Preparation method and application of nickel-based electrocatalyst rich in multi-void defects

Abstract

The application discloses a preparation method and application of a nickel-based electrocatalyst rich in multi-vacancy defects. The nickel-based electrocatalyst is prepared by using foamed nickel as a nickel source, metal sodium salt or metal nitrate as a metal precursor, and sodium salt as an anion precursor. A high-valence metal-doped nickel-based catalyst precursor is constructed by a one-step hydrothermal method. On this basis, the anion vacancy is regulated by using a hydrogen peroxide etching strategy. In an electrochemical in-situ reconstruction, the anion is replaced by hydroxyl in the solution, and the high-valence metal is leached to form a cation vacancy, so that a nickel-based hydroxide / oxide (V M,N -Ni(O x H y )) catalyst with cation vacancies and anion vacancies is obtained. The nickel-based electrocatalyst preparation process has the characteristics of simplicity, easy operation and control, can be extended to the preparation of other multi-vacancy defect metal hydroxides / oxides, and provides a new idea and method for designing and developing a new type of efficient biomass oxidation electrocatalyst.

Description

Technical Field

[0001] This invention relates to a method for preparing a nickel-based electrocatalyst rich in multi-vacancy defects, specifically, a one-step hydrothermal method for synthesizing metal-doped nickel-based (M-Ni) catalysts containing anionic vacancies. x N y -N V The catalyst precursor was then obtained through electrochemical in-situ reconstruction to yield nickel-based hydroxides / oxides (V) containing various vacancy defects. M,N -Ni(O x H y Catalyst method. Background Technology

[0002] The increasing reliance on petroleum energy for power generation and value-added chemical production exacerbates the dangers of global warming. Therefore, there is growing interest in developing sustainable clean energy storage and conversion technologies to mitigate the adverse effects of climate change. Biomass, primarily produced through plant photosynthesis, is the only renewable resource that possesses both energy and feedstock properties. Selectively converting hydrocarbons from biomass into fuels and high-value chemicals offers a green pathway to minimizing our dependence on non-renewable resources. 5-Hydroxymethylfurfural (HMF) is one of the most promising cellulose-derived platform chemicals, capable of being oxidized to produce a variety of key chemical products, including synthetic polymer monomers, fine chemicals, pharmaceutical precursors, fuel additives, and liquid fuels, demonstrating extremely broad development prospects. Among these, 2,5-furandicarboxylic acid (FDCA) is the most valuable product of 5-hydroxymethylfurfural oxidation and is used as an important monomer in the production of biopolymers to replace petroleum-based polyethylene terephthalate. However, the classic chemical oxidation of organic compounds involves high-valent chromium, manganese, copper oxides, lead salts, reactive dimethyl sulfoxide, iodine, and organic amino oxides. These methods suffer from significant drawbacks: they are either toxic (except for those using manganese-containing catalysts) or limited to small-scale reactions due to the use of non-catalytic materials (such as alumina or alumina catalysts) for oxidative conversion, and are challenged by product yield and separation, thus restricting their industrial-scale application. In stark contrast, electrochemical energy has emerged as a more efficient and sustainable alternative, capable of oxidizing organic molecules without the need for additional expensive or toxic oxidants. The electrooxidation process can be precisely controlled in terms of product yield and selectivity simply by adjusting the operating potential, electrode materials, battery configuration, electrolyte, etc. Furthermore, most electrooxidations are carried out at room temperature and atmospheric pressure, offering a significant advantage in energy reduction compared to traditional chemical oxidation methods.

[0003] Nickel-based catalysts (such as nickel hydroxide, nickel sulfide, nickel phosphide, and nickel boride) have proven to be highly efficient catalysts for biomass electrooxidation and have been extensively studied due to their excellent structures. It has been reported that by doping molybdenum atoms into nickel sulfide, and then leaching molybdenum and sulfur atoms after electrochemical in-situ reconstruction, nickel oxide / nickel hydroxide (VO / NH) with metal vacancies is obtained. M -NiO x H y Catalysts, metal vacancies can promote the development of high-valence Ni 3+ The formation of -O active sites enhances the catalytic performance of 5-hydroxymethylfurfural (5-HMF). Furthermore, the introduction of oxygen vacancies into nickel-iron layered hydroxides promotes the adsorption of 5-HMF molecules, which is also beneficial for their oxidation. With the development of defect chemistry, researchers have gradually recognized the importance of vacancy defects (metal vacancy defects and oxygen vacancy defects) in heterogeneous catalysis (such as electrocatalysis) based on vacancy-rich nanocatalysts. Studies have shown that in electrochemical processes, nickel-based catalysts with vacancy defects are generally more prone to irreversible surface reconstruction in the electrolyte, leading to nickel oxide / nickel hydroxide (NiO) oxidation. x H y The formation of species. However, there have been no reports on catalysts for the efficient catalysis of 5-hydroxymethylfurfural oxidation by multi-vacancy nickel-based catalysts, and the research and application of multi-vacancy synergistic promotion of 5-hydroxymethylfurfural oxidation has not yet been realized, which has always been a bottleneck.

[0004] In view of the above shortcomings, the subject of this invention is to provide a method for preparing a nickel-based electrocatalyst rich in multi-vacancy defects that can efficiently catalyze the oxidation of 5-hydroxymethylfurfural. Summary of the Invention

[0005] This invention addresses the technical problem of overcoming the shortcomings of existing technologies by providing a nickel-based hydroxide / oxide catalyst (V) rich in multi-vacancy defects. M,N -Ni(O x H y It is used in the oxidation reaction of 5-hydroxymethylfurfural; and a one-step hydrothermal synthesis of metal-doped nickel-based (M-Ni) containing anion vacancies is performed. x N y -N V The method of catalyst precursors is simple, easy to operate and control, which is conducive to large-scale industrial production and has significant economic and social benefits.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention first discloses a method for preparing a nickel-based electrocatalyst rich in multi-vacancy defects, comprising the following steps:

[0008] (1) Dissolve the metal precursor and the anion precursor in 30 mL of ultrapure water respectively, and use an ultrasonic machine to dissolve and disperse them for 30 min to obtain the first solution;

[0009] (2) Place the nickel foam in the first solution; use magnetic stirring to completely impregnate the nickel foam to obtain the second product;

[0010] (3) The second product was placed vertically in the lining of a sealed reactor for hydrothermal reaction, and then washed and dried to obtain the third product.

[0011] (4) The third product was immersed in hydrogen peroxide solution for 60 seconds, followed by washing and drying to obtain metal-doped nickel-based (M-Ni) containing anion vacancies. x N y -N V Catalyst precursor;

[0012] (5) Metal-doped nickel-based (M-Ni) containing anion vacancies x N y -N V The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing 1 mol / L potassium hydroxide to obtain a nickel-based electrocatalyst rich in multi-vacancy defects.

[0013] Furthermore, the metal precursor mentioned in step (1) includes, but is not limited to:

[0014] Any one of the following: sodium tungstate dihydrate, sodium molybdate dihydrate, sodium vanadate dodecyl hydrate, manganese nitrate tetrahydrate, cadmium nitrate nonhydrate, aluminum nitrate nonhydrate, and zinc nitrate hexahydrate;

[0015] The anion precursor includes, but is not limited to:

[0016] Sodium sulfide nonahydrate, sodium hypophosphite hydrate, and sodium borohydride are all selected from these three.

[0017] In the first solution, the purity of both the metal precursor and the anion precursor is above 99.5%, the mass fraction of hydrogen peroxide is 30% ± 1%, and the foamed nickel is commercially available foamed nickel with a thickness of 1.6 nm.

[0018] Further, in step (1), the molar ratio of anions to metal ions in the first solution is 10:1.

[0019] Furthermore, the nickel foam described in step (2) also includes the following treatment before use:

[0020] Cut the nickel foam into 1cm*2cm blocks, and then sequentially treat them with 3mol / L hydrochloric acid, ultrapure water, anhydrous ethanol and ultrapure water for 15min each. Hydrochloric acid solution treats the oxides on the surface of the nickel foam, anhydrous ethanol treats the organic matter on the surface of the nickel foam, and ultrapure water washes away the surface residues. Place the treated nickel foam in a vacuum oven and dry it at 60℃ for 12h to obtain the final product.

[0021] Further, the conditions for the hydrothermal reaction in step (3) are: hydrothermal temperature ≥ 160℃, hydrothermal time ≥ 8h; the washing is: ultrasonic washing with ultrapure water for 10min, washing twice, and ultrasonic washing with anhydrous ethanol for 10min once, and the washed product is placed in a vacuum oven and dried at 60℃ for 12h.

[0022] Further, the washing in step (4) includes: ultrasonic washing with ultrapure water twice and ultrasonic washing with anhydrous ethanol once, with each ultrasonic washing time being 10 min; the drying conditions are: drying at 60℃ for 12 h.

[0023] Furthermore, the electrochemical in-situ reconstruction in step (5) adopts a three-electrode system, including: a working electrode, a reference electrode, and a counter electrode; wherein: the working electrode is a metal-doped nickel-based catalyst precursor containing anion vacancies, the reference electrode is mercury / mercury oxide, and the counter electrode is a carbon rod.

[0024] Further, the in-situ reconstruction conditions in step (5) are: using cyclic voltammetry, within a potential range of 0.80V to 1.70V, at a rate of 50mV s. -1 The scanning rate is more than 50 revolutions.

[0025] The present invention also discloses a nickel-based electrocatalyst rich in multiple vacancy defects, prepared according to any of the above-described preparation methods.

[0026] The present invention also discloses the application of the nickel-based electrocatalyst rich in multi-vacancy defects described above in the electro-oxidation process of 5-hydroxymethylfurfural.

[0027] Furthermore, the application includes:

[0028] 63 mg of 5-hydroxymethylfurfural was dissolved in the anode of an H-type cell containing 10 mL of potassium hydroxide solution, and the cathode also contained 10 mL of potassium hydroxide solution. Its catalytic performance was investigated by linear sweep voltammetry, electrolysis was performed by potentiostatic polarization, and the conversion rate of 5-hydroxymethylfurfural and the Faraday efficiency of 2,5-furandicarboxylic acid were quantitatively detected by high performance liquid chromatography.

[0029] Furthermore, the concentration of the potassium hydroxide solution is 1 mol / L; the potential range of the linear scan voltammetry is 0.80 V to 1.70 V, and the potential of the potentiostatic polarization method is 1.45 V;

[0030] The formulas for calculating the conversion rate of 5-hydroxymethylfurfural and the Faraday efficiency of 2,5-furandicarboxylic acid are as follows:

[0031] Conversion rate of 5-hydroxymethylfurfural (%) = number of moles of 5-hydroxymethylfurfural consumed / number of moles of initial 5-hydroxymethylfurfural × 100% Faraday efficiency of 2,5-furandicarboxylic acid FE (%) = charge of product / charge passing through × 100%.

[0032] Electron microscopy results show that after electrochemical in-situ reconstruction, amorphous NiO appears on the catalyst surface. x The thin layer, containing coarse lattice fringes and localized lattice distortions, indicates the presence of a large number of atomic vacancies.

[0033] The advantages of this invention compared to the prior art are:

[0034] (1) The present invention adopts a one-step hydrothermal method, which is simple, easy to operate and control, and is conducive to large-scale industrial production, and has significant economic and social benefits.

[0035] (2) The present invention uses a non-precious metal catalyst, which has low cost consumption and is universally applicable.

[0036] (3) The present invention has high efficiency and the catalyst obtained has excellent performance. It can obtain higher oxidation capacity at a lower potential, which is conducive to large-scale application.

[0037] (4) The present invention adopts a strategy of multiple vacancy defects to improve catalyst performance, which is insufficient in existing research and provides ideas for the future design of defect-type catalysts. Attached Figure Description

[0038] Figure 1 The nickel-based hydroxide / oxide (V) obtained in Example 1 after electrochemical in-situ reconstruction is rich in multi-vacancy defects. W,S -Ni(O x H y High-resolution electron microscope images of the catalyst;

[0039] Figure 2 This is a performance comparison chart of nickel-based hydroxide / oxide catalysts with different vacancy defects obtained in Examples 1-3 of this invention;

[0040] Figure 3 It is the nickel-based hydroxide / oxide (V) containing multi-vacancy defects obtained in Example 1 of this invention. W,S -Ni(O x H y Stability diagram of the catalyst. Detailed Implementation

[0041] To further illustrate the present invention, the following specific embodiments are provided; however, the scope of the claims of the present invention is not limited to these embodiments. Furthermore, the embodiments only provide some conditions for achieving this objective, and do not imply that all these conditions must be met to achieve this objective. To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0042] Example 1

[0043] 960.7 mg of sodium sulfide nonahydrate and 131.9 mg of sodium tungstate dihydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain tungsten-doped nickel-based (W-Ni3S2-S) containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. W,S -Ni(O x H y Electrocatalyst.

[0044] Figure 1 Nickel-based hydroxides / oxides (V) rich in multi-vacancy defects after electrochemical in-situ reconstruction W,S -Ni(O x H y High-resolution electron microscopy image of the catalyst. Amorphous NiO appears on the catalyst surface. x The thin layer, containing coarse lattice fringes and localized lattice distortions, indicates the presence of a large number of atomic vacancies.

[0045] Example 2

[0046] 960.7 mg of sodium sulfide nonahydrate and 131.9 mg of sodium tungstate dihydrate were dissolved in 30 mL of ultrapure water and ultrasonically dispersed. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, a tungsten-doped nickel-based (W-Ni3S2) catalyst precursor was obtained. This precursor was then electrochemically reconstructed in situ in an H-type cell containing 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V... M -Ni(O x H y Electrocatalyst.

[0047] Example 3

[0048] 960.7 mg of sodium sulfide nonahydrate was dissolved in 30 mL of ultrapure water and ultrasonically dispersed. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain nickel-based (Ni3S2-S) compounds containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) with anion vacancy defects. S -Ni(O x H y Electrocatalyst.

[0049] Example 4

[0050] 960.7 mg of sodium sulfide nonahydrate and 96.8 mg of sodium molybdate dihydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain molybdenum-doped nickel-based (M) containing sulfur vacancies. O -Ni3S2-S v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Mo,S -Ni(O x H y Electrocatalyst.

[0051] Example 5

[0052] 960.7 mg of sodium sulfide nonahydrate and 152.0 mg of sodium vanadate dodecahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain vanadium-doped nickel-based (V-Ni3S2-S) containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. V,S -Ni(O x H y Electrocatalyst.

[0053] Example 6

[0054] 960.7 mg of sodium sulfide nonahydrate and 100.4 mg of manganese nitrate tetrahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain manganese-doped nickel-based (Mn-Ni3S2-S) containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Mn,S -Ni(O x H y Electrocatalyst.

[0055] Example 7

[0056] 960.7 mg of sodium sulfide nonahydrate and 160.1 mg of cadmium nitrate nonahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain chromium-doped nickel-based (Cr-Ni3S2-S) containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Cr,S -Ni(O x H y Electrocatalyst.

[0057] Example 8

[0058] 960.7 mg of sodium sulfide nonahydrate and 150.1 mg of aluminum nitrate nonahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain aluminum-doped nickel-based (Al-Ni3S2-S) containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Al,S -Ni(O x H y Electrocatalyst.

[0059] Example 9

[0060] 960.7 mg of sodium sulfide nonahydrate and 128.9 mg of zinc nitrate hexahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 8 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain zinc-doped nickel-based (Zn-Ni3S2-S) containing sulfur vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Zn,S -Ni(O x H y Electrocatalyst.

[0061] Example 10

[0062] 351.9 mg of sodium hypophosphite dihydrate and 131.9 mg of sodium tungstate dihydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain tungsten-doped nickel-based (W-Ni2P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. W,P -Ni(O x H y Electrocatalyst.

[0063] Example 11

[0064] 351.9 mg of sodium hypophosphite dihydrate and 96.8 mg of sodium molybdate dihydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain molybdenum-doped nickel-based (Mo-Ni2P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Mo,P -Ni(O x H y Electrocatalyst.

[0065] Example 12

[0066] 351.9 mg of sodium hypophosphite dihydrate and 152.0 mg of sodium vanadate dodecyl hydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain vanadium-doped nickel-based (V-Ni2P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. V,P -Ni(O x H y Electrocatalyst.

[0067] Example 13

[0068] 351.9 mg of sodium hypophosphite dihydrate and 100.4 mg of manganese nitrate tetrahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain manganese-doped nickel-based (Mn-Ni2P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Mo,P -Ni(O x H y Electrocatalyst.

[0069] Example 14

[0070] 351.9 mg of sodium hypophosphite dihydrate and 160.1 mg of cadmium nitrate nonahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain chromium-doped nickel-based (Cr-Ni2P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Cr,P -Ni(O x H y Electrocatalyst.

[0071] Example 15

[0072] 351.9 mg of sodium hypophosphite dihydrate and 150.1 mg of aluminum nitrate nonahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain aluminum-doped nickel-based (Al-Ni2P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Al,P -Ni(O x H y Electrocatalyst.

[0073] Example 16

[0074] 351.9 mg of sodium hypophosphite dihydrate and 128.9 mg of zinc nitrate hexahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain zinc-doped nickel-based (Zn-Ni₂P-P) containing phosphorus vacancies. v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Zn,P -Ni(O x H y Electrocatalyst.

[0075] Example 17

[0076] 148.1 mg of sodium borohydride and 131.9 mg of sodium tungstate dihydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain tungsten-doped nickel-based (W-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. W,B -Ni(O x H y Electrocatalyst.

[0077] Example 18

[0078] 148.1 mg of sodium borohydride and 96.8 mg of sodium molybdate dihydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain molybdenum-doped nickel-based (Mo-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Mo,B -Ni(O x H y Electrocatalyst.

[0079] Example 19

[0080] 148.1 mg of sodium borohydride and 152.0 mg of sodium vanadate dodecyl hydrate were dissolved in 30 mL of ultrapure water and ultrasonically dispersed. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain vanadium-doped nickel-based (V-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. V,B -Ni(O x H y Electrocatalyst.

[0081] Example 20

[0082] 148.1 mg of sodium borohydride and 100.4 mg of manganese nitrate tetrahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain manganese-doped nickel-based (Mn-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Mn,B -Ni(O x Hy Electrocatalyst.

[0083] Example 21

[0084] 148.1 mg of sodium borohydride and 160.1 mg of cadmium nitrate nonahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain chromium-doped nickel-based (Cr-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Cr,B -Ni(O x H y Electrocatalyst.

[0085] Example 22

[0086] 148.1 mg of sodium borohydride and 150.1 mg of aluminum nitrate nonahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain aluminum-doped nickel-based (Al-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects. Al,B -Ni(O x H y Electrocatalyst.

[0087] Example 23

[0088] 148.1 mg of sodium borohydride and 128.9 mg of zinc nitrate hexahydrate were dissolved in 30 mL of ultrapure water and dispersed by ultrasonication. Nickel foam was placed in the solution and then hydrothermally heated in a sealed reactor liner at 160 °C for 12 h. After washing and drying, the product was placed in hydrogen peroxide solution for 60 s, washed, and dried to obtain zinc-doped nickel-based (Zn-NiB) containing boron vacancies. x -B v The catalyst precursor was electrochemically reconstructed in situ in an H-type cell containing a 1 mol / L potassium hydroxide solution to obtain a nickel-based hydroxide / oxide (V) rich in multi-vacancy defects.Zn,B -Ni(O x H y Electrocatalyst.

[0089] Application examples

[0090] The catalysts obtained in Examples 1-3 of this invention were used in the oxidation process of 5-hydroxymethylfurfural (HMF) according to the method of this invention, as follows:

[0091] 63 mg of 5-hydroxymethylfurfural (HMF) was weighed and dissolved in the anode of an H-type cell containing 10 mL of 1 mol / L potassium hydroxide solution (1 M KOH). The cathode also contained 10 mL of 1 mol / L potassium hydroxide solution. A three-electrode system was used, with the working electrode being a metal-doped nickel-based electrode containing anion vacancies (M-Ni). x N y -N V The catalyst precursor, reference electrode (mercury / mercuric oxide), and counter electrode (carbon rod) were used to investigate their catalytic performance using linear sweep voltammetry.

[0092] Figure 2 The figure shows a performance comparison of nickel-based hydroxide / oxide catalysts with different vacancy defects obtained in Examples 1-3. As shown in the figure, the catalyst rich in multi-vacancy defects (V W,S -Ni(O x H y It exhibits optimal performance, displaying 490.7 mA cm⁻¹ at a potential of 1.45V. -2 The current density is much higher than V. W -Ni(O x H y (316.1mA cm) -2 ) and V S -Ni(O x H y (203.3mA cm) -2 This indicates that metal vacancies and oxygen vacancies synergistically enhance the catalytic performance of the catalyst in 5-hydroxymethylfurfural.

[0093] Figure 3 It is the nickel-based hydroxide / oxide (V) rich in multi-vacancy defects obtained in Example 1 of this invention. W,S -Ni(O x H y The stability graph of the catalyst is shown in the figure. After six electrolysis cycles at a potential of 1.45V, it exhibits a near 100% conversion rate of 5-hydroxymethylfurfural (HMF) and a Faradaic efficiency of 2,5-furandicarboxylic acid (FDCA), demonstrating excellent stability.

[0094] The above embodiments are provided merely for the purpose of describing the present invention and are not intended to limit the scope of the invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications made without departing from the spirit and principles of the invention should be covered within the scope of the invention.

Claims

1. A method for preparing a nickel-based electrocatalyst rich in multi-vacancy defects, comprising: (1) separately dissolving a metal precursor and an anion precursor in 30 mL of ultrapure water, and using an ultrasonic machine to ultrasonically disperse for 30 min to obtain a first solution; (2) placing a foamed nickel in the first solution to obtain a second product; (3) placing the second product in a closed autoclave inner liner for hydrothermal treatment, and then washing and drying to obtain a third product; (4) immersing the third product in a hydrogen peroxide solution for 60 s, and then washing and drying to obtain a metal-doped anion-vacancy-containing nickel-based catalyst precursor; (5) electrochemically reconstructing the metal-doped anion-vacancy-containing nickel-based catalyst precursor in situ in an H-type cell containing 1 mol / L potassium hydroxide to obtain the nickel-based electrocatalyst rich in multi-vacancy defects, characterized in that: in step (1), the metal precursor is selected from any one of sodium tungstate dihydrate, sodium molybdate dihydrate, sodium vanadate dodecahydrate, manganese nitrate tetrahydrate, cadmium nitrate nonahydrate, aluminum nitrate nonahydrate, and zinc nitrate hexahydrate; the anion precursor is selected from any one of sodium sulfide nonahydrate, sodium hypophosphite hydrate, and sodium borohydride; and in the first solution, the molar ratio of anions to metal ions is 10:

1. 2.The method of claim 1, wherein: The electrochemical in-situ reconstruction in step (5) adopts a three-electrode system, including a working electrode, a reference electrode and a counter electrode; wherein the working electrode is a metal-doped nickel-based catalyst precursor containing anion vacancies, the reference electrode is mercury / mercury oxide, and the counter electrode is a carbon rod; the electrochemical in-situ reconstruction condition is that a cyclic voltammetry method is used, and the potential interval is 0.80 V ~ 1.70 V, the scanning rate is 50 mV s −1 , and more than 50 circles are scanned. in step (2), the foamed nickel before use further comprises the following treatment: cutting the foamed nickel into 1 cm*2 cm blocks, and then sequentially ultrasonically treating with 3 mol / L hydrochloric acid, ultrapure water, ethanol, and ultrapure water for 15 min each time, and finally placing in a vacuum oven for drying at 60 ℃ for 12 h. 3.The method of claim 1, wherein: in step (3), the hydrothermal treatment has a hydrothermal temperature of ≥160 ℃ and a hydrothermal time of ≥8 h. 4.The method of claim 1, wherein: in step (4), the washing comprises: ultrasonically washing twice with ultrapure water and ultrasonically washing once with anhydrous ethanol, each ultrasonic washing time being 10 min; and the drying condition is: drying at 60 ℃ for 12 h. 5.A nickel-based electrocatalyst rich in multi-vacancy defects containing multiple vacancy defects, prepared by the method of any one of claims 1-4. 6.Use of the nickel-based electrocatalyst rich in multi-vacancy defects of claim 5 in a 5-hydroxymethylfurfural electrooxidation reaction process. 7.The use of claim 6, comprising: weighing 63 mg of 5-hydroxymethylfurfural and dissolving it into an anode of an H-type cell containing 10 mL of a potassium hydroxide solution, and the cathode also has 10 mL of a potassium hydroxide solution; investigating the catalytic performance by linear sweep voltammetry, electrolyzing by constant potential polarization method, and quantitatively detecting the 5-hydroxymethylfurfural conversion rate and 2,5-furandicarboxylic acid Faraday efficiency by high performance liquid chromatography. 8.The use of claim 7, wherein: the concentration of the potassium hydroxide solution is 1 mol / L; the potential range of the linear sweep voltammetry is 0.80 V-1.70 V, and the potential of the constant potential polarization method is 1.45 V. ​

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