolyte after CA test was quantitatively analyzed by GC. Specific test procedure: After the CA test, 2 mL of electrolyte was extracted with a syringe and injected into a certain amount of deionized water for dilution, then a small amount of 1M HCl was added to adjust the pH value of the solution, and then dichloromethane was added for extraction. The organic phase was transferred to a sample bottle, and then a small amount of Na2SO4 was added for dehydration. 2 μL of the sample was injected into the injector. GC test parameters: The detector was an FID detector, the chromatographic column was a DB-5ms capillary column, and the carrier gas was N2. The inlet temperature was 250 °C, the FID detector temperature was 300 °C, the H2 flow rate was 30 mL / min, the air flow rate was 400 mL / min, and the tail blow N2 flow rate was 25 mL / min. Subsequently, qualitative analysis was carried out by GC-MS.

[0173] This application example tested the CYCOR performance of Example 6 (AlF / NiCoSc-OH-C 60 ) and Comparative Example 8 (AlF / NiCoSc-OH). The LSV results are shown in Figure 12 . As can be seen from the figure, for the CYCOR performance, the AlF / NiCoSc-OH-C 60 nanorod array material has a smaller E 50 , and E 50 vs. RHE are AlF / NiCoSc-OH-C 60 (1.434 V) < AlF / NiCoSc-OH (1.579 V), preliminarily indicating that the nanorod array material prepared in the embodiment of the present invention has better CYCOR performance.

[0174] According to HPLC test, the adipic acid production rate of Example 6 (AlF / NiCoSc-OH-C 60 ) at 1.45 V vs. RHE is 0.068 mmol / (h·cm 2 ), and the Faraday efficiency is 90.3%; the adipic acid production rate of Comparative Example 8 (AlF / NiCoSc-OH) at 1.45 V vs. RHE is 0.042 mmol / (h·cm 2The Faraday efficiency is 57.1%. Based on the above performance results, it can be seen that Example 6 (AlF / NiCoSc-OH-C) 60 The HMFOR performance of ) is better than that of Comparative Example 8 (AlF / NiCoSc-OH).

[0175] 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 transition metal hydroxide nanoarray material, characterized in that, Includes the following steps: S1. Preparation of transition metal hydroxide nanoarrays; S2. The transition metal hydroxide nanoarray obtained in step S1 is placed in a silane coupling agent solution containing amino groups for grafting modification and post-treatment to obtain a transition metal hydroxide nanoarray material with amino-modified surface. S3. The amino-modified transition metal hydroxide nanoarray material obtained in step S2 is placed in a solvent containing fullerene for fullerene modification and post-treatment to obtain fullerene-modified transition metal hydroxide nanoarray material. The specific steps for preparing the transition metal hydroxide nanoarray are as follows: the current collector is placed in a mixed solution containing transition metal salt and precipitant, a solvothermal reaction is carried out, and post-treatment is performed to obtain the transition metal hydroxide nanoarray; The transition metal in the transition metal salt is selected from one or more of Ni, Fe, Co, Cu, Zn, Mn, Mo, V, Ce, W, Ti, Zr, Cr, Sc, and Y.

2. The preparation method according to claim 1, characterized in that, The temperature of the solvothermal reaction is 50~250 ℃.

3. The preparation method according to claim 1, characterized in that, In step S2, the amino-containing silane coupling agent is selected from at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminoethylaminomethyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminohexylaminomethyltrimethoxysilane, methylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, aminoethylaminopropylmethyldimethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, methylaminopropylmethyldiethoxysilane, and methylaminomethylmethyldiethoxysilane.

4. The preparation method according to claim 1, characterized in that, In step S2, the grafting modification temperature is 25~150 ℃.

5. The preparation method according to claim 1, characterized in that, In step S3, the fullerene is selected from C 20 C 60 C 70 C 72 C 76 C 80 C 84 C 96 At least one of them.

6. The preparation method according to claim 1, characterized in that, In step S3, the fullerene modification temperature is 20~150 °C.

7. Fullerene-modified transition metal hydroxide nanoarray materials prepared by any of the preparation methods described in claims 1 to 6.

8. The application of the fullerene-modified transition metal hydroxide nanoarray material of claim 7 in organic electro-oxidation reactions.

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