Defect-engineered transition metal-based nanomesh electrode and preparation method and application thereof

Abstract

The application belongs to the technical field of electro-catalytic oxidation, and particularly relates to a transition metal-based nano-array electrode regulated by defect engineering and a preparation method and application thereof. The method takes a current collector as a carrier, and sequentially undergoes a solvothermal reaction, a selenization or tellurization reaction and subsequent vacancy introduction to obtain a transition metal-based nano-array electrode with element doping and vacancies. Element doping cooperates with vacancy engineering to give the transition metal-based nano-array electrode an optimized electronic structure of a catalytic active center, which can improve intrinsic catalytic activity of the catalytic electrode on one hand and reduce the poisoning effect of sulfur-containing solutions on the other hand. 2‑ on the catalytic active sites of metals. Benefited from the above structural composition advantages, the transition metal-based nano-array electrode regulated by defect engineering exhibits excellent activity and stability in electro-catalytic sulfide oxidation reaction.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of electrocatalytic oxidation. More particularly, it relates to a defect-engineered transition metal-based nanometer array electrode and a preparation method and application thereof. BACKGROUND

[0002] Sulfur-containing wastewater is a kind of toxic, corrosive and odor-polluting water source commonly existing in daily and industrial activities. Traditional emission reduction strategies include acid recovery, precipitation, biochemical treatment and oxidation methods, etc. Although their effectiveness in degrading sulfur-containing wastewater has been proven, they require a large amount of chemicals and high energy input, resulting in huge operating costs. In addition, the frequent transportation, treatment and storage of chemicals pose occupational health and safety problems (Xu Zhiwei, Wang Xiaomei, Wang Jian, etc. Resource treatment of high-concentration sulfur-containing wastewater [J]. Sulfuric acid industry, 2022 (05): 39-43 + 47.).

[0003] Electrochemical oxidation treatment of sulfur-containing wastewater technology has the advantages of low cost and sustainability, and is promising and expected to replace traditional treatment technology. The core of electrochemical oxidation technology is electrocatalyst, and designing a catalyst with high activity and stability is the key to electrocatalytic sulfide oxidation reaction (SOR). Current SOR catalyst research mainly focuses on noble metals and transition metal sulfides. However, the above-mentioned catalysts have the problem of unsatisfactory catalytic activity and stability, and the development of new electrocatalysts has become a research hotspot in this field. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the defects and deficiencies of the existing SOR electrocatalytic material in catalytic activity and stability, and to provide a preparation method of a defect-engineered transition metal-based nanometer array electrode.

[0005] The purpose of the present application is to provide a defect-engineered transition metal-based nanometer array electrode prepared by the preparation method.

[0006] Another purpose of the present application is to provide the application of the defect-engineered transition metal-based nanometer array electrode.

[0007] The above purposes of the present application are achieved by the following technical solutions:

[0008] The present application protects a preparation method of a defect-engineered transition metal-based nanometer array electrode, comprising the following steps:

[0009] S1, mixed transition metal salt and precipitant are added to a solvent to be fully dissolved to form a uniform mixed solution, a current collector is added to the obtained mixed solution, and a solvothermal reaction is carried out at 80-250 DEG C, fully reacted, and post-treated to obtain an array precursor grown in situ on the current collector;

[0010] S2, adding the array precursor obtained in step S1 into a selenium source or tellurium source solution to perform a liquid-solid reaction at 80-250°C; or placing a selenium source or tellurium source upstream of a protective gas and placing the array precursor obtained in step S1 downstream of the gas to perform a high-temperature gas-solid blowing reaction at 250-900°C to obtain a transition metal-based nanometer array grown in situ on the current collector;

[0011] S3, introducing vacancies into the transition metal-based nanometer array obtained in step S2 by H2O2 treatment, H2 treatment or plasma treatment to obtain a defect-engineering-regulated transition metal-based nanometer array electrode.

[0012] The inventors have found in a large number of previous experiments that defect engineering such as element doping and vacancy introduction can effectively improve the catalytic activity and stability of bulk catalytic materials. On the basis of transition metal selenides or transition metal tellurides, element doping and vacancy design can be used to construct high-activity and high-stability electrocatalysts for SOR, thereby realizing efficient treatment of sulfur-containing wastewater.

[0013] Preferably, in step S1, the temperature of the solvothermal reaction is 100-200°C, more preferably 120-180°C.

[0014] Preferably, in step S1, the time of the solvothermal reaction is 1-96h, preferably 2-30h.

[0015] Preferably, in step S1, the mixed transition metal salt contains at least two transition metal salts, and the transition metals are selected from at least two of Ni, Co, Fe, Cu, Mn, Zn, Sc, Ti, Cr, Nb, Y, Tc, Cd, Ce, Ga, In, Ge, Sn, W, V, Mo. When one of them is selected as the main catalytically active transition metal, the other transition metals in the above-mentioned transition metals are selected as doping metals, and a small amount of addition can optimize the electronic structure of the catalytically active center of the obtained electrode and thus improve the catalytic activity. Generally, Ni, Co, Fe, Cu and Mn are common catalytically active transition metals in sulfide oxidation reactions and are used as the main metals in the mixed transition metal salt, while Zn, Sc, Ti, Cr, Y, Nb, Tc, Cd, Ce, Ga, In, Ge, Sn, W, V and Mo are used as doping metals in the mixed transition metal salt, i.e. as conventional dopants, and appropriate doping is beneficial to further improve the activity of the obtained catalytic material.

[0016] More preferably, in step S1, the main transition metal in the mixed transition metal salt is selected from at least one of Fe, Mn, Co, Ni and Cu.

[0017] Further, in step S1, the doped transition metal in the mixed transition metal salt is selected from at least one of Ni, Co, Fe, Cu, Mn, Zn, Sc, Ti, Cr, In, Sn, W, V, Mo.

[0018] Preferably, in step S1, the doped transition metal in the mixed transition metal salt is selected from at least one of Ni, Fe, Co, Cu, Mn, Zn, Mo, W, Ti, Cr.

[0019] More preferably, in step S1, the doped transition metal in the mixed transition metal salt is selected from at least one of Fe, Cu, Mn, Mo, W.

[0020] Preferably, in step S1, the salt of the mixed transition metal salt is one or more of nitrate, acetate, chloride, carbonate, sulfate.

[0021] Further, the total amount of the mixed transition metal salt is 0.001-5 mol / L.

[0022] Further, the total amount of the mixed transition metal salt is 0.01-3 mol / L.

[0023] More specifically, the total amount of the mixed transition metal salt is 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.10 mol / L, 0.20 mol / L, 0.30 mol / L, 0.50 mol / L, 1.00 mol / L, 2.00 mol / L or 3.00 mol / L.

[0024] Further, in step S1, the amount of substance ratio of the doped metal and the main metal in the mixed transition metal salt is 1:(1-100), preferably 1:(1-20), specifically 1:1, 1:2, 1:3, 1:4, 1:8, 1:10, 1:20.

[0025] Preferably, in step S1, the precipitant can be one or more of hexamethylenetetramine, sodium hydroxide, potassium hydroxide, urea, ammonia, sodium carbonate, sodium bicarbonate.

[0026] Further, in step S1, the amount of substance ratio of the transition metal ion of the mixed transition metal salt and the precipitant is 1:(0.2-20), more preferably 1:(0.5-16), specifically 1:0.5, 1:1, 1:2, 1:4, 1:8 or 1:16.

[0027] Preferably, in step S1, the solvent can be any one or more 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, ethyl acetate.

[0028] Preferably, in step S1, the current collector is carbon cloth, carbon paper or a metal current collector.

[0029] More preferably, the metal current collector is a metal foam, a metal foil, a metal plate or a metal mesh.

[0030] Further, the metal of the metal current collector is any one of Fe, Co, Ni, Zn, Al, Ti, stainless steel.

[0031] Further, in step S2, when the liquid-solid reaction is performed, the selenium source is sodium hydroselenide and the tellurium source is sodium hydrotelluride.

[0032] Further, the sodium hydroselenide and the sodium hydrotelluride are respectively obtained by reacting selenium powder or tellurium powder with sodium borohydride.

[0033] Further, in step S2, the molar concentration of the selenium source or the tellurium source solution is 0.001-3 mol / L, preferably 0.01-3 mol / L, and specifically 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.10 mol / L, 0.20 mol / L, 0.30 mol / L, 0.50 mol / L, 1.00 mol / L, 2.00 mol / L or 3.00 mol / L.

[0034] Preferably, in step S2, the temperature of the liquid-solid reaction is 100-200°C, and more preferably 120-180°C.

[0035] Further, in step S2, the time of the liquid-solid reaction is 1-48 h, and preferably 2-30 h.

[0036] Further, in step S2, when the high-temperature gas-solid purging reaction is performed, the selenium source is selenium powder and the tellurium source is tellurium powder.

[0037] Preferably, in the high-temperature gas-solid purging reaction, the protective gas is at least one selected from nitrogen, argon and helium.

[0038] Preferably, in the high-temperature gas-solid purging reaction, the gas flow rate of the protective gas is 1-70 mL / min, and specifically 2 mL / min, 5 mL / min, 10 mL / min, 15 mL / min, 30 mL / min or 70 mL / min.

[0039] Preferably, the temperature of the high-temperature gas-solid purging reaction is 250°C, 300°C, 350°C, 400°C, 500°C, 600°C, 700°C, or 800°C.

[0040] Preferably, the time of the high-temperature gas-solid purging reaction is 1-10 h, more preferably 1-6 h, and specifically 1 h, 2 h, 4 h, or 6 h.

[0041] Further, the mass ratio of the precursor nanoarray to the selenium powder or tellurium powder in the high-temperature gas-solid purging reaction is 1:(1-100), preferably 1:(1-50), and specifically 1:1, 1:5, 1:10, 1:20, or 1:50.

[0042] Further, the heating rate of the high-temperature gas-solid purging reaction is 1-20°C / min, preferably 1-10°C / min, and specifically 2°C / min, 3°C / min, 5°C / min, or 8°C / min.

[0043] Specifically, the H2O2 treatment is to place the transition metal-based nanoarray in an H2O2 solution for reaction.

[0044] Further, the molar concentration of H2O2 is 0.01-10 mol / L, preferably 0.1-5 mol / L, and more specifically 0.10 mol / L, 0.50 mol / L, 1.00 mol / L, 2.00 mol / L, 3.00 mol / L, 4.00 mol / L, or 5.00 mol / L.

[0045] Further, the temperature of the reaction is 0-50°C, preferably 10-30°C.

[0046] Further, the time of the reaction can be 1-7200 s.

[0047] Further, the H2 treatment is performed at 250-950°C, preferably 500-900°C, and more specifically 600°C, 700°C, 800°C, or 900°C.

[0048] Further, the gas selected for the plasma treatment is any one of hydrogen, argon, nitrogen, and helium.

[0049] Specifically, in step S1, the post-treatment includes cooling, washing, and drying.

[0050] The application also protects a defect engineering regulated transition metal-based nano array electrode prepared by the preparation method. The electrode material is a transition metal-based nano array electrode with high activity and stability obtained through the synergistic effect of element doping and vacancy introduction, wherein the element doping and vacancy engineering can endow the catalytic active center with an optimized electronic structure, which improves the intrinsic catalytic activity of the catalytic electrode and reduces the poisoning effect of sulfur-containing solutions on the metal catalytic active sites, thereby improving the stability of the electrode. 2- The application also protects a defect engineering regulated transition metal-based nano array electrode prepared by the preparation method. The electrode material is a transition metal-based nano array electrode with high activity and stability obtained through the synergistic effect of element doping and vacancy introduction, wherein the element doping and vacancy engineering can endow the catalytic active center with an optimized electronic structure, which improves the intrinsic catalytic activity of the catalytic electrode and reduces the poisoning effect of sulfur-containing solutions on the metal catalytic active sites, thereby improving the stability of the electrode.

[0051] The application also protects the application of the defect engineering regulated transition metal-based nano array electrode in a sulfide oxidation reaction.

[0052] The application has the following beneficial effects:

[0053] The application uses a current collector as a carrier, and a defect engineering regulated transition metal-based nano array electrode is prepared through a solvothermal reaction, a selenization or tellurization reaction, and vacancy introduction in sequence. The synergistic effect of element doping and vacancy introduction can endow the prepared transition metal-based nano array electrode material with an optimized electronic structure, which improves the intrinsic catalytic activity of the catalytic electrode and reduces the poisoning effect of sulfur-containing solutions on the metal catalytic active sites, thereby improving the stability of the electrode. 2- The application also protects a defect engineering regulated transition metal-based nano array electrode prepared by the preparation method. The electrode material is a transition metal-based nano array electrode with high activity and stability obtained through the synergistic effect of element doping and vacancy introduction, wherein the element doping and vacancy engineering can endow the catalytic active center with an optimized electronic structure, which improves the intrinsic catalytic activity of the catalytic electrode and reduces the poisoning effect of sulfur-containing solutions on the metal catalytic active sites, thereby improving the stability of the electrode. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1 SEM image of a selenium vacancy and iron doping synergistically regulated copper selenide nano array electrode prepared in Example 1.

[0055] Figure 2 SEM image of a selenium vacancy and iron doping synergistically regulated copper selenide nano array electrode prepared in Example 1.

[0056] Figure 3 SEM image of a selenium vacancy and iron doping synergistically regulated copper selenide nano array electrode prepared in Example 1.

[0057] Figure 4 SEM image of a selenium vacancy and iron doping synergistically regulated copper selenide nano array electrode prepared in Example 1.

[0058] Figure 5 SEM image of a selenium vacancy and iron doping synergistically regulated copper selenide nano array electrode prepared in Example 1.

[0059] Figure 6SEM image of tellurium vacancy and cooper and iron co-doped nickel telluride nanowire array electrode prepared for Example 6.

[0060] Figure 7 SEM image of selenium vacancy and manganese co-doped nickel selenide nanowire array electrode prepared for Example 7.

[0061] Figure 8 SEM image of tellurium vacancy and cooper and manganese co-doped nickel telluride nanowire array electrode prepared for Example 8.

[0062] Figure 9 Linear sweep voltammetry (LSV) plot of SOR of nanowire array electrodes for Example 1 and Comparative Example 1, Comparative Example 2, Comparative Example 3 at room temperature.

[0063] Figure 10 Stability test data statistical plot of SOR of nanowire array electrodes for Example 1 and Comparative Example 1 using chronopotentiometry at room temperature.

[0064] Figure 11 Linear sweep voltammetry (LSV) plot of SOR of nanowire array electrodes for Example 3 and Comparative Example 4, Comparative Example 5, Comparative Example 6 at room temperature.

[0065] Figure 12 Stability test data statistical plot of SOR of nanowire array electrodes for Example 3 and Comparative Example 4 using chronopotentiometry at room temperature.

[0066] Figure 13 Linear sweep voltammetry (LSV) plot of SOR of nanowire array electrodes for Example 4 and Comparative Example 7, Comparative Example 8, Comparative Example 9 at room temperature.

[0067] Figure 14 Stability test data statistical plot of SOR of nanowire array electrodes for Example 4 and Comparative Example 7 using chronopotentiometry at room temperature.

[0068] Figure 15 Linear sweep voltammetry (LSV) plot of SOR of nanowire array electrodes for Example 6 and Comparative Example 10, Comparative Example 11, Comparative Example 12 at room temperature.

[0069] Figure 16 Stability test data statistical plot of SOR of nanowire array electrodes for Example 6 and Comparative Example 10 using chronopotentiometry at room temperature.

[0070] Figure 17 Linear sweep voltammetry (LSV) plot of SOR of nanowire array electrodes for Example 8 and Comparative Example 13, Comparative Example 14, Comparative Example 15 at room temperature.

[0071] Figure 18The stability test data graph of SOR of the nanometer array electrode for example 8 and comparative example 13 was carried out by chronopotentiometry at room temperature. DETAILED DESCRIPTION

[0072] The present application will be further described by the following description and specific examples in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field.

[0073] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0074] Example 1 Selenium vacancy and iron-doped synergistically regulated copper selenide nanometer array electrode (NF / Fe-CuSe-V Se )

[0075] The preparation method of the selenium vacancy and iron-doped synergistically regulated copper selenide nanometer array electrode includes the following steps:

[0076] S1, 0.4 mmol Cu(CH3COO)2·H2O, 0.1 mmol Fe(NO3)3·9H2O and 1 mmol hexamethylenetetramine were dissolved in 15 mL ultrapure water to form a uniformly mixed solution, 2 pieces of clean 1×3 cm foam nickel (NF) were placed in it, and after stirring for 30 min, it was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner to carry out hydrothermal reaction in a 120℃ blast drying oven for 8 h. After the reaction was completed, it was naturally cooled, the cooled material was washed with anhydrous ethanol for 3 times, and dried in a blast drying oven at 60℃ for 12 h to obtain an iron-doped copper hydroxide nanometer array precursor (NF / Fe-CuOH) grown in situ on the NF;

[0077] S2, the NF / Fe-CuOH obtained in step S1 was placed in 30 mL 0.20 mol / L sodium hydroselenide solution generated by the reaction of selenium powder with sodium borohydride, and after stirring for 10 min under N2, it was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner to carry out hydrothermal reaction in a 140℃ blast drying oven for 12 h. After the reaction was completed, it was naturally cooled, the cooled material was washed with anhydrous ethanol for 3 times, and dried in a vacuum drying oven at 60℃ for 12 h to obtain an iron-doped copper selenide nanometer array (NF / Fe-CuSe) grown in situ on the NF;

[0078] S3, the NF / Fe-CuSe obtained in step S2 was placed in a prepared 20 mL 3 mol / L H2O2 solution, and after reacting for 60 s, it was washed with alcohol for 3 times to obtain a selenium vacancy and iron-doped synergistically regulated copper selenide nanometer array (NF / Fe-CuSe-V Se ) grown in situ on the NF;

[0079] Material characterization:

[0080] The obtained product was characterized by SEM to characterize the morphology of the material, and it was found that Figure 1 As can be seen from the figure, the nanosheet structure is uniformly distributed on the NF current collector.

[0081] Example 2 Selenium vacancy and iron and molybdenum doping synergistically regulated manganese selenide nanometer array electrode (TM / FeMo-MnSe-V Se )

[0082] The preparation method of the selenium vacancy and iron and molybdenum doping synergistically regulated manganese selenide nanometer array electrode includes the following steps:

[0083] S1, take 0.08mmol MnCl2·4H2O, 0.01mmol Fe(NO3)3·9H2O, 0.01mmol (NH4)6Mo7O 24 ·4H2O and 1.6mmol urea are dissolved in 15mL ultrapure water to form a uniform mixed solution, 2 pieces of 1×3cm titanium mesh (TM) are placed in it, and after stirring for 30min, it is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner to carry out hydrothermal reaction in a 180℃ air drying oven for 12h, after the reaction is completed, it is naturally cooled, the cooled material is washed with anhydrous ethanol for 3 times, and dried in a forced air drying oven at 80℃ for 12h, to obtain an iron and molybdenum doped manganese hydroxide nanometer array precursor (TM / FeMo-MnOH) grown in situ on TM;

[0084] S2, the TM / FeMo-MnOH obtained in step S1 is placed in 30mL 0.01mol / L sodium hydroselenide solution generated by the reaction of selenium powder and sodium borohydride, and after stirring for 10min under N2, it is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner, and hydrothermal reaction is carried out in a 160℃ air drying oven for 12h, after the reaction is completed, it is naturally cooled, the cooled material is washed with anhydrous ethanol for 3 times, and dried in a vacuum drying oven at 60℃ for 12h, to obtain an iron and molybdenum doped manganese selenide nanometer array (TM / FeMo-MnSe) grown in situ on TM;

[0085] S3, the TM / FeMo-MnSe obtained in step S2 is placed in a prepared 20mL 5mol / L H2O2 solution, and after reacting for 20s, it is washed with alcohol for 3 times, to obtain a selenium vacancy and iron and molybdenum doping synergistically regulated manganese selenide nanometer array (TM / FeMo-MnSe-V Se ) grown in situ on TM;

[0086] Material characterization:

[0087] The obtained product was characterized by SEM to characterize the morphology of the material, and it was found that Figure 2It can be seen from the figure that the nanosheet structure is uniformly distributed on the TM current collector.

[0088] Example 3 Tellurium vacancy and manganese-doped synergistically regulated cobalt telluride nanometer array electrode (SS / Mn-CoTe-V Te )

[0089] The preparation method of the tellurium vacancy and manganese-doped synergistically regulated cobalt telluride nanometer array electrode comprises the following steps:

[0090] S1, 2mmol Co(NO3)2·6H2O, 1mmol MnCl2.4H2O and 3mmol sodium bicarbonate were dissolved in 20mL acetonitrile and 30mL ethanol mixed solvent to form a uniform mixed solution, 2 pieces of 1*3cm stainless steel (SS) were placed in it, and after stirring for 30min, it was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a 140℃ air drying oven for 8h, and after the reaction was completed, it was naturally cooled, the cooled material was washed with anhydrous ethanol for 3 times, and dried in a 60℃ air drying oven for 12h to obtain manganese-doped cobalt hydroxide nanometer array precursor (SS / Mn-CoOH) grown in situ on SS;

[0091] S2, the SS / Mn-CoOH obtained in step S1 was placed in 30mL 2mol / L sodium telluride solution generated by the reaction of tellurium powder with sodium borohydride, and after stirring for 10min under N2, it was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a 200℃ air drying oven for 15h, and after the reaction was completed, it was naturally cooled, the cooled material was washed with anhydrous ethanol for 3 times, and dried in a 60℃ vacuum drying oven for 12h to obtain manganese-doped cobalt telluride nanometer array (SS / Mn-CoTe) grown in situ on SS;

[0092] S3, the SS / Mn-CoTe obtained in step S2 was placed in a prepared 50mL 1mol / L H2O2 solution, and after reaction for 60s, it was washed with alcohol for 3 times to obtain tellurium vacancy and manganese-doped synergistically regulated cobalt telluride nanometer array (SS / Mn-CoTe-V Te ) grown in situ on SS;

[0093] Material characterization:

[0094] The obtained product was characterized by SEM to obtain the material morphology. Figure 3 It can be seen from the figure that the nanosheet structure is uniformly distributed on the SS current collector.

[0095] Example 4 Selenium vacancy and tungsten-doped synergistically regulated iron selenide nanometer array electrode (CC / W-FeSe-V Se )

[0096] The preparation method of the selenium vacancy and tungsten-doped synergistically regulated iron selenide nanometer array electrode comprises the following steps:

[0097] S1, take 1.5 mmol Fe(NO3)3·9H2O, 0.5 mmol (NH4) 10 H2(W2O7)6 and 8 mmol of sodium hydroxide are dissolved in 10 mL of ethanol and 20 mL of methanol mixed solvent to form a uniform mixed solution, 2 pieces of 1*3 cm carbon cloth (CC) are placed in it, and after stirring for 30 min, it is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner to carry out hydrothermal reaction in a 120℃ air drying oven for 8h, after the reaction is completed, it is naturally cooled, the cooled material is washed with anhydrous ethanol for 3 times, and dried in a blowing drying oven at 60℃ for 12h, to obtain a tungsten-doped iron hydroxide nanometer array precursor (CC / W-FeOH) grown in situ on the CC;

[0098] S2, the CC / W-FeOH obtained in step S1 is placed downstream in a tube furnace, and selenium powder is placed upstream, the mass ratio of CC / W-FeOH to selenium powder is 1:5, the N2 flow rate is controlled at 10 mL / min, and the temperature is raised from room temperature to 600℃ at a rate of 3℃ / min, and then heat treated at 600℃ for 1.5h, and after natural cooling, a tungsten-doped iron selenide nanometer array (CC / W-FeSe) grown in situ on the CC is obtained;

[0099] S3, the CC / W-FeSe obtained in step S2 is placed in a prepared 20mL 0.5mol / L H2O2 solution, and after reacting for 120s, it is washed with alcohol for 3 times to obtain a selenium vacancy and tungsten-doped synergistically regulated iron selenide nanometer array (CC / W-FeSe-V Se ) grown in situ on the CC;

[0100] Material characterization:

[0101] The obtained product is characterized by SEM to obtain the material morphology Figure 4 As can be seen from the figure, the nanosheet structure is uniformly distributed on the CC current collector.

[0102] Example 5: Tellurium vacancy and copper-doped synergistically regulated nickel telluride nanometer array electrode (IF / Cu-NiTe-V Te )

[0103] The preparation method of the tellurium vacancy and copper-doped synergistically regulated nickel telluride nanometer array electrode comprises the following steps:

[0104] S1, 0.1 mmol of NiCl2.6H2O, 0.1 mmol of CuSO4.5H2O, 0.5 mmol of hexamethylenetetramine and 0.8 mmol of potassium hydroxide were dissolved in 15 mL of ethanol to form a uniform mixed solution, two pieces of 1x3 cm of clean foam iron (IF) were placed in it, after stirring for 30 min, it was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and subjected to hydrothermal reaction at 200℃ in a blast drying oven for 15 h, after the reaction was completed, it was naturally cooled, the cooled material was washed with anhydrous ethanol for 3 times, and dried at 60℃ in a blast drying oven for 12 h, to obtain a copper-doped nickel hydroxide nanometer array precursor (IF / Cu-NiOH) grown in situ on the IF;

[0105] S2, the IF / Cu-NiOH obtained in step S1 was placed downstream in a tube furnace, and a tellurium source tellurium powder was placed upstream, the mass ratio of IF / Cu-NiOH to tellurium source tellurium powder was 1:20, the N2 flow rate was controlled at 70 mL / min, the temperature was raised from room temperature to 800℃ at a rate of 8℃ / min, and the heat treatment was carried out at 800℃ for 4.0 h, after natural cooling, a copper-doped nickel telluride nanometer array (IF / Cu-NiTe) grown in situ on the IF was obtained;

[0106] S3, the IF / Cu-NiTe obtained in step S2 was placed in a prepared 100 mL 0.01 mol / L H2O2 solution, after reaction for 7200 s, it was washed with alcohol for 3 times, to obtain a tellurium vacancy and copper-doped synergistically regulated nickel telluride nanometer array (IF / Cu-NiTe-V Te ) grown in situ on the IF;

[0107] Material characterization:

[0108] The obtained product was characterized by SEM to obtain the material morphology Figure 5 As can be seen from the figure, the nanosheet structure is uniformly distributed on the IF current collector.

[0109] Example 6 Tellurium vacancy and copper and iron-doped synergistically regulated nickel telluride nanometer array electrode (NF / CuFe-NiTe-V Te

[0110] The preparation method of the tellurium vacancy and copper and iron-doped synergistically regulated nickel telluride nanometer array electrode comprises the following steps:

[0111] ​S1, 2.0 mmol of Ni(NO3)2·6H2O, 0.5 mmol of Cu(NO3)2·3H2O, 0.5 mmol of Fe(NO3)3·9H2O, and 6 mmol of sodium carbonate were dissolved in a mixed solvent containing 20 mL of methanol and 30 mL of ultrapure water to form a uniform mixed solution, 2 pieces of 1 x 3 cm NF cleaned and dried were placed in the solution, and after stirring for 30 min, the solution was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and subjected to hydrothermal reaction at 180℃ in a blast drying oven for 10 h. After the reaction was completed, the material was naturally cooled, washed with anhydrous ethanol 3 times, and dried at 60℃ in a blast drying oven for 12 h to obtain a copper and iron doped nickel hydroxide nanometer array precursor (NF / CuFe-NiOH) grown in situ on the NF;

[0112] S2, the NF / CuFe-NiOH obtained in step S1 was placed downstream in a tube furnace, and a tellurium source, tellurium powder, was placed upstream. The mass ratio of NF / CuFe-NiOH to tellurium source, tellurium powder, was 1:1, the N2 flow rate was controlled at 2 mL / min, and the temperature was raised from room temperature to 800℃ at a rate of 2℃ / min. After heating at 800℃ for 1.5 h, the material was naturally cooled to obtain a copper and iron doped nickel telluride nanometer array (NF / CuFe-NiTe) grown in situ on the NF;

[0113] S3, the NF / CuFe-NiTe obtained in step S2 was placed in a prepared 20 mL 4 mol / L H2O2 solution, and after reacting for 120 s, the material was washed with alcohol 3 times to obtain a tellurium vacancy and copper and iron doped synergistically regulated nickel telluride nanometer array (NF / CuFe-NiTe-V Te );

[0114] Material characterization:

[0115] The obtained product was characterized by SEM to obtain the material morphology Figure 6 As can be seen from the figure, the NF current collector is uniformly distributed with nanosheet structures.

[0116] Example 7 selenium vacancy and manganese doped synergistically regulated nickel selenide nanometer array electrode (TP / Mn-NiSe-V Se

[0117] The preparation method of the selenium vacancy and manganese doped synergistically regulated nickel selenide nanometer array electrode comprises the following steps:

[0118] ​S1, 0.4 mmol of Ni(CH3COO)2·4H2O, 0.1 mmol of Mn(NO3)2 and 1 mmol of ammonia were dissolved in a mixed solvent of 10 mL of acetonitrile and 5 mL of isopropyl alcohol to form a uniform mixed solution, two pieces of 1x3 cm titanium plate (TP) were placed in the solution, and after stirring for 30 min, the solution was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a 120°C blast drying oven for 8 h. After the reaction was completed, the material was naturally cooled, washed with anhydrous ethanol three times, and dried in a blast drying oven at 60°C for 12 h to obtain a manganese-doped nickel hydroxide nanometer array precursor (TP / Mn-NiOH) grown in situ on the TP;

[0119] S2, the TP / Mn-NiOH obtained in step S1 was placed in 30 mL of 0.20 mol / L sodium hydroselenide solution generated by the reaction of selenium powder with sodium borohydride, and after stirring for 10 min under N2, the solution was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a 140°C blast drying oven for 12 h. After the reaction was completed, the material was naturally cooled, washed with anhydrous ethanol three times, and dried in a vacuum drying oven at 60°C for 12 h to obtain a manganese-doped nickel selenide nanometer array (TP / Mn-NiSe) grown in situ on the TP;

[0120] S3, the TP / Mn-NiSe obtained in step S2 was placed downstream of a tube furnace, and the H2 flow rate was controlled at 10 mL / min. The temperature was increased from room temperature to 800°C at a rate of 5°C / min, and the material was heat-treated at 800°C for 2.0 h. After natural cooling, a selenium vacancy and manganese-doped cooperatively regulated nickel selenide nanometer array (TP / Mn-NiSe-V Se ) grown in situ on the TP was obtained;

[0121] Material characterization:

[0122] The obtained product was characterized by SEM to obtain the material morphology, and Figure 7 As can be seen from the figure, the nanosheet structure is uniformly distributed on the TP current collector.

[0123] Example 8: Tellurium vacancy and copper and manganese-doped cooperatively regulated nickel telluride nanometer array electrode (TM / CuMn-NiTe-V Te )

[0124] The preparation method of the tellurium vacancy and copper and manganese-doped cooperatively regulated nickel telluride nanometer array electrode comprises the following steps:

[0125] S1, 0.4 mmol of Ni(NO3)2·6H2O, 0.05 mmol of Cu(NO3)2·3H2O, 0.05 mmol of MnCl2·4H2O and 1 mmol of sodium hydroxide were dissolved in 15 mL of ultrapure water to form a homogeneous mixed solution, 2 pieces of clean titanium mesh (TM) with a size of 1x3 cm were placed in it, stirred for 30 min, and then transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner to carry out hydrothermal reaction at 120°C in a blast drying oven for 8 h. After the reaction was completed, it was allowed to cool naturally. The cooled material was washed with anhydrous ethanol 3 times and dried in a blast drying oven at 60°C for 12 h to obtain a copper and manganese doped nickel hydroxide nanometer array precursor (TM / CuMn-NiOH) grown in situ on the TM;

[0126] S2, the TM / CuMn-NiOH obtained in step S1 was placed in 30 mL of 0.30 mol / L sodium telluride solution generated by the reaction of tellurium powder with sodium borohydride, and stirred for 10 min under N2. Then it was transferred to a high-pressure reaction kettle with a polytetrafluoroethylene liner and hydrothermal reaction was carried out at 180°C in a blast drying oven for 15 h. After the reaction was completed, it was allowed to cool naturally. The cooled material was washed with anhydrous ethanol 3 times and dried in a vacuum drying oven at 60°C for 12 h to obtain a copper and manganese doped nickel telluride nanometer array (TM / CuMn-NiTe) grown in situ on the TM;

[0127] S3, the TM / CuMn-NiTe obtained in step S2 was placed in a plasma generator and treated under an Ar atmosphere at a flow rate of 3 mL / min, with a temperature increase rate of 10°C / min from room temperature to 400°C, and then treated at a power of 200 W and a pressure of 70 Pa for 10 min to obtain a tellurium vacancy and copper and manganese doped synergistically regulated nickel telluride nanometer array (TM / CuMn-NiTe-V) grown in situ on the TM; -1 Te ;

[0128] Material characterization:

[0129] The obtained product was characterized by SEM to obtain the material morphology Figure 8 As can be seen from the figure, the TM current collector is uniformly distributed with nanosheet structure.

[0130] Comparative Example 1: Copper selenide nanometer array electrode (NF / CuSe)

[0131] The preparation method of the copper selenide nanometer array electrode comprises the following steps:

[0132] Compared with Example 1, the difference of Comparative Example 1 is that no Fe(NO3)3·9H2O is added for iron element doping in step S1 and step S3 of vacancy preparation is not carried out; ​

[0133] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 1.

[0134] Comparative Example 2 Iron-doped copper selenide nanorarray electrode (NF / Fe-CuSe)

[0135] The preparation method of the iron-doped copper selenide nanorarray electrode comprises the following steps:

[0136] Comparative Example 2 is different from Example 1 in that the vacancy preparation of step S3 is not performed;

[0137] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 1.

[0138] Comparative Example 3 Selenium vacancy-doped copper selenide nanorarray electrode (NF / CuSe-V Se )

[0139] The preparation method of the selenium vacancy-doped copper selenide nanorarray electrode comprises the following steps:

[0140] Comparative Example 3 is different from Example 1 in that Fe(NO3)3·9H2O is not added for iron element doping in step S1.

[0141] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 1.

[0142] Comparative Example 4 Cobalt telluride nanorarray electrode (SS / CoTe)

[0143] The preparation method of the cobalt telluride nanorarray electrode comprises the following steps:

[0144] Comparative Example 4 is different from Example 3 in that MnCl2.4H2O is not added for manganese element doping in step S1 and the vacancy preparation of step S3 is performed;

[0145] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 3.

[0146] Comparative Example 5 Manganese-doped cobalt telluride nanorarray electrode (SS / Mn-CoTe)

[0147] The preparation method of the manganese-doped cobalt telluride nanorarray electrode comprises the following steps:

[0148] Comparative Example 5 is different from Example 3 in that the vacancy preparation of step S3 is not performed;

[0149] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 3.

[0150] Comparative Example 6 Tellurium vacancy regulated cobalt telluride nanorarray electrode (SS / CoTe-V Te )

[0151] The preparation method of the tellurium vacancy regulated cobalt telluride nanorarray electrode comprises the following steps:

[0152] Compared with Example 3, the difference of Comparative Example 6 lies in that MnCl2.4H2O is not added for manganese element doping in step S1;

[0153] The other steps, reagents, parameters (including the total amount of substance of transition metal) are consistent with Example 3.

[0154] Comparative Example 7 Iron selenide nanorarray electrode (CC / FeSe)

[0155] The preparation method of the iron selenide nanorarray electrode comprises the following steps:

[0156] Compared with Example 4, the difference of Comparative Example 7 lies in that Fe(NO3)3.9H2O is not added for iron element doping in step S1 and the vacancy preparation of step S3 is not performed;

[0157] The other steps, reagents, parameters (including the total amount of substance of transition metal) are consistent with Example 4.

[0158] Comparative Example 8 Tungsten-doped regulated iron selenide nanorarray electrode (CC / W-FeSe)

[0159] The preparation method of the tungsten-doped regulated iron selenide nanorarray electrode comprises the following steps:

[0160] Compared with Example 4, the difference of Comparative Example 8 lies in that the vacancy preparation of step S3 is not performed;

[0161] The other steps, reagents, parameters (including the total amount of substance of transition metal) are consistent with Example 4.

[0162] Comparative Example 9 Selenium vacancy regulated iron selenide nanorarray electrode (CC / FeSe-V Se )

[0163] The preparation method of the selenium vacancy regulated iron selenide nanorarray electrode comprises the following steps:

[0164] Compared with Example 4, the difference of Comparative Example 9 lies in that Fe(NO3)3.9H2O is not added for iron element doping in step S1;

[0165] The other steps, reagents, parameters (including the total amount of substance of transition metal) are consistent with Example 4.

[0166] Comparative Example 10 Nickel telluride nanomaterial electrode (NF / NiTe-V Te )

[0167] The preparation method of the nickel telluride nanomaterial electrode comprises the following steps:

[0168] Comparative Example 10 is different from Example 6 in that no element doping with Cu(NO3)2·3H2O and Fe(NO3)3·9H2O is performed in step S1, and no vacancy preparation of step S3 is performed.

[0169] The other steps, reagents, and parameters (including the total amount of substance of transition metals) are consistent with Example 6.

[0170] Comparative Example 11 Copper and iron doping regulated nickel telluride nanomaterial electrode (NF / CuFe-NiTe)

[0171] The preparation method of the copper and iron doping regulated nickel telluride nanomaterial electrode comprises the following steps:

[0172] Comparative Example 11 is different from Example 6 in that no vacancy preparation of step S3 is performed.

[0173] The other steps, reagents, and parameters (including the total amount of substance of transition metals) are consistent with Example 6.

[0174] Comparative Example 12 Tellurium vacancy regulated nickel telluride nanomaterial electrode (NF / NiTe-V Te )

[0175] The preparation method of the tellurium vacancy regulated nickel telluride nanomaterial electrode comprises the following steps:

[0176] Comparative Example 12 is different from Example 6 in that no element doping with Cu(NO3)2·3H2O and Fe(NO3)3·9H2O is performed in step S1.

[0177] The other steps, reagents, and parameters (including the total amount of substance of transition metals) are consistent with Example 6.

[0178] Comparative Example 13 Nickel telluride nanomaterial electrode (TM / NiTe)

[0179] The preparation method of the nickel telluride nanomaterial electrode comprises the following steps:

[0180] Comparative Example 13 is different from Example 8 in that no element doping with Cu(NO3)2·3H2O and MnCl2·4H2O is performed in step S1, and no vacancy preparation of step S3 is performed.

[0181] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 8.

[0182] Comparative Example 14 Copper and manganese doped controlled tellurium nickel nanometer array electrode (TM / CuMn-NiTe)

[0183] The preparation method of the copper and manganese doped controlled tellurium nickel nanometer array electrode comprises the following steps:

[0184] Compared with Example 8, the difference of Comparative Example 14 is that the vacancy preparation of step S3 is not carried out;

[0185] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 8.

[0186] Comparative Example 15 Tellurium vacancy controlled tellurium nickel nanometer array electrode (TM / NiTe-V Te )

[0187] The preparation method of the tellurium vacancy controlled tellurium nickel nanometer array electrode comprises the following steps:

[0188] Compared with Example 8, the difference of Comparative Example 15 is that the vacancy preparation of step S3 is not carried out in step S1;

[0189] Other steps, reagents, parameters (including total amount of substance of transition metal) are consistent with Example 8.

[0190] Performance test object

[0191] The following takes Examples 1, 3, 4, 6, 8 and Comparative Examples 1-15 as examples to measure the activity and stability of the prepared material in electrocatalytic sulfide oxidation reaction at room temperature, and other example results are similar to those of Examples 1, 3, 4, 6, 8.

[0192] Application Example 1 Performance test of electrocatalytic sulfide oxidation reaction (SOR)

[0193] The electrochemical test adopts a computer-controlled electrochemical workstation (Autolab, PGSTAT302N), and a standard three-electrode system is used for measurement. The indicators for evaluating the activity of the electrocatalytic material are: the current density reaches 100 mA cm -2 The required voltage (E 100 ), the lower the voltage value, the better the electrocatalytic activity (or the faster the current density rises, the smaller the change in voltage value, the better the electrocatalytic activity); the method for evaluating the stability of the electrocatalytic material is: the change of voltage with time under constant current (0.10 A), i.e. chronopotentiometry (CP), the smaller the amplitude of the change of voltage with time, the better the electrocatalytic stability.

[0194] Array electrodes (cut into 1 x 1 cm 2 ) prepared in Examples or Comparative Examples were investigated for electrocatalytic activity and stability of samples in a three-electrode system with the array electrode as the working electrode, a carbon rod as the counter electrode, and a Hg / HgO (immersed in 1.0 M KOH solution) electrode as the reference electrode. For electrocatalytic activity testing, the catalyst was activated by CV (-0.90-0 V vs. Hg / HgO) scanning in a sulfide-containing electrolyte (1 M NaOH + 1 M Na2S, pH = 13.74) under stirring, and after the CV scanning results were stable, LSV curves were tested (-0.90-0 V vs. Hg / HgO), and 95% iR compensation was performed on the LSV curves. For electrocatalytic stability testing, the catalyst was activated by CV (-0.90-0 V vs. Hg / HgO) scanning in a sulfide-containing electrolyte (1 M NaOH + 1 M Na2S, pH = 13.74) under stirring, and after the CV scanning results were stable, chronoamperometry stability testing was performed at a current density of 100 mA cm -2 . The testing process was to ensure that the electrolyte solution contained sufficient sulfide, and the solution was replaced every 24 h. According to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 x pH, the potential value E(RHE) was converted from E(Hg / HgO), where pH was the pH of the sulfide-containing electrolyte.

[0195] The SOR activity of the selenium vacancy and iron doping synergistically regulated copper selenide nanometer array electrode (NF / Fe-CuSe-V Se ) of Example 1 and the copper selenide nanometer array electrode (NF / CuSe) of Comparative Example 1, the iron doping regulated copper selenide nanometer array electrode (NF / Fe-CuSe) of Comparative Example 2, and the selenium vacancy regulated copper selenide nanometer array electrode (NF / CuSe-V Se ) of Comparative Example 3 was tested, and the results are shown in Figure 9 ; the SOR stability of the selenium vacancy and iron doping synergistically regulated copper selenide nanometer array electrode (NF / Fe-CuSe-V Se ) of Example 1 and the copper selenide nanometer array electrode (NF / CuSe) of Comparative Example 1 was tested, and the results are shown in Figure 10 .

[0196] As can be seen from Figure 9 , for the activity of SOR, compared with NF / CuSe, NF / Fe-CuSe, and NF / CuSe-V Se , NF / Fe-CuSe-V Se has a smaller E 100 , and E 100 vs. RHE is NF / Fe-CuSe-V Se(0.303 V) < NF / Fe-CuSe (0.344 V) < NF / CuSe-V Se (0.340 V) < NF / CuSe (0.413 V). From Figure 10 It can be seen that, for the stability of SOR, NF / Fe-CuSe-V Se could be operated stably for 96 h at a current density of 100 mA cm -2 , while the performance of NF / CuSe decreased significantly after 24 h of operation. With the increase of time, the voltage values of both NF / Fe-CuSe-V Se and NF / CuSe increased, but the voltage value of NF / CuSe increased faster. After replacing the sulfide-containing electrolyte solution, the voltage value of NF / Fe-CuSe-V Se could recover to the previous one, but the voltage value of NF / CuSe could not. It can be seen that NF / Fe-CuSe-V Se has excellent stability. It can be seen that, compared with the copper selenide nanometer array electrode, the selenium vacancy and iron-doped cooper selenide nanometer array electrode has more excellent activity and stability in SOR.

[0197] Application Example 2 Performance test of electrocatalytic sulfide oxidation reaction (SOR)

[0198] The SOR activity test was performed on the tellurium vacancy and manganese-doped cooper selenide nanometer array electrode (SS / Mn-CoTe-V Te ) of Example 3, the cooper selenide nanometer array electrode (SS / CoTe) of Comparative Example 4, the manganese-doped cooper selenide nanometer array electrode (SS / Mn-CoTe) of Comparative Example 5, and the tellurium vacancy-doped cooper selenide nanometer array electrode (SS / CoTe-V Te ) of Comparative Example 6; the SOR stability test was performed on the tellurium vacancy and manganese-doped cooper selenide nanometer array electrode (SS / Mn-CoTe-V Te ) of Example 3 and the cooper selenide nanometer array electrode (SS / CoTe) of Comparative Example 4; the test method was the same as that of Application Example 1, and the results were shown in Figure 11 and Figure 12 .

[0199] From Figure 11 it can be seen that, for the activity of SOR, compared with SS / CoTe, SS / Mn-CoTe and SS / CoTe-V Te , SS / Mn-CoTe-V Te has a smaller E 100 , and the E 100 vs. RHE of SS / Mn-CoTe-V Te(0.328V) < SS / Mn-CoTe (0.403V) < SS / CoTe-V Te (0.426V) < SS / CoTe (0.483V). From Figure 12 It can be seen that, for the stability of SOR, SS / Mn-CoTe-V Te can be stably operated for 96h at a current density of 100mA cm -2 , while the performance of SS / CoTe decreases significantly after 24h of operation. With the increase of time, the voltage values of SS / Mn-CoTe-V Te and SS / CoTe are both increasing, but the voltage value of SS / CoTe increases faster. After replacing the sulfide-containing electrolyte solution, the voltage value of SS / Mn-CoTe-V Te can recover to the previous one, while the voltage value of SS / CoTe cannot. It can be seen that SS / Mn-CoTe-V Te has excellent stability. It can be seen that, compared with the cobalt telluride nanometer array electrode, the cobalt telluride nanometer array electrode synergistically regulated by tellurium vacancy and manganese doping has more excellent activity and stability in SOR.

[0200] Application Example 3 Performance test of electrocatalytic sulfide oxidation reaction (SOR)

[0201] The SOR activity test was performed on the selenium vacancy and tungsten doping synergistically regulated iron selenide nanometer array electrode (CC / W-FeSe-V Se ) of Example 4, the iron selenide nanometer array electrode (CC / FeSe) of Comparative Example 7, the tungsten doping regulated iron selenide nanometer array electrode (CC / W-FeSe) of Comparative Example 8, and the selenium vacancy regulated iron selenide nanometer array electrode (CC / FeSe-V Se ) of Comparative Example 9; the SOR stability test was performed on the selenium vacancy and tungsten doping synergistically regulated iron selenide nanometer array electrode (CC / W-FeSe-V Se ) of Example 4 and the iron selenide nanometer array electrode (CC / FeSe) of Comparative Example 7; the test method was the same as that of Application Example 1, and the results were seen in Figure 13 and Figure 14 .

[0202] From Figure 13 it can be seen that, for the activity of SOR, compared with CC / FeSe, CC / W-FeSe and CC / FeSe-V Se , CC / W-FeSe-V Se has a smaller E 100 , E 100 vs. RHE of CC / W-FeSe-V Se (0.328V) < CC / FeSe-V Se(0.403 V) < CC / W-FeSe (0.426 V) < CC / FeSe (0.526 V). From Figure 14 It can be seen that for the stability of SOR, CC / W-FeSe-V Se can operate stably at a current density of 100 mA cm -2 for 96 h, while the performance of CC / FeSe decreases significantly after 24 h of operation. As time increases, the voltage values of both CC / W-FeSe-V Se and CC / FeSe increase, but the voltage value of CC / FeSe increases faster. After replacing the sulfide-containing electrolyte solution, the voltage value of CC / W-FeSe-V Se can return to the previous level, while the voltage value of CC / FeSe cannot. It can be seen that CC / W-FeSe-V Se has excellent stability. Thus, compared with the iron selenide nanorod array electrode, the iron selenide nanorod array electrode co-regulated by selenium vacancies and tungsten doping has more excellent activity and stability in SOR.

[0203] Application Example 4 Performance Test of Electrocatalytic Sulfide Oxidation Reaction (SOR)

[0204] Perform SOR activity tests on the nickel telluride nanorod array electrode (NF / CuFe-NiTe-V Te ) co-regulated by tellurium vacancies and copper and iron doping in Example 6, the nickel telluride nanorod array electrode (NF / NiTe) in Comparative Example 10, the nickel telluride nanorod array electrode (NF / CuFe-NiTe) regulated by copper and iron doping in Comparative Example 11, and the nickel telluride nanorod array electrode (NF / NiTe-V Te ) regulated by tellurium vacancies; perform SOR stability tests on the nickel telluride nanorod array electrode (NF / CuFe-NiTe-V Te ) co-regulated by tellurium vacancies and copper and iron doping in Example 6 and the nickel telluride nanorod array electrode (NF / NiTe) in Comparative Example 10; the test method is the same as that in Application Example 1, and the results are shown in Figure 15 and Figure 16 .

[0205] From Figure 15 it can be seen that for the activity of SOR, compared with NF / NiTe, NF / CuFe-NiTe, and NF / NiTe-V Te , NF / CuFe-NiTe-V Te has a smaller E 100 , and E 100 vs. RHE are NF / CuFe-NiTe-V Te (0.382 V) < NF / NiTe-V Te(0.483 V) < NF / CuFe-NiTe (0.486 V) < NF / NiTe (0.675 V). From Figure 16 It can be seen that, for the stability of SOR, NF / CuFe-NiTe-V Te At a current density of 100 mA cm -2 , it can be stably operated for 96 h, while the performance of NF / NiTe is significantly reduced after 24 h of operation. With the increase of time, the voltage values of NF / CuFe-NiTe-V Te and NF / NiTe are both increasing, but the voltage value of NF / NiTe increases faster. After replacing the sulfide-containing electrolyte solution, the voltage value of NF / CuFe-NiTe-V Te can be restored to before, but the voltage value of NF / NiTe cannot, which shows that NF / CuFe-NiTe-V Te has excellent stability. Therefore, compared with the nickel telluride nanometer array electrode, the nickel telluride nanometer array electrode synergistically regulated by tellurium vacancies and copper and iron doping has more excellent activity and stability in SOR.

[0206] Application Example 5 Performance test of electrocatalytic sulfide oxidation reaction (SOR)

[0207] The SOR activity test was performed on the nickel telluride nanometer array electrode synergistically regulated by tellurium vacancies and copper and manganese doping (TM / CuMn-NiTe-V Te ) of Example 8 and the nickel telluride nanometer array electrode (TM / NiTe) of Comparative Example 13, the nickel telluride nanometer array electrode regulated by copper and manganese doping (TM / CuMn-NiTe) of Comparative Example 14 and the nickel telluride nanometer array electrode regulated by tellurium vacancies (TM / NiTe-V Te ) of Comparative Example 15; the SOR stability test was performed on the nickel telluride nanometer array electrode synergistically regulated by tellurium vacancies and copper and manganese doping (TM / CuMn-NiTe-V Te ) of Example 8 and the nickel telluride nanometer array electrode (TM / NiTe) of Comparative Example 13; the test method was the same as that of Application Example 1, and the results were shown in Figure 17 and Figure 18 .

[0208] From Figure 17 it can be seen that, for the activity of SOR, compared with TM / NiTe, TM / CuMn-NiTe and TM / NiTe-V Te , TM / CuMn-NiTe-V Te has a smaller E 100 , E 100 vs. RHE is TM / CuMn-NiTe-V Te (0.326 V) < TM / NiTe-VTe (0.368 V) <TM / CuMn-NiTe(0.372 V) <TM / NiTe(0.559 V). From the results, it can be seen that the TM / CuMn-NiTe-V Figure 18 It can be seen that the TM / CuMn-NiTe-V Te At a current density of 100 mA cm-2, the TM / CuMn-NiTe-V -2 can be stably operated for 96 h, while the performance of the TM / NiTe is significantly reduced after 24 h of operation. With the increase of time, the voltage values of both the TM / CuMn-NiTe-V Te and the TM / NiTe are increasing, but the voltage value of the TM / NiTe increases faster. After replacing the sulfide-containing electrolyte solution, the voltage value of the TM / CuMn-NiTe-V Te can be restored to the previous one, but the voltage value of the TM / NiTe cannot, which indicates that the TM / CuMn-NiTe-V Te has excellent stability. It can be seen that, compared with the nickel telluride nanomaterial electrode, the nickel telluride nanomaterial electrode synergistically regulated by tellurium vacancies and copper and manganese doping has more excellent activity and stability in the SOR.

[0209] In summary, the electrocatalytic SOR activity and stability of the electrode of the embodiment are both superior to those of the comparative examples. It can be seen that the defect-engineered transition metal-based nanomaterial electrode prepared in the present application has great application prospects in the SOR.

[0210] The above embodiment is a preferred embodiment of the present application, but the embodiment of the present application is not limited by the above embodiment, and any change, modification, substitution, combination, simplification made without departing from the spirit and principle of the present application should be an equivalent replacement mode, which is included in the protection scope of the present application.

Claims

1. A defect-engineered transition metal-based nanoarray electrode, characterized in that, It is prepared by the following steps: S1. Add the mixed transition metal salt and precipitant to the solvent and dissolve them completely to form a homogeneous mixed solution. Add the current collector to the obtained mixed solution and carry out a solvothermal reaction at 80~250℃. After the reaction is complete, the product is post-treated to obtain the array precursor grown in situ on the current collector. S2. Add the array precursor obtained in step S1 to a selenium source or tellurium source solution and carry out a liquid-solid reaction at 80~250℃; or in a protective gas atmosphere, place a selenium source or tellurium source upstream of the gas and place the array precursor obtained in step S1 downstream of the gas and carry out a high-temperature gas-solid purging reaction at 250~900℃ to obtain a transition metal-based nanoarray grown in situ on the current collector. S3. The transition metal-based nanoarray obtained in step S2 is treated with H2O2, H2, or plasma to introduce vacancies, thus obtaining a defect-engineered transition metal-based nanoarray electrode. In step S1, the mixed transition metal salt contains at least two transition metal salts, the main transition metal in the mixed transition metal salt is selected from at least one of Fe, Mn, Co, Ni, and Cu; the doped transition metal in the mixed transition metal salt is selected from at least one of Fe, Cu, Mn, Mo, and W; and the molar ratio of the doped metal to the main metal in the mixed transition metal salt is 1:(1 to 100).

2. The defect-engineered transition metal-based nanoarray electrode according to claim 1, characterized in that, In step S1, the mixed transition metal salt is one or more of nitrates, acetates, chlorides, carbonates, and sulfates.

3. The defect-engineered transition metal-based nanoarray electrode according to claim 1, characterized in that, In step S1, the precipitant is one or more of hexamethylenetetramine, sodium hydroxide, potassium hydroxide, urea, ammonia, sodium carbonate, and sodium bicarbonate.

4. The defect-engineered transition metal-based nanoarray electrode according to claim 1, characterized in that, In step S1, the solvent is one or more of the following: 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.

5. The defect-engineered transition metal-based nanoarray electrode according to claim 1, characterized in that, In step S1, the current collector is carbon cloth, carbon paper, or a metal current collector.

6. The defect-engineered transition metal-based nanoarray electrode according to claim 1, characterized in that, In step S2, during the liquid-solid reaction, the selenium source is sodium selenide and the tellurium source is sodium telluride.

7. The defect-engineered transition metal-based nanoarray electrode according to claim 1, characterized in that, In step S2, during the high-temperature gas-solid purging reaction, the selenium source is selenium powder and the tellurium source is tellurium powder.

8. The application of the defect-engineered transition metal-based nanoarray electrode according to any one of claims 1 to 7 in sulfide oxidation reactions.

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