Fullerol-modified noble metal-based alloy nanocluster material, and preparation method and application thereof

Abstract

The application belongs to the technical field of electrocatalytic materials, and particularly relates to a fullerol-modified noble metal-based alloy nanocluster material and a preparation method and application thereof. The application obtains a precursor material by immersing a current collector modified with a rare earth metal oxide in a mixed solution containing fullerol and metal ions (containing at least one noble metal ion and at least one non-noble metal ion), and then performs heat treatment to obtain the fullerol-modified noble metal-based alloy nanocluster material. Alloy design cooperates with fullerol modification to endow the noble metal with an optimized electronic structure, improve electrocatalytic hydrogenation activity; surface fullerol modification is beneficial to the adsorption and enrichment of unsaturated organic substrates on the surface of the catalytic material, and improves the mass transfer efficiency. Benefiting from the above-mentioned improvement mechanism, the obtained fullerol-modified noble metal-based alloy nanocluster material exhibits excellent catalytic performance when treating unsaturated organic compounds by electrocatalytic hydrogenation, and provides a green and low-carbon approach for the resource treatment of organic wastewater.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic materials technology. More specifically, it relates to a fullerol-modified noble metal-based alloy nanocluster material, its preparation method, and its application. Background Technology

[0002] Organic wastewater is rich in various recalcitrant organic pollutants, which typically contain unsaturated bonds. Due to their high toxicity, poor biodegradability, and strong bioaccumulation, these pollutants pose a threat to ecological security and human health. Traditional treatment technologies such as adsorption, Fenton oxidation, and biodegradation suffer from secondary pollution, high energy consumption, and low treatment efficiency, and often fail to simultaneously address environmental remediation and resource recovery. Electrocatalytic hydrogenation technology, by generating adsorbed active hydrogen species (*H) on the electrode surface in situ, allows for addition reactions with the unsaturated bonds in organic pollutants, transforming organic waste (such as aromatic organic compounds) into high-value-added chemicals (such as alcohols, ketones, and amines). This not only provides a green treatment solution for organic wastewater but also achieves "waste-to-resource" transformation. In this context, the key to the widespread application of this technology lies in exploring high-performance electrocatalytic hydrogenation catalysts.

[0003] Noble metals such as Pt, Ru, and Rh are currently the most commonly used electrocatalytic hydrogenation catalysts; however, their electrocatalytic performance is still not ideal. On the one hand, the electronic structure of a single noble metal is not well-tuned, resulting in poor catalytic activity; on the other hand, organic substrates have limited solubility and low molecular diffusion coefficients in aqueous electrolytes, leading to poor mass transfer kinetics.

[0004] Therefore, developing noble metal-based electrocatalysts with optimized electronic structure and excellent mass transfer kinetics is key to breaking through the bottleneck of electrocatalytic hydrogenation technology and realizing the resource utilization of organic wastewater. Summary of the Invention

[0005] The technical problem to be solved by this invention is to address the unsatisfactory catalytic activity and mass transfer efficiency of existing electrocatalytic hydrogenation catalysts. The primary objective is to provide a method for preparing fullerol-modified noble metal-based alloy nanoclusters.

[0006] A second objective of this invention is to provide fullerol-modified noble metal-based alloy nanoclusters prepared by the aforementioned preparation method.

[0007] A third objective of this invention is to provide the application of the fullerol-modified noble metal-based alloy nanoclusters in electrocatalytic hydrogenation reactions.

[0008] The above-mentioned objective of this invention is achieved through the following technical solution:

[0009] This invention provides a method for preparing fullerol-modified noble metal-based alloy nanoclusters, comprising the following steps: S1: Preparation of rare earth metal oxide modified current collectors; S2: The rare earth metal oxide modified current collector obtained in S1 is immersed in a mixed solution containing fullerol and metal ions, and after full reaction and post-treatment, a noble metal-based alloy nanocluster precursor material modified with fullerol is obtained. S3: The precursor material obtained in S2 is placed in a protective gas atmosphere and heat-treated at 200~500 ℃ to react fully, thereby obtaining a fullerol-modified noble metal-based alloy nanocluster material. The metal ions include at least one noble metal ion and at least one non-noble metal ion.

[0010] This invention reveals that by immersing a rare-earth metal oxide-modified current collector in a mixed solution containing fullerols and metal ions (including at least one noble metal and at least one non-noble metal), a precursor material is obtained. Subsequently, heat treatment under a protective atmosphere yields a fullerol-modified noble metal-based alloy nanocluster material. Firstly, the alloy design, in conjunction with fullerol modification, imparts an optimized electronic structure to the noble metal, enhancing electrocatalytic hydrogenation activity. Furthermore, surface fullerol modification facilitates the adsorption and enrichment of unsaturated organic substrates (such as aromatic organic compounds) on the catalytic material surface, accelerating the mass transfer process. Leveraging these advantages, the obtained fullerol-modified noble metal-based alloy nanocluster material exhibits excellent electrocatalytic hydrogenation performance. This material can efficiently promote the electrocatalytic hydrogenation reaction of unsaturated organic substrates, ultimately converting them into high-value-added alcohol products or their derivatives (such as cyclohexanol, 2-methoxycyclohexanol, aniline, and other high-value-added chemicals and their derivatives). Comparative experiments have shown that if the step of modifying the current collector with rare earth metal oxides is omitted, or if other carbon nanomaterials such as graphene and carbon black are used to replace fullerol for modification, the electrocatalytic hydrogenation performance of the prepared materials will decrease significantly. This fully demonstrates that the fullerol-modified noble metal-based alloy nanoclusters prepared by the method of this application have important application potential in the field of electrocatalytic hydrogenation.

[0011] Preferably, in step S1, the rare earth metal oxide modified current collector is prepared by electrodeposition or chemical deposition.

[0012] More preferably, in step S1, the rare earth metal oxide modified current collector is prepared by electrodeposition.

[0013] More preferably, the electrodeposition method specifically includes the following steps: The current collector is immersed in a solution containing rare earth metal ions, and a rare earth metal oxide modification layer is formed on the surface of the current collector by electrodeposition. After post-processing, a rare earth metal oxide modified current collector is obtained.

[0014] Optionally, the electrodeposition method is a constant potential electrodeposition method or a constant current electrodeposition method.

[0015] Further, optionally, the constant potential electrodeposition method is performed in... 8~ Electrodeposition is performed in the 1 V vs. RHE potential range, specifically... 5~ 3 V vs. RHE.

[0016] Further optionally, the constant current electrodeposition method is performed at 1~100 mA / cm². 2 Electrodeposition is performed within a current density range; more preferably, it is 40–60 mA / cm². 2 Specifically, it can be selected as 50 mA / cm. 2 .

[0017] Preferably, the electrodeposition time is 100~800 s; more preferably, it is 120~600 s.

[0018] Preferably, the concentration of the rare earth metal ions is 0.05~1 mol / L; more preferably, it is 0.1~0.3 mol / L.

[0019] Preferably, the rare earth metal in the rare earth metal oxide is selected from at least one of Ce, Sm, Eu, and Yb.

[0020] More preferably, the rare earth metal in the rare earth metal oxide is Ce.

[0021] Optionally, the solution containing rare earth metal ions is a rare earth metal salt solution.

[0022] Preferably, the rare earth metal salt is a cerium salt.

[0023] Preferably, the cerium salt is at least one selected from nitrate, acetate, chloride, carbonate, and sulfate.

[0024] Preferably, the post-processing includes washing and drying.

[0025] Optionally, the washing process involves washing with anhydrous ethanol 1 to 3 times, specifically once.

[0026] Optionally, the drying process is carried out at 40-80 °C for 6-48 h; specifically, it can be carried out at 60 °C for 12 h.

[0027] Preferably, in step S1, the current collector is selected from at least one of carbon cloth, carbon paper, or metal current collector.

[0028] More preferably, the metal current collector is selected from at least one of Fe, Co, Ni, Zn, Al, Ti, and stainless steel.

[0029] Optionally, the metal current collector may be in the form of at least one of metal foam, metal foil, metal plate or metal mesh.

[0030] Specifically, in step S2, the fullerol is C 20+2k (OH) m k is an integer ≥ 0.

[0031] Preferably, in step S2, the number of carbon atoms in the fullerol is 20+2k, where k is an integer of 20≤k≤32.

[0032] More preferably, in step S2, the fullerol is C 60 Type Fullerol, C 70 Type Fullerol, C 76 Type Fullerol, C 84 At least one of the fullerols.

[0033] Preferably, in step S2, the concentration of fullerol is 0.5~8 mmol / L; more preferably, it is 1~5 mmol / L.

[0034] Furthermore, the fullerol is prepared by commercial purchase or in-house preparation.

[0035] As an optional implementation, when prepared in-house, the fullerol is obtained from fullerene via an alkaline-catalyzed oxidation method, comprising the following steps: (1) Disperse fullerene in an organic solvent, add an alkaline solution, and allow it to react fully to obtain a mixed solution; (2) Add a phase transfer catalyst and an oxidant to the mixed solution in step (1), react fully, and then perform post-treatment to obtain the fullerol.

[0036] Optionally, in step (1) of the alkaline catalytic oxidation method, the organic solvent is selected from at least one of toluene, xylene, chlorobenzene, o-dichlorobenzene, carbon tetrachloride, and carbon disulfide.

[0037] Optionally, in step (1) of the alkaline catalytic oxidation method, the alkaline solution is selected from at least one of sodium hydroxide solution and potassium hydroxide solution.

[0038] Preferably, in step (1) of the alkaline catalytic oxidation method, the ratio of the fullerene to the organic solvent is (20~40) mg:100 mL; more preferably, it is 30 mg:100 mL.

[0039] Preferably, in step (1) of the alkaline catalytic oxidation method, the mass ratio of the alkaline solution to fullerene is 1:(50~100); more preferably, it is 1:(80~85).

[0040] Optionally, in step (2) of the alkaline catalytic oxidation method, the phase transfer catalyst includes tetrabutylammonium hydroxide.

[0041] Optionally, in step (2) of the alkaline catalytic oxidation method, the oxidant includes hydrogen peroxide.

[0042] Preferably, in step (2) of the alkaline catalytic oxidation method, the ratio of the amount of phase transfer catalyst added per hour to the amount of fullerene is (100~150) mg:1 mL; more preferably, it is 120 mg:1 mL.

[0043] Preferably, in step (2) of the alkaline catalytic oxidation method, the volume ratio of the phase transfer catalyst to the oxidant is (1~2):(1~2); more preferably, it is 1:1.

[0044] Optionally, in step (2) of the alkaline catalytic oxidation method, the post-treatment includes centrifugation and washing.

[0045] Specifically, in step (2) of the alkaline catalytic oxidation method, the washing is performed by washing with anhydrous ethanol 3 to 5 times, optionally 5 times.

[0046] Under alkaline conditions, OH - As a nucleophile, it attacks the double bond of fullerene to generate a hydroxyl addition product. Due to the high symmetry and reactivity of the carbon atoms in fullerene, the hydroxyl addition process lacks site selectivity, resulting in a mixed system of fullerol homologues with different numbers of hydroxyl groups (the number of hydroxyl groups m of fullerols is continuously distributed) rather than a compound with a single defined structure. Moreover, it is difficult to completely separate them by conventional separation methods (such as chromatography and crystallization). Therefore, the number of hydroxyl groups of fullerols cannot be accurately determined, so it is represented by m.

[0047] Optionally, in step S2, the metal ions in the mixed solution containing fullerol and metal ions may be derived from metal salts.

[0048] Preferably, in step S2, the concentration of the metal ions is 2~30 mmol / L; more preferably, it is 5~20 mmol / L.

[0049] Preferably, the metal salt is selected from at least one of chloride, ammonium, nitrate, sulfate, and sodium salts.

[0050] Preferably, in step S2, the solvent of the mixed solution containing fullerol and metal ions is selected from at least one of water, methanol, ethanol, propanol, butanol, isopropanol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,2,4-butanetriol, 1,6-hexanediol, pentanediol, glycerol, benzyl alcohol, cyclohexanol, acetone, diethylene glycol, triethylene glycol, acetonitrile, methyl acetate, and ethyl acetate.

[0051] Preferably, the noble metal element of the noble metal ion is selected from at least one of Pt, Ru, Rh, Pd, Ir, and Au.

[0052] More preferably, the noble metal element of the noble metal ion is selected from at least one of Ru, Rh, Pd, Pt, and Au.

[0053] More preferably, the noble metal element of the noble metal ion is selected from any one of Ru, Rh, Pd, Pt, and Au.

[0054] Preferably, the metal element in the non-noble metal ion is selected from at least one of Ni, Fe, Co, Cu, Zn, Mo, V, W, Ti, Zr, Cr, Sc, and Y.

[0055] More preferably, the metal element in the non-noble metal ion is selected from at least one of Ni, Fe, Co, Cu, Zn, Mo, W, and Cr.

[0056] More preferably, the metal element in the non-noble metal ion is selected from any one or any two of Ni, Fe, Co, Cu, Zn, Mo, W, and Cr.

[0057] Preferably, in step S2, the molar ratio of the metal element in the metal ion, the noble metal ion and the non-noble metal ion is (0.05~15):1; more preferably, it is (0.1~9):1.

[0058] Preferably, in step S2, the reaction temperature is 20~100 ℃; more preferably, it is 40~80 ℃.

[0059] Preferably, in step S2, the reaction time is 2 to 15 hours; more preferably, it is 4 to 12 hours.

[0060] Preferably, in step S2, the post-processing includes washing and drying.

[0061] Optionally, the washing process involves washing with water and anhydrous ethanol 1 to 3 times in sequence, specifically washing with water twice and then washing with anhydrous ethanol once.

[0062] Optionally, the drying process involves drying at 60-100°C for 8-16 hours, specifically at 80°C for 12 hours.

[0063] Preferably, in step S3, the protective gas is selected from at least one of nitrogen (N2), argon (Ar), and helium (He).

[0064] More preferably, in step S3, the protective gas is selected from nitrogen and / or argon.

[0065] Preferably, in step S3, the temperature of the heat treatment is 300~400 ℃.

[0066] Preferably, in step S3, the flow rate of the protective gas is 5~20 mL / min; more preferably, it is 10~15 mL / min.

[0067] Preferably, in step S3, the heat treatment heating rate is 1~10 ℃ / min; more preferably, the heat treatment heating rate is 3~8 ℃ / min.

[0068] Preferably, in step S3, the heat treatment time is 1 to 5 hours, more preferably 1.5 to 3 hours.

[0069] The present invention also provides fullerol-modified noble metal-based alloy nanoclusters prepared by the preparation method described above.

[0070] The present invention also provides the application of the fullerol-modified noble metal-based alloy nanoclusters in electrocatalytic hydrogenation reactions.

[0071] Furthermore, the electrocatalytic hydrogenation (ECH) reaction is a process in which active hydrogen species (*H) on the surface of a catalytic electrode are used to add to and reduce organic compounds containing unsaturated chemical bonds under the assistance of an electric field.

[0072] Optionally, the unsaturated bonds include carbon-carbon double bonds (C=C), carbon-carbon triple bonds (C≡C), carbon-nitrogen double bonds (C=N), carbonyl groups (C=O), and nitrogen-oxygen double bonds (N=O).

[0073] Specifically, the organic compound containing unsaturated chemical bonds may be a phenolic compound, such as phenol, guaiacol, 2,4-dichlorophenol, or nitrobenzene.

[0074] The present invention has the following beneficial effects: This invention involves immersing a rare-earth metal oxide-modified current collector in a mixed solution containing fullerols and metal ions (including at least one noble metal ion and at least one non-noble metal ion) to obtain a precursor material. This precursor material is then heat-treated under a protective atmosphere to yield a fullerol-modified noble metal-based alloy nanocluster material. The synergistic effect of alloy design and fullerol modification endows the noble metal with an optimized electronic structure, enhancing electrocatalytic hydrogenation activity. Simultaneously, the surface-modified fullerols facilitate the adsorption and enrichment of organic substrates on the catalytic material surface, thereby improving mass transfer efficiency. With the dual enhancement of reaction kinetics and mass transfer kinetics, this material exhibits excellent catalytic performance in the electrocatalytic hydrogenation treatment of unsaturated organic compounds, providing a green and low-carbon pathway for the resource-based treatment of organic wastewater. Attached Figure Description

[0075] Figure 1 C obtained in Example 1 84 Scanning electron microscope (SEM) image of ruthenium-tungsten alloy nanoclusters modified with fullerol.

[0076] Figure 2 The image shows the X-ray diffraction (XRD) pattern of CeO2 obtained by electrodeposition in Example 1.

[0077] Figure 3 C obtained in Example 2 84 SEM image of rhodium-nickel alloy nanoclusters modified with fullerol.

[0078] Figure 4 C obtained in Example 3 76 SEM image of palladium-iron alloy nanoclusters modified with fullerol.

[0079] Figure 5 C obtained in Example 4 70 SEM image of ruthenium cobalt copper alloy nanoclusters modified with fullerol.

[0080] Figure 6 C obtained in Example 5 60 SEM image of platinum-zinc-molybdenum alloy nanoclusters modified with type-fullerol.

[0081] Figure 7 C obtained in Example 6 60 SEM image of gold cobalt chromium alloy nanoclusters modified with fullerol.

[0082] Figure 8 The image shows the Linear Sweep Voltammetry (LSV) results of the electrocatalytic hydrogenation (ECH) of nanocluster materials in Example 1 and Comparative Examples 1, 2, 3, and 4 at room temperature.

[0083] Figure 9 The LSV plots of ECH for Example 2 and Comparative Example 5 nano-cluster materials at room temperature are shown.

[0084] Figure 10 The LSV plots of ECH for Example 3 and Comparative Example 6 nano-cluster materials at room temperature are shown.

[0085] Figure 11 The LSV plots of ECH for Example 4 and Comparative Example 7 nanocluster materials at room temperature are shown.

[0086] Figure 12 The LSV plots of ECH for Example 5 and Comparative Example 8 nanocluster materials at room temperature are shown.

[0087] Figure 13 The LSV plots of ECH for Example 6 and Comparative Example 9 nano-cluster materials at room temperature are shown. Detailed Implementation

[0088] 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.

[0089] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0090] Provide the source of the fullerenes used in this application (including the manufacturer and product number): C 84 Type II fullerene: Zhongke Leiming, catalog number ZKC05-1; C 76 Fullerene type: Shanghai Maclean, item number F708705; C 70 Fullerene type: Shanghai Maclean, item number F809595; C 60 Fullerene type: Shanghai Maclean, item number F708343; Carbon black: Shanghai Maclean, item number 1333-86-4; Graphene: Shanghai McLean, item number S992593; Different types of fullerols are prepared by hydroxylation of corresponding types of fullerenes, as follows: 30 mg C 84Fullerene of type C was dispersed in 100 mL of toluene, followed by the addition of 5 mL of an aqueous solution containing 2.5 g NaOH, and stirred vigorously at room temperature. Then, 0.25 mL of tetrabutylammonium hydroxide and 0.25 mL of hydrogen peroxide were added hourly until the toluene became colorless, and stirring was continued for 12 h. The reaction solution was centrifuged, and the resulting solid was washed five times with anhydrous ethanol to obtain C... 84 Fullerol type.

[0091] Under alkaline conditions, OH - As a nucleophile, it attacks the double bond of fullerenes, generating hydroxyl addition products. Due to the high symmetry of the carbon atoms in fullerenes, the hydroxyl addition process lacks site selectivity, resulting in a mixed system of fullerol homologues with different numbers of hydroxyl groups (the number of hydroxyl groups m in fullerols exhibits a continuous distribution), rather than a single compound with a defined structure. Furthermore, it is difficult to completely separate them using conventional methods (such as chromatography and crystallization), thus the average number of hydroxyl groups in fullerols cannot be accurately quantified. To facilitate the calculation of the amount of fullerol used, the number of hydroxyl groups is estimated based on a carbon-to-hydroxyl ratio of 5:2, and the molar mass of fullerol is determined accordingly.

[0092] Example 1 C 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters (CC / CeO2-C) 84 (OH) m -RuW) The C 84 The preparation method of ruthenium-tungsten alloy nanoclusters modified with fullerol includes the following steps: (1) Carbon cloth (CC) was used as the working electrode and immersed in 50 mL of 0.1 M Ce(NO3)3·6H2O aqueous solution, with Ag / AgCl reference electrode and platinum sheet as the counter electrode, at 50 mA / cm 2 The current density was maintained at 600 s for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 ℃ for 12 h to finally obtain the CC / CeO2 current collector; (2) Place the CC / CeO2 obtained in step (1) in 50 mL of 1 mM (0.08 g) C solution with water as the solvent. 84 (OH) m 3 mM LuCl3·3H2O and 2 mM (NH4) 10 In a mixed solution of H2(W2O7)6, the mixture was stirred at 40 °C for 6 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain C. 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters precursor material; (3) Take the C obtained in step (2) 84Fullerol-modified ruthenium-tungsten alloy nanoclusters precursor material was placed in a tube furnace. The N2 flow rate was controlled at 10 mL / min, and the temperature was increased from room temperature to 300 °C at a rate of 5 °C / min. The material was then heat-treated at 300 °C for 1.5 h, followed by natural cooling to obtain C2. 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters (CC / CeO2-C) 84 (OH) m -RuW); Material characterization: The obtained product was characterized by SEM morphology. Figure 1 It can be seen that the C loaded on CC / CeO2 84 Ruthenium-tungsten alloy nanoclusters modified with fullerol.

[0093] The CC / CeO2 current collector obtained by electrodeposition was characterized by XRD to determine its crystal structure. Figure 2 It can be seen that the diffraction peaks can be well assigned to CeO2 (PDF # 34-0394).

[0094] Example 2 C 84 Fullerol-modified rhodium-nickel alloy nanoclusters (NF / CeO2-C) 84 (OH) m -RhNi) The C 84 The preparation method of rhodium-nickel alloy nanoclusters modified with fullerol includes the following steps: (1) Nickel foam (NF) was immersed in 50 mL of 0.2 M (CH3COO)3Ce·xH2O aqueous solution as the working electrode, and an Ag / AgCl reference electrode and a platinum sheet counter electrode were used. The reaction was carried out at a potential of 3 V vs. RHE for 120 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 °C for 12 h to finally obtain the NF / CeO2 current collector.

[0095] (2) Place the NF / CeO2 obtained in step (1) in a 50 mL container of 3 mM (0.239 g) C solution containing water and methanol (volume ratio 1:1). 84 (OH) m The solution was stirred at 60 °C for 4 h in a mixed solution of 6 mM RhCl3·3H2O and 2 mM Ni(NO3)2·6H2O. The solution was then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain C. 84 Rhodium-nickel alloy nanocluster precursor materials modified with type fullerol; (3) Take the C obtained in step (2) 84Rhodium-nickel alloy nanoclusters modified with type-fullerol were placed in a tube furnace. The Ar flow rate was controlled at 15 mL / min, and the temperature was increased from room temperature to 400 °C at a rate of 8 °C / min. The mixture was then heat-treated at 400 °C for 2 h, followed by natural cooling to obtain C2. 84 Fullerol-modified rhodium-nickel alloy nanoclusters (NF / CeO2-C) 84 (OH) m -RhNi).

[0096] Material characterization: The obtained product was characterized by SEM morphology. Figure 3 It can be seen that the C loaded on NF / CeO2 84 Rhodium-nickel alloy nanoclusters modified with fullerol.

[0097] Example 3 C 76 Fullerol-modified palladium-iron alloy nanoclusters (IF / CeO2-C) 76 (OH) m -PdFe) The C 76 The preparation method of palladium-iron alloy nanoclusters modified with fullerol includes the following steps: (1) Immerse the foamed iron (IF) as the working electrode in 50 mL of 0.3 M (CH3COO)3Ce·xH2O aqueous solution, and use an Ag / AgCl reference electrode and a platinum sheet as the counter electrode. The reaction was carried out at a potential of 5 V vs. RHE for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 °C for 12 h to finally obtain the IF / CeO2 current collector.

[0098] (2) Place the IF / CeO2 obtained in step (1) in a 50 mL container of 5 mM (0.356 g) C solution containing water and acetonitrile (volume ratio 1:1). 76 (OH) m The solution was stirred at 60 °C for 6 h in a mixed solution of 12 mM Pd(NO3)2 and 3 mM Fe(NO3)3·9H2O, followed by washing twice with deionized water and once with anhydrous ethanol, and then drying in a forced-air drying oven at 80 °C for 12 h to obtain C. 76 Palladium-iron alloy nanocluster precursor material modified with fullerol; (3) Take the C obtained in step (2) 76 Fullerol-modified palladium-iron alloy nanoclusters precursor material was placed in a tube furnace, with N2 flow rate controlled at 10 mL / min, and the temperature was increased from room temperature to 400 ℃ at a heating rate of 3 ℃ / min. The material was then heat-treated at 400 ℃ for 3 h, followed by natural cooling to obtain C2.76 Fullerol-modified palladium-iron alloy nanoclusters (IF / CeO2-C) 76 (OH) m -PdFe).

[0099] Material characterization: The obtained product was characterized by SEM morphology. Figure 4 It can be seen that the C loaded on IF / CeO2 76 Palladium-iron alloy nanoclusters modified with fullerol.

[0100] Example 4 C 70 Ruthenium cobalt copper alloy nanoclusters modified with fullerol (SS / CeO2-C) 70 (OH) m -RuCoCu) The C 70 The preparation method of ruthenium-cobalt-copper alloy nanoclusters modified with fullerol includes the following steps: (1) Stainless steel (SS) was used as the working electrode and immersed in 50 mL of 0.3 M CeCl3·7H2O aqueous solution, with an Ag / AgCl reference electrode and a platinum sheet as the counter electrode, at 50 mA / cm 2 The current density was maintained at 600 s for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 °C for 12 h to finally obtain the SS / CeO2 current collector; (2) Place the SS / CeO2 obtained in step (1) in 50 mL of 4 mM (0.263 g) C solution with water as the solvent. 70 (OH) m The solution was stirred at 80 °C for 4 h in a mixed solution of 12 mM RuCl3·3H2O, 2 mM CoCl2·6H2O, and 2 mM CuSO4·5H2O. The solution was then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain C. 70 Fullerol-modified ruthenium cobalt copper alloy nanocluster precursor materials; (3) Take the C obtained in step (2) 70 Fullerol-modified ruthenium-cobalt-copper alloy nanoclusters were placed in a tube furnace. The Ar flow rate was controlled at 10 mL / min, and the temperature was increased from room temperature to 300 °C at a rate of 5 °C / min. The mixture was then heat-treated at 300 °C for 3 h, followed by natural cooling to obtain C2. 70 Ruthenium cobalt copper alloy nanoclusters modified with fullerol (SS / CeO2-C) 70 (OH) m -RuCoCu).

[0101] Material characterization: The obtained product was characterized by SEM morphology. Figure 5 It can be seen that the C loaded on SS / CeO2 70 Ruthenium-cobalt-copper alloy nanoclusters modified with fullerol.

[0102] Example 5 C 60 Fullerol-modified platinum-zinc-molybdenum alloy nanoclusters (CC / CeO2-C) 60 (OH) m -PtZnMo) The C 60 The preparation method of type-fullerol modified platinum-zinc-molybdenum alloy nanoclusters includes the following steps: (1) Immerse CC as the working electrode in 50 mL of 0.2 M Ce(NO3)3·6H2O aqueous solution, and use Ag / AgCl reference electrode and platinum sheet counter electrode. The reaction was carried out at a potential of 5 V vs. RHE for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 °C for 12 h to finally obtain the CC / CeO2 current collector; (2) Place the CC / CeO2 obtained in step (1) in 50 mL of 5 mM (0.282 g) C solution with water as the solvent. 60 (OH) m The solution was stirred at 40 °C for 12 h in a mixed solution of 18 mM H₂PtCl₆·6H₂O, 1 mM ZnSO₄·H₂O, and 1 mM Na₂MoO₄. The solution was then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain C. 60 Fullerol-modified platinum-zinc-molybdenum alloy nanocluster precursor materials; (3) Take the C obtained in step (2) 60 The fullerol-modified platinum-zinc-molybdenum alloy nanocluster precursor material was placed in a tube furnace, with the N2 flow rate controlled at 10 mL / min, and the temperature was increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min. After heat treatment at 300 ℃ for 3 h, and then allowed to cool naturally, C was obtained. 60 Fullerol-modified platinum-zinc-molybdenum alloy nanoclusters (CC / CeO2-C) 60 (OH) m -PtZnMo).

[0103] Material characterization: The obtained product was characterized by SEM morphology. Figure 6 It can be seen that the C loaded on CC / CeO2 60 Platinum-zinc-molybdenum alloy nanoclusters modified with fullerol.

[0104] Example 6 C 60 Fullerol-modified gold cobalt chromium alloy nanoclusters (CC / CeO2-C) 60 (OH) m -AuCoCr) The C 60 The preparation method of gold-cobalt-chromium alloy nanoclusters modified with fullerol includes the following steps: (1) Immerse CC as the working electrode in 50 mL of 0.2 M Ce(NO3)3·6H2O aqueous solution, and use Ag / AgCl reference electrode and platinum sheet counter electrode. The reaction was carried out at a potential of 5 V vs. RHE for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 °C for 12 h to finally obtain the CC / CeO2 current collector; (2) Place the CC / CeO2 obtained in step (1) in 50 mL of 3 mM (0.170 g) C solution with water as the solvent. 60 (OH) m The solution was prepared by stirring in a mixed solution of 10 mM HAuCl4·3H2O, 1 mM Co(NO3)2·6H2O, and 1 mM CrCl3·6H2O at 40 °C for 12 h. The solution was then washed twice with deionized water and once with anhydrous ethanol, and finally dried in a forced-air drying oven at 80 °C for 12 h to obtain C. 60 Gold-cobalt-chromium alloy nanocluster precursor material modified with type fullerol; (3) Take the C obtained in step (2) 60 Fullerol-modified gold-cobalt-chromium alloy nanoclusters precursor material was placed in a tube furnace, with N2 flow rate controlled at 10 mL / min, and the temperature was increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min. The material was then heat-treated at 300 ℃ for 3 h, followed by natural cooling to obtain C. 60 Fullerol-modified gold cobalt chromium alloy nanoclusters (CC / CeO2-C) 60 (OH) m -AuCoCr).

[0105] Material characterization: The obtained product was characterized by SEM morphology. Figure 7 It can be seen that the load C on CC / CeO2 60 Gold-cobalt-chromium alloy nanoclusters modified with fullerol.

[0106] Comparative Example 1: Carbon-modified ruthenium-tungsten alloy nanoclusters (CC / CeO2-Carbon-RuW) Compared to Example 1, Comparative Example 1 differs in that C was not performed.84 Instead of surface modification with fullerol, an equal mass of carbon black was used for modification.

[0107] Specifically, the preparation method of the Carbon-modified ruthenium-tungsten alloy nanoclusters includes the following steps: (1) The CC electrode was immersed in 50 mL of 0.1 M Ce(NO3)3·6H2O aqueous solution as the working electrode, and an Ag / AgCl reference electrode and a platinum sheet counter electrode were used. The electrode was subjected to a flow rate of 50 mA / cm. 2 The current density was maintained at 600 s for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 ℃ for 12 h to finally obtain the CC / CeO2 current collector; (2) Place the CC / CeO2 obtained in step (1) into 50 mL (0.08 g) Carbon, 3 mM LuCl3·3H2O and 2 mM (NH4) solvent. 10 In a mixed solution of H2(W2O7)6, the mixture was stirred at 40 °C for 6 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain a Carbon-modified ruthenium-tungsten alloy nanocluster precursor material. (3) The Carbon-modified ruthenium-tungsten alloy nanocluster precursor material obtained in step (2) was placed in a tube furnace, the N2 flow rate was controlled at 10 mL / min, the temperature was increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min, and the material was heat-treated at 300 ℃ for 1.5 h. After natural cooling, the Carbon-modified ruthenium-tungsten alloy nanocluster material (CC / CeO2-Carbon-RuW) was obtained.

[0108] Comparative Example 2: Graphene-modified ruthenium-tungsten alloy nanoclusters (CC / CeO2-Graphene-RuW) Compared to Example 1, Comparative Example 2 differs in that C was not performed. 84 Instead of surface modification with fullerols, the same mass of graphene was used for modification.

[0109] Specifically, the preparation method of the graphene-modified ruthenium-tungsten alloy nanoclusters includes the following steps: (1) The CC electrode was immersed in 50 mL of 0.1 M Ce(NO3)3·6H2O aqueous solution as the working electrode, and an Ag / AgCl reference electrode and a platinum sheet counter electrode were used. The electrode was subjected to a flow rate of 50 mA / cm. 2The current density was maintained at 600 s for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol and dried, and then dried at 60 ℃ for 12 h to finally obtain the CC / CeO2 current collector; (2) Place the CC / CeO2 obtained in step (1) into 50 mL (0.08 g) of Graphene, 3 mM LuCl3·3H2O and 2 mM (NH4) in a solution of water. 10 In a mixed solution of H2(W2O7)6, the mixture was stirred at 40 °C for 6 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain a Graphene-modified ruthenium-tungsten alloy nanocluster precursor material. (3) The graphene-modified ruthenium-tungsten alloy nanocluster precursor material obtained in step (2) was placed in a tube furnace, the N2 flow rate was controlled at 10 mL / min, the temperature was increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min, and the material was heat-treated at 300 ℃ for 1.5 h. After natural cooling, the carbon-modified ruthenium-tungsten alloy nanocluster material (CC / CeO2-Graphene-RuW) was obtained.

[0110] Comparative Example 3: Ruthenium-tungsten alloy nanoclusters (CC / CeO2-RuW) Compared to Example 1, Comparative Example 3 differs in that C was not performed. 84 Surface modification of fullerols.

[0111] Specifically, the preparation method of the ruthenium-tungsten alloy nanocluster material includes the following steps: (1) The CC electrode was immersed in 50 mL of 0.1 M Ce(NO3)3·6H2O aqueous solution as the working electrode, and an Ag / AgCl reference electrode and a platinum sheet counter electrode were used. The electrode was subjected to a flow rate of 50 mA / cm. 2 The current density was maintained at 600 s for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol and dried, and then dried at 60 ℃ for 12 h to finally obtain the CC / CeO2 current collector; (2) Place the CC / CeO2 obtained in step (1) in 50 mL of 3 mM RuCl3·3H2O and 2 mM (NH4) solution with water as solvent. 10 In a mixed solution of H2(W2O7)6, the mixture was stirred at 40 °C for 6 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain ruthenium-tungsten alloy nanocluster precursor material. (3) The ruthenium-tungsten alloy nanocluster precursor material obtained in step (2) is placed in a tube furnace, the N2 flow rate is controlled at 10 mL / min, the temperature is increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min, and the heat treatment is carried out at 300 ℃ for 1.5 h. After natural cooling, the ruthenium-tungsten alloy nanocluster material (CC / CeO2-RuW) is obtained.

[0112] Comparative Example 4: C without CeO2 substrate support 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters (CC / C) 84 (OH) m -RuW) Compared with Example 1, the difference in Comparative Example 4 is that the current collector was not modified with CeO2.

[0113] Specifically, the C without CeO2 substrate support 84 The preparation method of ruthenium-tungsten alloy nanoclusters modified with fullerol includes the following steps: (1) Place CC in 50 mL of 1 mM (0.080 g) C solution with water as the solvent. 84 (OH) m 3 mM RuCl3·3H2O and 2 mM (NH4) 10 In a mixed solution of H2(W2O7)6, the mixture was stirred at 40 °C for 6 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain C without CeO2 substrate support. 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters precursor material; (2) The C without CeO2 substrate support obtained in step (1) 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters precursor material was placed in a tube furnace. The N2 flow rate was controlled at 10 mL / min, and the temperature was increased from room temperature to 300 °C at a rate of 5 °C / min. The mixture was then heat-treated at 300 °C for 1.5 h, followed by natural cooling to obtain CeO2-free C-type alloy nanoclusters. 84 Fullerol-modified ruthenium-tungsten alloy nanoclusters (CC / C) 84 (OH) m -RuW).

[0114] Comparative Example 5: Rhodium-nickel alloy nanocluster material (NF / CeO2-RhNi) Compared to Example 2, Comparative Example 5 differs in that C was not performed. 84 Modification of fullerol.

[0115] Specifically, the preparation method of the rhodium-nickel alloy nanocluster material includes the following steps: (1) Immerse NF as the working electrode in 50 mL of 0.2 M (CH3COO)3Ce·xH2O aqueous solution, and use Ag / AgCl reference electrode and platinum sheet counter electrode. The reaction was carried out at a potential of 3 V vs. RHE for 120 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol and dried, and then dried at 60 °C for 12 h to finally obtain the NF / CeO2 current collector.

[0116] (2) The NF / CeO2 obtained in step (1) was placed in a 50 mL mixed solution of 6 mM MRhCl3·3H2O and 2 mM Ni(NO3)2·6H2O in water and methanol (volume ratio 1:1) as solvents, stirred at 60 °C for 4 h, then washed twice with deionized water and once with anhydrous ethanol, and dried at 80 °C in a forced-air drying oven for 12 h to obtain the rhodium-nickel alloy nanocluster precursor material; (3) Place the rhodium-nickel alloy nanocluster precursor material obtained in step (2) in a tube furnace, A r The flow rate was controlled at 15 mL / min, and the temperature was increased from room temperature to 400 ℃ at a heating rate of 8 ℃ / min. After heat treatment at 400 ℃ for 2 h, and then cooled naturally, rhodium-nickel alloy nanocluster material (NF / CeO2-RhNi) was obtained.

[0117] Comparative Example 6: Palladium-iron alloy nanoclusters (IF / CeO2-PdFe) Compared to Example 3, Comparative Example 6 differs in that C was not performed. 76 Modification of fullerol.

[0118] Specifically, the preparation method of the palladium-iron alloy nanocluster material includes the following steps: (1) Immerse IF as the working electrode in 50 mL of 0.3 M (CH3COO)3Ce·xH2O aqueous solution, with an Ag / AgCl reference electrode and a platinum sheet as the counter electrode. The reaction was carried out at a potential of 5 V vs. RHE for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol and dried, and then dried at 60 °C for 12 h to finally obtain the IF / CeO2 current collector.

[0119] (2) The IF / CeO2 obtained in step (1) was placed in a 50 mL mixed solution of 12 mM MPd(NO3)2 and 3 mM Fe(NO3)3·9H2O in water and acetonitrile (volume ratio 1:1), stirred at 60 °C for 6 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain palladium-iron alloy nanocluster precursor material; (3) The palladium-iron alloy nanocluster precursor material obtained in step (2) is placed in a tube furnace, the N2 flow rate is controlled at 10 mL / min, the temperature is increased from room temperature to 400 ℃ at a heating rate of 3 ℃ / min, and heat-treated at 400 ℃ for 3 h. After natural cooling, palladium-iron alloy nanocluster material (IF / CeO2-PdFe) is obtained.

[0120] Comparative Example 7: Ruthenium-Cobalt-Copper Alloy Nanoclusters (SS / CeO2-RuCoCu) Compared to Example 4, Comparative Example 7 differs in that C was not performed. 70 Modification of fullerol.

[0121] Specifically, the preparation method of the ruthenium-cobalt-copper alloy nanocluster material includes the following steps: (1) The SS was used as the working electrode and immersed in 50 mL of 0.3 M CeCl3·7H2O aqueous solution, with an Ag / AgCl reference electrode and a platinum sheet as the counter electrode, at 50 mA / cm 2 The current density was maintained at 600 s for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol and dried, and then dried at 60 ℃ for 12 h to finally obtain the SS / CeO2 current collector; (2) The SS / CeO2 obtained in step (1) was placed in a 50 mL mixed solution of 12 mM RuCl3·3H2O, 2 mM CoCl2·6H2O and 2 mM CuSO4·5H2O with water as solvent, stirred at 80 °C for 4 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain ruthenium cobalt copper alloy nanocluster precursor material; (3) The ruthenium cobalt copper alloy nanocluster precursor material obtained in step (2) was placed in a tube furnace, the Ar flow rate was controlled at 10 mL / min, the temperature was increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min, and the heat treatment was carried out at 300 ℃ for 3 h. After natural cooling, the ruthenium cobalt copper alloy nanocluster material (SS / CeO2-RuCoCu) was obtained.

[0122] Comparative Example 8: Platinum-Zinc-Mo alloy nanocluster material (CC / CeO2-PtZnMo) Compared to Example 5, Comparative Example 8 differs in that C was not performed. 60 Modification of fullerol.

[0123] Specifically, the preparation method of the platinum-zinc-molybdenum alloy nanocluster material includes the following steps: (1) Immerse CC as the working electrode in 50 mL of 0.2 M Ce(NO3)3·6H2O aqueous solution, and use Ag / AgCl reference electrode and platinum sheet counter electrode. The reaction was carried out at a potential of 5 V vs. RHE for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol and dried, and then dried at 60 °C for 12 h to finally obtain the CC / CeO2 current collector; (2) The CC / CeO2 obtained in step (1) was placed in a 50 mL mixed solution of 18 mM H2PtCl6·6H2O, 1 mM ZnSO4·H2O and 1 mM Na2MoO4 with water as solvent, stirred at 40 °C for 12 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain the platinum-zinc-molybdenum alloy nanocluster precursor material; (3) The platinum-zinc-molybdenum alloy nanocluster precursor material obtained in step (2) is placed in a tube furnace, the N2 flow rate is controlled at 10 mL / min, the temperature is increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min, and the heat treatment is carried out at 300 ℃ for 3 h. After natural cooling, the platinum-zinc-molybdenum alloy nanocluster material (CC / CeO2-PtZnMo) is obtained.

[0124] Comparative Example 9: Gold-Cobalt-Chromium Alloy Nanoclusters (CC / CeO2-AuCoCr) Compared to Example 6, Comparative Example 9 differs in that C was not performed. 60 Modification of fullerol.

[0125] Specifically, the preparation method of the gold-cobalt-chromium alloy nanocluster material includes the following steps: (1) Immerse CC as the working electrode in 50 mL of 0.2 M Ce(NO3)3·6H2O aqueous solution, and use Ag / AgCl reference electrode and platinum sheet counter electrode. The reaction was carried out at a potential of 5 V vs. RHE for 600 s. After the reaction was completed, the electrode was removed, washed with anhydrous ethanol, and dried at 60 °C for 12 h to finally obtain the CC / CeO2 current collector; (2) The CC / CeO2 obtained in step (1) was placed in a mixed solution of 50 mL of 10 mM HAuCl4·3H2O, 1 mM Co(NO3)2·6H2O and 1 mM CrCl3·6H2O with water as solvent, stirred at 40 °C for 12 h, then washed twice with deionized water and once with anhydrous ethanol, and dried in a forced-air drying oven at 80 °C for 12 h to obtain gold cobalt chromium alloy nanocluster precursor material; (3) The gold cobalt chromium alloy nanocluster precursor material obtained in step (2) was placed in a tube furnace, the N2 flow rate was controlled at 10 mL / min, the temperature was increased from room temperature to 300 ℃ at a heating rate of 5 ℃ / min, and the temperature was heat-treated at 300 ℃ for 3 h. After natural cooling, the gold cobalt chromium alloy nanocluster material (CC / CeO2-AuCoCr) was obtained.

[0126] Application Example 1: Performance Testing of Electrocatalytic Hydrogenation of Phenol Electrochemical measurements were performed using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. Key performance indicators for evaluating the activity of the nanoclusters prepared in the examples or comparative cases included a current density reaching 30 mA / cm². 2 Required voltage (E) 30 (The lower the absolute value of the voltage, the better the electrocatalytic activity), conversion rate of phenolic pollutants, formation rate of target products, and Faraday efficiency.

[0127] Nanoclusters prepared according to examples or comparative examples (cut into 1×1 cm) 2 The electrocatalytic performance of the samples was studied in a three-electrode system with a Pt sheet (1×1 cm) as the working electrode, an Ag / AgCl electrode (immersed in 3.0 M KCl solution) as the reference electrode. The electrolyte used was a perchloric acid solution containing phenol (0.2 M HClO4 + 10 mM phenol, pH=0.67).

[0128] Before each electrochemical data acquisition, the solution resistance (R0) of all materials was measured at the open-circuit potential. s The values ​​are all in 0.60 ~ The CV curve was repeatedly swept within the voltage range of 0.1 V vs. Ag / AgCl until it stabilized, and then... 0.60 ~ LSV testing was performed within a voltage range of 0.1 V vs. Ag / AgCl, and the LSV curve was 95% IR compensated. The potential value E(Ag / AgCl) was converted to E(RHE) according to the formula E(RHE) = E(Ag / AgCl) + 0.197 + 0.0591 × pH. Furthermore, the ECH performance of the material was tested for 2 h using chronoamperometry (CA test), and the products were quantitatively analyzed by GC. The specific test procedure was as follows: After the CA test, 1 mL of the reaction solution was drawn with a syringe, and then an equal volume of ethyl acetate was added for extraction. The organic phase was transferred to a sample vial, and the sample was injected into the autosampler. GC test parameters: The detector was an FID detector, the column was an HP-INNOWAX capillary column, and the carrier gas was N2. The injection port temperature was 250 ℃, the FID detector temperature was 300 ℃, the H2 flow rate was 30 mL / min, the air flow rate was 400 mL / min, and the make-up N2 flow rate was 25 mL / min. Qualitative analysis will be performed using GC-MS in the future.

[0129] For Example 1 (CC / CeO2-C) 84 (OH) m Comparative Examples 1 (CC / CeO2-Carbon-RuW), 2 (CC / CeO2-Graphene-RuW), 3 (CC / CeO2-RuW), and 4 (CC / CeO2-RuW) are: CC / CeO2-Carbon-RuW, CC / CeO2-Graphene-RuW, CC / CeO2 ... 84 (OH) m The ECH performance of -RuW was tested, and the LSV results are available in [link to LSV results]. Figure 8 .Depend on Figure 8 It is evident that, for the electrocatalytic hydrogenation performance of phenol, CC / CeO2-C 84 (OH) m -RuW and CC / CeO2-Carbon-RuW, CC / CeO2-Graphene-RuW, CC / CeO2-RuW, CC / C 84 (OH) m Compared to RuW, it achieves the same current density of 30 mA / cm². 2 Time potential (E) 30 The absolute value is smaller, E 30 vs. RHE absolute values ​​are CC / CeO2-C respectively. 84 (OH) m -RuW (0.206 V) <CC / CeO2-Graphene-RuW(0.224 V)<CC / CeO2-Carbon-RuW(0.235V)<CC / CeO2-RuW(0.251 V)<CC / C 84 (OH) m-RuW (0.287 V) indicates that the fullerol-modified noble metal-based alloy nanoclusters prepared in the embodiments of the present invention have better electrocatalytic hydrogenation performance of phenol.

[0130] GC test results show that Example 1 (CC / CeO2-C) 84 (OH) m -RuW) in At 0.15 V vs. RHE, the phenol conversion rate was 96.3%, and the formation rate of the target product cyclohexanol (cyclohexanol is the target product of this reaction, hence it is used as the representative product) was 0.045 mmol / (h·cm). 2 The Faraday efficiency was 75.2%; Comparative Example 1 (CC / CeO2-Carbon-RuW) showed an efficiency of 75.2%. At 0.15 V vs. RHE, the phenol conversion rate was 68.2%, and the formation rate of the target product cyclohexanol was 0.028 mmol / (h·cm). 2 The Faraday efficiency was 45.7%; Comparative Example 2 (CC / CeO2-Graphene-RuW) showed an efficiency of 45.7%. At 0.15 V vs. RHE, the phenol conversion rate was 74.5%, and the formation rate of the target product cyclohexanol was 0.031 mmol / (h·cm). 2 The Faraday efficiency was 53.7%; Comparative Example 3 (CC / CeO2-RuW) showed an efficiency of 53.7%. At 0.15 V vs. RHE, the phenol conversion rate was 53.6%, and the formation rate of the target product cyclohexanol was 0.021 mmol / (h·cm). 2 The Faraday efficiency is 42.8%, compared to Comparative Example 4 (CC / C). 84 (OH) m -RuW) in At 0.15 V vs. RHE, the phenol conversion rate was 40.3%, and the formation rate of the target product cyclohexanol was 0.015 mmol / (h·cm). 2 The Faraday efficiency is 21.7%. Based on the above performance results, it can be seen that Example 1 (CC / CeO2-C) 84 (OH) m The electrocatalytic hydrogenation performance of phenol by CC / CeO2-Carbon-RuW was superior to that of Comparative Example 1 (CC / CeO2-Carbon-RuW), Comparative Example 2 (CC / CeO2-Graphene-RuW), Comparative Example 3 (CC / CeO2-RuW), and Comparative Example 4 (CC / C-RuW). 84 (OH) m-RuW). The above differences in experimental effects indicate that, on the one hand, only the alloy nanocluster material prepared by fullerenol modification has good electrocatalytic hydrogenation catalytic effect, and its Faraday efficiency is increased by 64.55% compared with the alloy nanocluster material modified by carbon black (Comparative Example 1), and is increased by 40.04% compared with the alloy nanocluster material modified by graphene (Comparative Example 2). On the other hand, it shows that CeO2 acting as a carrier can also well promote the electrocatalytic hydrogenation performance, and its Faraday efficiency is increased by 2.46 times compared with the alloy nanocluster material without CeO2 modification (Comparative Example 4).

[0131] Application Example 2 Performance Test of Electro-Catalytic Hydrogenation of Phenol For Example 2 (NF / CeO2-C 84 (OH) m -RhNi) and Comparative Example 5 (NF / CeO2-RhNi), their ECH performances were tested. The test method was the same as that in Application Example 1. For the LSV results, see Figure 9 . From Figure 9 it can be seen that for the electrocatalytic hydrogenation performance of phenol, for NF / CeO2-C 84 (OH) m -RhNi compared with NF / CeO2-RhNi, when reaching the same current density of 30 mA / cm 2 , the absolute value of the potential (E 30 ) is smaller. The absolute values of E 30 vs. RHE are NF / CeO2-C 84 (OH) m -RhNi (0.202 V) < NF / CeO2-RhNi (0.253 V), indicating that the noble metal-based alloy nanocluster material modified by fullerenol prepared in the examples of the present invention has better electrocatalytic hydrogenation performance of phenol.

[0132] The GC test results show that in Example 2 (NF / CeO2-C 84 (OH) m -RhNi), the phenol conversion rate is 96.8% at 0.15 V vs. RHE, the production rate of the target product cyclohexanol is 0.043 mmol / (h·cm ), and the Faraday efficiency is 69.7%; in Comparative Example 5 (NF / CeO2-RhNi), the phenol conversion rate is 52.7% at 0.15 V vs. RHE, the production rate of the target product cyclohexanol is 0.019 mmol / (h·cm 2 ), and the Faraday efficiency is 38.7%. According to the above performance results, it can be seen that in Example 2 (NF / CeO2-C (OH) 2 ) 84 (OH)m The electrocatalytic hydrogenation performance of (IF / CeO2-C(OH)-PdFe) is better than that of Comparative Example 5 (NF / CeO2-RhNi).

[0133] Application Example 3 Performance Test of Electrocatalytic Hydrogenation of 2,4-Dichlorophenol For Example 3 (IF / CeO2-C 76 (OH) m (OH)-PdFe) and Comparative Example 6 (IF / CeO2-PdFe), their ECH performances were tested. The test method was the same as that in Application Example 1, except that the electrolyte was a perchloric acid solution containing 2,4-dichlorophenol (0.2 M HClO4 + 10 mM 2,4-dichlorophenol, pH = 0.67). The LSV results are shown in Figure 10 . From Figure 10 it can be seen that for the electrocatalytic hydrogenation performance of 2,4-dichlorophenol, when reaching the same current density of 30 mA / cm 76 (OH) m , the absolute value of the potential (E 2 ) of IF / CeO2-C 30 (OH) 30 -PdFe is smaller than that of IF / CeO2-PdFe. The absolute values of E 76 (OH) m vs. RHE are IF / CeO2-C

[0134] (OH)-PdFe (0.213 V) < IF / CeO2-PdFe (0.254 V), indicating that the fullerol-modified noble metal-based alloy nanocluster material prepared in the embodiment of the present invention has better electrocatalytic hydrogenation performance for 2,4-dichlorophenol. 76 (OH) m -PdFe) at 0.18 V vs. RHE, the conversion rate of 2,4-dichlorophenol is 94.8%, the production rate of the target product cyclohexanol (cyclohexanol is the target product of this reaction, so it is used as a representative product) is 0.038 mmol / (h·cm 2 ), and the Faraday efficiency is 62.8%; for Comparative Example 6 (IF / CeO2-PdFe) at 0.18 V vs. RHE, the conversion rate of 2,4-dichlorophenol is 58.3%, the production rate of the target product cyclohexanol is 0.020 mmol / (h·cm 2 ), and the Faraday efficiency is 42.6%. According to the above performance results, it can be seen that Example 3 (IF / CeO2-C 76 (OH) mThe electrocatalytic hydrogenation performance of 2,4-dichlorophenol on (IF / CeO2-PdFe) is better than that of Comparative Example 6 (IF / CeO2-PdFe).

[0135] Application Example 4 Performance Test of Electro-Catalytic Hydrogenation of Guaiacol For Example 4 (SS / CeO2-C 70 (OH) m -RuCoCu) and Comparative Example 7 (SS / CeO2-RuCoCu), their ECH performances were tested. The testing method was the same as that of Application Example 1, except that the electrolyte was a perchloric acid solution containing guaiacol (0.2 M HClO4 + 10 mM guaiacol, pH = 0.67). The LSV results are shown in Figure 11 . From Figure 11 it can be seen that for the electrocatalytic hydrogenation performance of guaiacol, when reaching the same current density of 30 mA / cm 70 (OH) m -RuCoCu, compared with SS / CeO2-RuCoCu, the absolute value of the potential (E 2 ) is smaller. The absolute values of E 30 vs. RHE are SS / CeO2-C 30 (OH) 70 (OH) m -RuCoCu (0.189 V) < SS / CeO2-RuCoCu (0.243 V), indicating that the fullerol-modified noble metal-based alloy nanocluster material prepared in the embodiment of the present invention has better electrocatalytic hydrogenation performance of guaiacol.

[0136] The GC test results show that for Example 4 (SS / CeO2-C 70 (OH) m -RuCoCu), at 0.15 V vs. RHE, the conversion rate of guaiacol is 86.5%, the production rate of the target product 2-methoxycyclohexanol (2-methoxycyclohexanol is the target product of this reaction, so it is used as a representative product) is 0.037 mmol / (h·cm ), and the Faraday efficiency is 58.7%; for Comparative Example 7 (SS / CeO2-RuCoCu), at 0.15 V vs. RHE, the conversion rate of guaiacol is 55.3%, the production rate of the target product 2-methoxycyclohexanol is 0.013 mmol / (h·cm 2 ), and the Faraday efficiency is 20.7%. According to the above performance results, it can be seen that for Example 4 (SS / CeO2-C (OH) 2 ) 70 (OH) mThe electrocatalytic hydrogenation performance of guaiacol on CC / CeO2-C(OH)-PtZnMo is better than that of Comparative Example 7 (SS / CeO2-RuCoCu).

[0137] Application Example 5 Performance Test of Electrocatalytic Hydrogenation of Guaiacol For Example 5 (CC / CeO2-C(OH)-PtZnMo) and Comparative Example 8 (CC / CeO2-PtZnMo), the ECH performance was tested. The test method was the same as that in Application Example 1, except that the electrolyte was a perchloric acid solution containing guaiacol (0.2 M HClO4 + 10 mM guaiacol, pH = 0.67). The LSV results are shown in 60 (OH) m It can be seen that for the electrocatalytic hydrogenation performance of guaiacol, when reaching the same current density of 30 mA / cm, the absolute value of the potential (E) of CC / CeO2-C(OH)-PtZnMo is smaller than that of CC / CeO2-PtZnMo. The absolute values of E vs. RHE are CC / CeO2-C(OH)-PtZnMo (0.138 V) < CC / CeO2-PtZnMo (0.203 V), indicating that the fullerol-modified noble metal-based alloy nanocluster material prepared in the examples of the present invention has better electrocatalytic hydrogenation performance of guaiacol. Figure 12 From Figure 12 It can be seen that for the electrocatalytic hydrogenation performance of guaiacol, CC / CeO2-C(OH)-PtZnMo 60 (OH) m -PtZnMo has a smaller absolute value of potential (E) than CC / CeO2-PtZnMo when reaching the same current density of 30 mA / cm 2 ². The absolute values of E 30 vs. RHE are CC / CeO2-C(OH)-PtZnMo (0.138 V) < CC / CeO2-PtZnMo (0.203 V), indicating that the fullerol-modified noble metal-based alloy nanocluster material prepared in the examples of the present invention has better electrocatalytic hydrogenation performance of guaiacol. 30 vs. RHE, with absolute values of CC / CeO2-C(OH)-PtZnMo (0.138 V) < CC / CeO2-PtZnMo (0.203 V), indicating that the fullerol-modified noble metal-based alloy nanocluster material prepared in the examples of the present invention has better electrocatalytic hydrogenation performance of guaiacol. 60 (OH) m -PtZnMo (0.138 V) < CC / CeO2-PtZnMo (0.203 V), indicating that the fullerol-modified noble metal-based alloy nanocluster material prepared in the examples of the present invention has better electrocatalytic hydrogenation performance of guaiacol.

[0138] The GC test results show that for Example 5 (CC / CeO2-C(OH)-PtZnMo), the conversion rate of guaiacol is 89.6% at 0.09 V vs. RHE, the production rate of the target product 2-methoxycyclohexanol is 0.039 mmol / (h·cm²), and the Faraday efficiency is 64.9%; for Comparative Example 8 (CC / CeO2-PtZnMo), the conversion rate of guaiacol is 60.5% at 0.09 V vs. RHE, the production rate of the target product 2-methoxycyclohexanol is 0.026 mmol / (h·cm²), and the Faraday efficiency is 33.2%. According to the above performance results, it can be seen that the electrocatalytic hydrogenation performance of guaiacol on Example 5 (CC / CeO2-C(OH)-PtZnMo) is better than that of Comparative Example 8 (CC / CeO2-PtZnMo). 60 (OH) m -PtZnMo) at 0.09 V vs. RHE, the conversion rate of guaiacol is 89.6%, the production rate of the target product 2-methoxycyclohexanol is 0.039 mmol / (h·cm²), and the Faraday efficiency is 64.9%; for Comparative Example 8 (CC / CeO2-PtZnMo) at 2 )², the conversion rate of guaiacol is 60.5%, the production rate of the target product 2-methoxycyclohexanol is 0.026 mmol / (h·cm²), and the Faraday efficiency is 33.2%. According to the above performance results, it can be seen that the electrocatalytic hydrogenation performance of guaiacol on Example 5 (CC / CeO2-C(OH)-PtZnMo) is better than that of Comparative Example 8 (CC / CeO2-PtZnMo). 0.09 V vs. RHE, the conversion rate of guaiacol is 60.5%, the production rate of the target product 2-methoxycyclohexanol is 0.026 mmol / (h·cm²), and the Faraday efficiency is 33.2%. According to the above performance results, it can be seen that the electrocatalytic hydrogenation performance of guaiacol on Example 5 (CC / CeO2-C(OH)-PtZnMo) is better than that of Comparative Example 8 (CC / CeO2-PtZnMo). 2 )², the conversion rate of guaiacol is 60.5%, the production rate of the target product 2-methoxycyclohexanol is 0.026 mmol / (h·cm²), and the Faraday efficiency is 33.2%. According to the above performance results, it can be seen that the electrocatalytic hydrogenation performance of guaiacol on Example 5 (CC / CeO2-C(OH)-PtZnMo) is better than that of Comparative Example 8 (CC / CeO2-PtZnMo). 60 (OH) m -PtZnMo) is better than that of Comparative Example 8 (CC / CeO2-PtZnMo).

[0139] Application Example 6 Performance Test of Electro - catalytic Hydrogenation of Nitrobenzene For Example 6 (CC / CeO2 - C 60 (OH) m -AuCoCr) and Comparative Example 9 (CC / CeO2 - AuCoCr), the ECH performance was tested. The testing method was the same as that of Application Example 1, except that the electrolyte was a perchloric acid solution containing nitrobenzene (0.2 M HClO4 + 10 mM nitrobenzene, pH = 0.67). The LSV results are shown in Figure 13 . From Figure 13 it can be seen that for the electro - catalytic hydrogenation performance of nitrobenzene, when reaching the same current density of 30 mA / cm 60 (OH) m -AuCoCr and CC / CeO2 - AuCoCr, the absolute value of the potential (E 2 ) is smaller. The absolute values of E 30 vs. RHE are CC / CeO2 - C 30 (OH) 60 (OH) m -AuCoCr (0.143 V) < CC / CeO2 - AuCoCr (0.202 V), indicating that the fullerol - modified noble - metal - based alloy nanocluster material prepared in the examples of this invention has better electro - catalytic hydrogenation performance of nitrobenzene.

[0140] The GC test results show that for Example 6 (CC / CeO2 - C 60 (OH) m -AuCoCr), the conversion rate of nitrobenzene is 93.6% at 0.09 V vs. RHE, the production rate of the target product aniline (aniline is the target product of this reaction, so it is used as a representative product) is 0.043 mmol / (h·cm ), and the Faraday efficiency is 67.4%; for Comparative Example 9 (CC / CeO2 - AuCoCr), the conversion rate of nitrobenzene is 57.5% at 0.09 V vs. RHE, the production rate of the target product aniline is 0.023 mmol / (h·cm 2 ), and the Faraday efficiency is 31.4%. According to the above performance results, it can be seen that the electro - catalytic hydrogenation performance of nitrobenzene of Example 6 (CC / CeO2 - C 0.09 V vs. RHE) is better than that of Comparative Example 9 (CC / CeO2 - AuCoCr). 2 ) and the Faraday efficiency is 31.4%. According to the above performance results, it can be seen that the electro - catalytic hydrogenation performance of nitrobenzene of Example 6 (CC / CeO2 - C 60 (OH) m -AuCoCr) is better than that of Comparative Example 9 (CC / CeO2 - AuCoCr).

[0141] In summary, this invention obtains a precursor material by immersing a rare-earth metal oxide-modified current collector in a mixed solution containing fullerols and metal ions (including at least one noble metal ion and at least one non-noble metal ion). The precursor material is then heat-treated under a protective atmosphere to obtain a fullerol-modified noble metal-based alloy nanoclusters. The alloy design, combined with fullerol modification, endows the noble metal with an optimized electronic structure, enhancing electrocatalytic hydrogenation activity. Furthermore, surface fullerol modification facilitates the adsorption and enrichment of organic substrates on the catalytic material surface, thereby improving mass transfer efficiency. Benefiting from these enhancement mechanisms, the obtained fullerol-modified noble metal-based alloy nanoclusters exhibit excellent catalytic performance in the electrocatalytic hydrogenation treatment of unsaturated organic compounds, providing a green and low-carbon pathway for the resource-based treatment of organic wastewater.

[0142] 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 fullerol-modified noble metal-based alloy nanoclusters, characterized in that, Includes the following steps: S1: Preparation of rare earth metal oxide modified current collectors; S2: The rare earth metal oxide modified current collector obtained in S1 is immersed in a mixed solution containing fullerol and metal ions, and after full reaction and post-processing, a fullerol modified noble metal-based alloy nanocluster precursor material is obtained. S3: The precursor material obtained in S2 is placed in a protective gas atmosphere and heat-treated at 200~500 ℃ to react fully, thereby obtaining a fullerol-modified noble metal-based alloy nanocluster material. The metal ions include at least one noble metal ion and at least one non-noble metal ion.

2. The preparation method according to claim 1, characterized in that, The fullerol has 20+2k carbon atoms, where k is an integer between 20 and 32.

3. The preparation method according to claim 1, characterized in that, The noble metal element of the noble metal ion is selected from at least one of Pt, Ru, Rh, Pd, Ir, and Au.

4. The preparation method according to claim 1, characterized in that, The metal element in the non-noble metal ion is selected from at least one of Ni, Fe, Co, Cu, Zn, Mo, V, W, Ti, Zr, Cr, Sc, and Y.

5. The preparation method according to claim 1, characterized in that, In the metal ions, the molar ratio of the noble metal ions to the non-noble metal ions is (0.05~15):

1.

6. The preparation method according to claim 1, characterized in that, The rare earth metal in the rare earth metal oxide is selected from at least one of Ce, Sm, Eu, and Yb.

7. The preparation method according to claim 1, characterized in that, The rare earth metal oxide modified current collector is prepared by electrodeposition or chemical deposition.

8. The preparation method according to claim 7, characterized in that, The electrodeposition method specifically includes the following steps: The current collector is immersed in a solution containing rare earth metal ions, and a rare earth metal oxide modification layer is formed on the surface of the current collector by electrodeposition. After post-processing, a rare earth metal oxide modified current collector is obtained.

9. Fullerol-modified noble metal-based alloy nanoclusters prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the fullerol-modified noble metal-based alloy nanoclusters of claim 9 in electrocatalytic hydrogenation reactions.

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