CN114318401B - Preparation method of surface hydrophilic adjustable nickel-molybdenum alloy material and application of surface hydrophilic adjustable nickel-molybdenum alloy material in high-current decomposition of water to produce hydrogen - Google Patents

Preparation method of surface hydrophilic adjustable nickel-molybdenum alloy material and application of surface hydrophilic adjustable nickel-molybdenum alloy material in high-current decomposition of water to produce hydrogen Download PDF

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CN114318401B
CN114318401B CN202111512369.7A CN202111512369A CN114318401B CN 114318401 B CN114318401 B CN 114318401B CN 202111512369 A CN202111512369 A CN 202111512369A CN 114318401 B CN114318401 B CN 114318401B
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nickel
molybdenum alloy
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deionized water
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CN114318401A (en
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施伟东
吴倩
郑伊旸
李逸欢
张正媛
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Jiangsu University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to the technical field of electrochemistry, and relates to a preparation method of a nickel-molybdenum alloy material electrode with a hydrophilic adjustable surface, which comprises the following steps: firstly, cleaning a base material to remove impurities, mixing nickel nitrate hexahydrate, sodium molybdate dihydrate, urea, ammonium fluoride and deionized water to form a solution, adding the base material, and carrying out hydrothermal treatment at 100-200 ℃ for 3-10 h; then NiMoO is carried out on the obtained nano precursor 4 Sub is transferred into a semi-closed porcelain boat and calcined for 0.5 to 4 hours at the temperature of 400 to 600 ℃ under the protection of inert gas; the prepared nickel-molybdenum alloy precursor has the electrolyte of 1 mol.L ‑1 Soaking in KOH solution for 5min, and fixing current density to-5-50 mA cm ‑2 The structure of the components is optimized for 0.5 to 3 hours. The invention has simple and easy operation process, can be attached to the surfaces of various different substrates, and is easy for industrialized implementation. The prepared composite electrode has good shape retention, good electrochemical performance and stability, low-cost and easily-obtained raw materials, no toxicity and simple process, and can be directly used as an electrode for high-current electrocatalytic decomposition water hydrogen evolution reaction.

Description

Preparation method of surface hydrophilic adjustable nickel-molybdenum alloy material and application of surface hydrophilic adjustable nickel-molybdenum alloy material in high-current decomposition of water to produce hydrogen
Technical Field
The invention belongs to the technical field of electrochemistry, relates to a preparation method of an adjustable nickel-molybdenum alloy material, and particularly relates to a preparation method of a surface hydrophilic adjustable nickel-molybdenum alloy material electrode and application of the electrode in high-current decomposition of water to hydrogen production.
Background
Hydrogen Evolution Reactions (HER) are an important element of water splitting and solar fuel cells, however, complex multi-step transport hampers their kinetic process. The surface hydrophilicity is one of the basic properties of the catalyst surface and plays a decisive role in the adsorption and mass transfer of the catalyst surface. In a catalytic system with good surface hydrophilicity, electrolyte ions can directly contact with the surface of the catalyst, so that a convenient electrolyte diffusion path is provided for the inside of the catalyst, and each nanoparticle participates in electrochemical reaction. Therefore, it is critical to improve the catalytic performance to adjust the surface hydrophilicity of the catalyst.
Surface functionalization and heteroatom doping have heretofore been common strategies to tailor the hydrophilicity of surfaces. Has been designed andn or S modified Ni nano particles and N-S co-doped Mo are synthesized 2 The C nano-sheet, the phosphorylated NiFe oxide and hydroxide improve the surface hydrophilicity and greatly improve the HER performance. However, the introduction of foreign groups or atoms complicates the overall catalytic system. In practical application, the synthesis method often needs great cost investment, and the overpotential and the stability still need to be further improved. Therefore, preparing the metal alloy hydrogen evolution electrocatalyst with high efficiency and good stability and controlled internal components is a challenging task.
In recent years, ni—mo alloys have been recognized as one of the best non-noble metal HER electrocatalysts in alkaline solutions. In order to explore the internal connection of the high performance of Ni-Mo alloys, the research on the regulation of the internal components of Ni-Mo alloys under various conditions has been greatly progressed, such as the influence of the organic nature and Mo content on the Ni-Mo alloys. In addition, the reactants or the intermediate products are utilized to selectively adsorb different crystal faces of the Ni-Mo alloy, so that the preferential oriented growth of the catalyst is induced, the crystal faces which have stronger affinity with the target reactants or the intermediate products, namely are combined more stably, and the prepared Ni-Mo alloy has high activity and high stability on the target reaction. However, to the inventors' knowledge, there is no report on the relationship between the regulation of Ni-Mo alloy composition and hydrophilicity and the performance of high-current decomposition of water to produce hydrogen. It is expected that improving surface hydrophilicity by compositional modulation in combination with high HER activity of Ni-Mo alloys is a promising approach to improve HER activity and stability.
To date, no research on preparation of the electrode of the nickel-molybdenum alloy material with the hydrophilic adjustable surface and application of the electrode to high-current decomposition of water to hydrogen under alkaline conditions has been disclosed.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, an object of the present invention is to disclose a method for preparing a nickel-molybdenum alloy material with a hydrophilic and adjustable surface.
A preparation method of a nickel-molybdenum alloy material with a hydrophilic adjustable surface comprises the following steps:
A. sequentially carrying out ultrasonic cleaning on the base material by using acetone, ethanol and deionized water to remove organic matters and other impurities on the surface;
B. nickel nitrate hexahydrate, sodium molybdate dihydrate, urea, ammonium fluoride and deionized water are uniformly stirred into a solution according to the solid-to-liquid ratio of 0.1g to 10g to 0.1g to 5g to 10 mL to 50mL, and the preferable solid-to-liquid ratio is 0.2908g to 0.2419g to 0.3003g to 0.074g to 35mL;
C. transferring the solution and a pretreated substrate into a Teflon-lined stainless steel autoclave, carrying out hydrothermal treatment at 100-200 ℃ for 3-10 h, cooling to room temperature, preferably 120 ℃ for 6h, fully washing the precipitate with deionized water and ethanol, and carrying out vacuum drying at 60 ℃ for 12h to obtain a nano precursor NiMoO 4 -Sub；
D. NiMoO as nanometer precursor 4 Transferring Sub into a semi-closed porcelain boat, adding a hydrogen source, transferring into a programmed heating tube furnace, calcining for 0.5-4 h at 400-600 ℃ under the protection of inert gas, preferably calcining for 1h at 500 ℃, and taking out after naturally cooling to room temperature to obtain a nickel-molybdenum alloy precursor;
E. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing the current density to-5 to-50 mA cm -2 Under the condition of optimizing the component structure for 0.5 to 3 hours, preferably-10 mA.cm -2 And (3) reacting for 2 hours, fully flushing the prepared nickel-molybdenum alloy with deionized water, and naturally airing to obtain the nickel-molybdenum alloy.
In the preferred embodiment of the present invention, the substrate in the step a is carbon paper CP, carbon cloth CC, nickel foam NF, conductive glass FTO or stainless steel mesh SSM, preferably carbon paper CP.
In a preferred embodiment of the present invention, the size of the substrate in step C is 4X 2cm 2 。
In a preferred embodiment of the present invention, the hydrogen source in the step D is H with a volume ratio of 5:95 2 /N 2 Mixture gas or H 2 Ar mixed gas; the temperature-programmed tube furnace has a temperature-increasing rate of 10 ℃/min, and the inert gas is nitrogen or argon.
Urea, chinese name also urea, carbamide, etc.
The invention also aims to apply the prepared nickel-molybdenum alloy material with the hydrophilic adjustable surface to the high-current electrocatalytic decomposition of the water-producing hydrogen cathode material.
The product is subjected to morphological structure analysis by using an X-ray diffraction (XRD), a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), an electrocatalytic decomposition water hydrogen evolution experiment is carried out by taking potassium hydroxide (KOH) solution as a target, and the electrocatalytic decomposition water hydrogen evolution activity is evaluated by analyzing an electrochemical polarization curve (LSV) and a stability test.
Electrocatalytic activity experiment of surface hydrophilic adjustable nickel-molybdenum alloy material:
(1) The concentration is 1 mol.L -1 KOH solution, sealing the prepared solution and placing the solution in a dark place;
(2) Electrochemical performance test is carried out on the sample in a three-electrode system by adopting a CHI660E electrochemical workstation (Shanghai Chen Hua instruments Co., ltd.); the carbon rod is used as a counter electrode, a mercury oxide electrode (Hg/HgO) is used as a reference electrode, and the prepared composite material is used as a working electrode, and the concentration of the carbon rod is 1 mol.L -1 The electrochemical performance of the electrode materials was tested in KOH electrolyte using Linear Sweep Voltammetry (LSV) and chronopotentiometry (P-t).
The nickel-molybdenum alloy precursor after calcination reaction is subjected to electrolysis hydrogen evolution reaction for a period of time under the condition of fixed current in alkali liquor, the structure of the material is optimized, the material grows to purer crystalline phases, the lower overpotential of the electrolysis hydrogen evolution reaction of water is shown, and the unexpected technical effect is achieved. The prepared simple nickel-molybdenum alloy has different degrees of hydrophilic performance by combining theoretical calculation and actual surface hydrophilicity test. Wherein Ni-Mo-500 corresponds to MoNi 4 The crystal phase has the lowest H 2 The O molecule surface adsorption energy (-1.07 eV) and the minimum water contact angle (57.4 degrees (0 s)) indicate that the Ni-Mo-500 surface is easier to adsorb H 2 And O molecules. When the prepared nickel-molybdenum alloy material with the hydrophilic adjustable surface is used as an electrocatalytic decomposition water negative electrode material, the current density of Ni-Mo-400/CP, ni-Mo-500/CP and Ni-Mo-600/CP is-10 mA cm -2 The overpotential can reach 68mV, 55mV and 282mV respectively, wherein the overpotential of Ni-Mo-500/CP is the lowest;in addition, ni-Mo-500/NF can also be used under high current (-2A cm) -2 ) The test is still good in stability after 11 hours.
Advantageous effects
The invention has simple and feasible operation process, can be attached to various different substrates, and is easy for industrialized implementation. The prepared composite electrode has good shape retention, good electrochemical performance and stability, low-cost and easily-obtained raw materials, no toxicity and simple process, and can be directly used as an electrode for electrocatalytic decomposition water hydrogen evolution reaction.
Drawings
FIG. 1 (a) is an X-ray diffraction (XRD) pattern of the Ni-Mo-400 precursor, ni-Mo-500 precursor and Ni-Mo-600 precursor prepared;
(b) X-ray diffraction (XRD) patterns for the prepared Ni-Mo-400, ni-Mo-500 and Ni-Mo-600 samples. Wherein, the abscissa is diffraction angle (2 theta), the unit is degree (°), the ordinate is diffraction Intensity (Intensity), and the unit is cps.
FIG. 2. (a) is a Scanning Electron Microscope (SEM) photograph of the prepared Ni-Mo-500 sample;
(b) Transmission Electron Microscope (TEM) photographs of Ni-Mo-500 samples;
(c) Elemental mapping of Ni, mo, O in nickel-molybdenum alloys.
FIG. 3 (a) is H 2 O molecule in MoNi 4 (001) And the free energy of NiMo (001) surface adsorption;
(b) Dynamic water contact angle measurements at a fixed tilt angle (12 °) for the prepared Ni-Mo-400, ni-Mo-500 and Ni-Mo-600 samples.
FIG. 4 (a) is a polarization graph (iR compensated) of electrocatalytic decomposition water hydrogen evolution for Ni-Mo/CP samples prepared at different annealing temperatures;
(b) Polarization curve (LSV) diagram (iR compensated) of Ni-Mo-500/CP sample before and after 3000 cycles;
(c) The Ni-Mo-500/CP sample has a current density of 10mA.cm -2 Testing for 12h under constant current, and changing current density to 100mA cm -2 Continuing the constant current test for 12h of performance chart (without iR compensation);
(d) Ni-Mo-500/NF sample in large electricityThe flow density was 2A cm -2 The performance graph (without iR compensation) for the lower constant current test 11 h.
Detailed Description
The present invention will be described in detail with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be interpreted to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo-400/CP alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried to obtain a Ni-Mo-400/CP sample.
The prepared Ni-Mo-400/CP sample has the current density of-10 mA cm -2 The time overpotential may reach 68mV.
Example 2
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo-500/CP alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried to obtain a Ni-Mo-500/CP sample.
The prepared Ni-Mo-500/CP sample has the current density of-10 mA cm -2 The time overpotential can reach 55mV, and the performance is still higher after 3000 circles of CV circulation; and the current density of the Ni-Mo-500/CP sample is respectively 10mA cm -2 And 100mA cm -2 Good stability is maintained after 12 hours of the test.
Example 3
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo-600/CP alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried to obtain a Ni-Mo-600/CP sample.
The prepared Ni-Mo-600/CP sample has the current density of-10 mA cm -2 The time overpotential can reach 282mV.
Example 4
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was combined with a clean foam Nickel (NF) (4X 2 cm) 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo-500/NF alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried to obtain a Ni-Mo-500/NF sample.
The prepared Ni-Mo-500/NF sample has the current density of-2A cm -2 Good stability is maintained after 11 hours of the test.
Example 5
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 6
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F is dissolved in 35mL deionized water and stirred for 30minThe method comprises the steps of carrying out a first treatment on the surface of the The solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 7
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 8
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 9
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 10
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 11
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was combined with a sheet of clean carbon paper (CP)(4×2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 12
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 13
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=)1:1, calcination temperature 600 ℃ and calcination time 1h, fixed current density-5 mA cm -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 14
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and Ni-Mo alloy precursor. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 15
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-50 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-50mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 16
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 2h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Transfer together to 50mL of TexPlacing the mixture in a stainless steel autoclave with a fluorine dragon lining at 120 ℃ for 6 hours, and cooling the mixture to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 17
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy is subjected to the electrolysis solution of 1 mol.L -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 18
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 400 ℃, calcination time 1h, fixationCurrent density-5 mA cm -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 19
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is electrically connectedThe solution is 1 mol.L -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 20
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 400 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 21
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 400 ℃, calcination time 2h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 c for 6h,cooling to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 22
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 400 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 23
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 400 ℃, calcination time 2h, fixed current density-30 mA cm) -2 Lower reaction 2 h) electrode preparationThe preparation method adopts a hydrothermal-calcining method: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 24
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 500 ℃, calcination time 1h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, then at a fixed current density of-5 mA cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 25
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 26
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 500 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; take out the sample with deionized water and B Washing with alcohol, and drying in vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 27
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 500 ℃, calcination time 2h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 28
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 500 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: weighing 0.1163gNi(NO 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 29
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 500 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 30
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 600 ℃, calcination time 1h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 31
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, fully washing with deionized water and ethanol, drying in a vacuum furnace at 60 ℃ for 12 hours,obtaining NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 32
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 600 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 33
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 600 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 34
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:4, calcination temperature 600 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1163g Ni (NO) 3 ) 2 ·6H 2 O、0.3870g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 Under the condition of optimizing the component structure for 2h, and the preparedThe nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 35
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 400 ℃, calcination time 1h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 36
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 37
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 400 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 38
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 400 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 39
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 400 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2h under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized waterNaturally airing.
Example 40
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 41
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 500 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 42
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 500 ℃, calcination time 2h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 43
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 500 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 44
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 500 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 45
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 600 ℃, calcination time 1h, fixed current density-5 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-5mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 46
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphereThe reduction temperature is 600 ℃, the temperature rising rate is 10 ℃ min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 47
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 600 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 48
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 600 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F is dissolved in 35mL deionized water and stirredStirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 49
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=7:3, calcination temperature 600 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4071g Ni (NO) 3 ) 2 ·6H 2 O、0.1451g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 50
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 51
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 400 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the temperature rising rate is10℃·min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 52
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 400 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 53
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 400 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; cleaning the solution and a sheetCarbon Paper (CP) (4X 2 cm) 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 54
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 55
Nickel-molybdenum alloy (Ni-Mo alloy)Ni: mo=3: 7, calcining at 500 ℃ for 1h, and fixing the current density of-30 mA cm -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 56
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 500 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 Reduction time is2h, synthesizing the Ni-Mo alloy precursor. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 57
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 500 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 58
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together with turningMoving to a stainless steel autoclave with a 50mL Teflon lining, standing at 120 ℃ for 6 hours, and cooling to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 59
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 600 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 60
Nickel molybdenum alloys (Ni-Mo alloys, ni: mo=3:7, calcination temperature 600 ℃,calcination time 2h, fixed current density-10 mA cm -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 61
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=3:7, calcination temperature 600 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.1745g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.3387g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The preparedThe nickel-molybdenum alloy precursor of (2) is 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 62
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 63
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) High pressure stainless steel transferred together to 50mL Teflon lined Placing in a kettle at 120 ℃ for 6 hours, and cooling to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 64
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 400 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 65
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 400 ℃, calcination time 2h, fixed current density-30 mA.c)m -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 66
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is subjected to electrolyte solution of 1mol DEGL -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 67
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 68
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 500 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL Teflon lined stainless steel autoclave, left at 120℃for 6h, cooled toAfter room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 69
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 500 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 70
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 Preparation of electrode in the lower reaction 2 h)The method of hydrothermal-calcination is adopted: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 71
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, then at a fixed current density of-30 mA cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 72
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 600 ℃, calcination time 2h, fixed current density-10 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 73
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=4:1, calcination temperature 600 ℃, calcination time 2h, fixed current density-30 mA cm) -2 The following reaction 2 h) the electrode was prepared by hydrothermal-calcination: 0.4653g Ni (NO) 3 ) 2 ·6H 2 O、0.0968g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; deionized water for taking out sampleWashing with ethanol, and drying in vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 2h, and the Ni-Mo alloy precursor is synthesized. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-30mA.cm -2 The component structure is optimized for 2 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 74
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 0.5 h) electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 0.5h under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 75
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 400 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 3 h) the electrode was prepared by hydrothermal-calcination:0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 400 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 3 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 76
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 0.5 h) electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing current density-10mA·cm -2 The component structure is optimized for 0.5h under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 77
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 500 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 3 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Ar (5:95)) atmosphere, the reduction temperature is 500 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 3 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 78
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 0.5 h) electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol thoroughly, and cooling to 60deg.CDrying in a vacuum furnace for 12h to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 0.5h under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
Example 79
Nickel-molybdenum alloy (Ni-Mo alloy, ni: mo=1:1, calcination temperature 600 ℃, calcination time 1h, fixed current density-10 mA cm) -2 The following reaction 3 h) the electrode was prepared by hydrothermal-calcination: 0.2908g Ni (NO) 3 ) 2 ·6H 2 O、0.2419g Na 2 MoO 4 ·2H 2 O, 0.3003g urea and 0.074g NH 4 F, dissolving the mixture into 35mL of deionized water, and stirring for 30min; the solution was mixed with a sheet of clean Carbon Paper (CP) (4X 2cm 2 ) Together transferred to a 50mL teflon lined stainless steel autoclave, left at 120 ℃ for 6h, cooled to room temperature; taking out the sample, washing with deionized water and ethanol, and drying in a vacuum furnace at 60deg.C for 12 hr to obtain NiMoO 4 -Sub; niMoO is carried out 4 Sub at H 2 /N 2 (5：95)(H 2 Under Ar (5:95)) atmosphere, the reduction temperature is 600 ℃, and the heating rate is 10 ℃ and min -1 The reduction time is 1h, and the Ni-Mo alloy precursor is obtained. The prepared nickel-molybdenum alloy precursor is prepared into a solution with the concentration of 1 mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing at a constant current density of-10mA.cm -2 The component structure is optimized for 3 hours under the condition of (1), and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (9)

1. The preparation method of the nickel-molybdenum alloy material with the hydrophilic adjustable surface is characterized by comprising the following steps of:
A. sequentially carrying out ultrasonic cleaning on the base material by using acetone, ethanol and deionized water to remove organic matters and other impurities on the surface;
B. nickel nitrate hexahydrate, sodium molybdate dihydrate, urea, ammonium fluoride and deionized water are uniformly stirred into a solution in a solid-to-liquid ratio of 0.2908g to 0.2419g to 0.3003g to 0.074g to 35mL, or a ratio of 0.1163g to 0.3870g to 0.3003g to 0.074g to 35mL, or a ratio of 0.4071g to 0.14510g to 0.3003g to 0.074g to 35mL, or a ratio of 0.1745g to 0.3387g to 0.3003g to 0.074g to 35mL, or a ratio of 0.4653g to 0.0968g to 0.3003g to 0.074g to 35 mL;
C. transferring the solution and a pretreated substrate into a Teflon-lined stainless steel autoclave, carrying out hydrothermal treatment at 100-200 ℃ for 3-10 h, cooling to room temperature, fully washing the precipitate with deionized water and ethanol, and carrying out vacuum drying at 60 ℃ for 12h to obtain a nano precursor NiMoO 4 -Sub；
D. NiMoO as nanometer precursor 4 Transferring Sub into a semi-closed porcelain boat, adding a hydrogen source, transferring into a programmed heating tube furnace, calcining for 0.5-4 h at 400-600 ℃ under the protection of inert gas, and taking out after naturally cooling to room temperature to obtain the nickel-molybdenum alloy;
E. The prepared nickel-molybdenum alloy is 1mol.L in electrolyte -1 Soaking in KOH solution for 5min, and fixing the current density to-5 to-50 mA.cm -2 The component structure is optimized for 0.5 to 3 hours under the condition, and the prepared nickel-molybdenum alloy is fully washed by deionized water and naturally dried to obtain the nickel-molybdenum alloy.
2. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: the substrate in the step A is carbon paper CP, carbon cloth CC, foam nickel NF, conductive glass FTO or stainless steel mesh SSM.
3. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: the substrate in the step A is carbon paper CP.
4. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: step C the solution and a piece of pretreated substrate were transferred to a Teflon lined stainless steel autoclave and hydrothermally heated at 120℃for 6h.
5. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: the size of the substrate in step C was 4X 2cm 2 。
6. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: the hydrogen source in the step D is H with the volume ratio of 5:95 2 /N 2 Mixture gas or H 2 Ar mixed gas; the temperature-programmed tube furnace has a temperature-increasing rate of 10 ℃/min, and the inert gas is nitrogen or argon.
7. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: and D, calcining at 500 ℃ for 1h under the protection of inert gas.
8. The method for preparing the nickel-molybdenum alloy material with the hydrophilic adjustable surface according to claim 1, which is characterized in that: step E at a fixed current density of-10 mA.cm -2 The reaction was carried out for 2 hours.
9. Use of a nickel-molybdenum alloy material with a surface hydrophilically adjustable, prepared by a method according to any one of claims 1-8, characterized in that: the material is used as a cathode material for high-current electrocatalytic decomposition of water to produce hydrogen.
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