CN113235122A - Mo-doped transition metal hydroxide electrocatalyst constructed through deep self-reconstruction and preparation method and application thereof - Google Patents
Mo-doped transition metal hydroxide electrocatalyst constructed through deep self-reconstruction and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction and a preparation method and application thereof. The method comprises the following steps: mixing MoS2The nano-sheet array is activated under the overpotential condition, then is soaked in a transition metal salt solution for ion adsorption, and then is subjected to deep self-reconstruction through a cyclic voltammetry scanning method to obtain the catalyst. In the method, the raw materials are low in price, high-temperature sintering is not needed, the energy consumption in the production process is less, and the production cost is low; the method adopts a transition metal ion adsorption strategy and an electrochemical self-reconstruction strategy, has a simple preparation process, and is suitable for large-scale production. The deep self-reconstruction Mo-doped transition metal hydroxide electrocatalyst provided by the invention has excellent intrinsic activity of oxygen precipitation reaction at 10mA/cm2Has an overpotential of 242mV and a mass-active current density at 300mV overpotentialIs 1910A/g.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to a Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction and a preparation method and application thereof.
Background
Currently, hydrogen is attracting attention as the highest energy density energy carrier among many new energy feedstocks. The hydrogen energy has high energy density, cleanness, zero pollution and wide source, and has wide prospect in the field of new energy development. At present, a large source of hydrogen is cracking of fossil fuels such as petroleum, and the main disadvantages include limited raw materials, severe energy consumption in the preparation process, low purity of the prepared hydrogen, and the like. The biggest disadvantage is that the hydrogen obtained by cracking the fossil fuel still contains S, P and other impurities, and further desulfurization is needed through a subsequent complex process, so that the production cost is additionally increased, and the desulfurization is not thorough and is extremely easy to poison catalysts such as Pt in a hydrogen energy utilization device. The most desirable way to produce hydrogen is by electrolysis of water. On one hand, raw materials are simple and easy to obtain, the hydrogen can be applied on a large scale, scattered energy such as solar energy and wind energy is converted into hydrogen energy to be stored, on the other hand, the prepared hydrogen is pure, further desulfurization is not needed, the process is simple, and the prepared hydrogen can be directly applied to electric vehicles and the like.
The hydrogen production by water electrolysis is mainly divided into two half reactions, wherein the anode generates Oxygen Evolution Reaction (OER) and the cathode generates Hydrogen Evolution Reaction (HER). HER and OER are two-electron transfer reactions and four-electron transfer reactions, respectively. Since OER has a large overpotential and slow kinetics, it is considered to be a bottleneck in the production of hydrogen by the electrolysis of water. At present, the catalyst for efficiently electrolyzing water to prepare hydrogen is mainly made of noble metal and noble metal oxide. For the OER reaction, the primary catalyst used is IrO2And RuO2And the like. However, the noble metal-based catalyst has the disadvantages of scarce raw materials, high price, easy poisoning and difficult large-scale application in practical application. In recent years, many researchers have been working on the development of a catalyst containing no noble metal element, in which the advantages of low price and excellent performance of a transition metal compound are considered to be very largePotential competes with noble metals.
In order to reduce the cost of hydrogen production by water electrolysis, a great deal of research is devoted to the development of non-noble metal catalysts. Transition metal-based catalysts have attracted the interest of researchers because of their high activity and low cost. However, most of the current transition metal compound catalysts are quite complex in preparation process, involve high-temperature calcination and other processes, consume a lot of energy, and are difficult to produce on a large scale (Advanced Functional Materials,2019,29(34): 1901783). For example, An et al (Advanced Functional Materials 2019,29(1),1805298.) synthesized NiMoO first by using a solvothermal method4As precursor, then in turn at NH3Calcining at high temperature under the atmosphere and the S atmosphere to carry out nitrogen doping and partial vulcanization on the mixed solution to obtain the composite electrocatalyst N-NiMoO4/NiS2. The method involves multi-step reaction, the preparation process is quite complex, high-temperature calcination is needed, the energy consumption is serious, the preparation cost is high, and large-scale commercial production is difficult to realize.
Furthermore, it has been reported from studies that the true active species of transition metal compounds (including perovskites, transition metal oxides, nitrides and phosphides) used for oxygen evolution reactions is the formation of transition metal oxy/oxy-hydroxides on the catalyst surface by self-reconstitution during OER (Energy environ. sci.,2015,8, 2347). However, the depth of the surface self-reconstruction layer is limited to-10 nm, and a core-shell structure is formed, so that the internal components of the catalyst cannot be fully utilized. Therefore, it is challenging to directly manufacture a catalyst with fully active species by deep self-reconstruction.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction and a preparation method and application thereof.
The primary object of the present invention is to provide a method for preparing a Mo-doped transition metal hydroxide electrocatalyst by deep self-reconstitution.
Another object of the present invention is to provide the use of the above electrocatalyst for oxygen evolution reactions.
The purpose of the invention is realized by at least one of the following technical solutions.
The preparation method of the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction provided by the invention comprises the steps of firstly preparing a molybdenum disulfide nanosheet array by using a hydrothermal method; activating the molybdenum disulfide nanosheet array under an overpotential condition; soaking the activated molybdenum disulfide nanosheet array in a transition metal salt solution for ion adsorption treatment; and carrying out deep self-reconstruction on the sample subjected to the ion adsorption treatment by a cyclic voltammetry scanning method to obtain the deep self-reconstruction Mo-doped transition metal hydroxide electrocatalyst.
The invention provides a preparation method for constructing a Mo-doped transition metal hydroxide electrocatalyst through deep self-reconstruction, which specifically comprises the following steps:
(1) preparation of molybdenum disulfide nanosheet array (MoS) on three-dimensional conductive substrate by hydrothermal method2A nanosheet array);
(2) activating the molybdenum disulfide nanosheet array in the step (1) under an overpotential condition to obtain an activated molybdenum disulfide nanosheet array;
(3) soaking the activated molybdenum disulfide nanosheet array in the step (2) in a transition metal salt solution for ion adsorption treatment, and taking out to obtain a molybdenum disulfide/hydroxide complex;
(4) and (3) soaking the molybdenum disulfide/hydroxide complex in the step (3) in an alkaline solution, then taking the molybdenum disulfide/hydroxide complex as a working electrode, and carrying out deep self-reconstruction treatment by a cyclic voltammetry scanning method to obtain the Mo-doped transition metal hydroxide electrocatalyst constructed by the deep self-reconstruction.
Further, the conductive substrate in the step (1) is one of carbon cloth, carbon paper and the like.
Preferably, the conductive substrate in step (1) is carbon cloth.
Preferably, the preparation of the molybdenum disulfide nanosheet array of step (1) comprises:
mixing ammonium molybdate [ (NH)4)6Mo7O24·4H2O]And thiourea (CH4N2S) dissolving in deionized water, uniformly stirring (the stirring time can be preferably 1 hour) to obtain a mixed solution, adjusting the pH value of the mixed solution to 3.0, then transferring the mixed solution to a high-pressure reaction kettle, putting a conductive substrate, heating for 24 hours under the condition of heating to 180 ℃, and cooling to room temperature to obtain the molybdenum disulfide nanosheet array.
Further preferably, in the mixture, the concentration of ammonium molybdate is 10 to 15mM and the concentration of thiourea is 0.4 to 0.5M.
Further, the potential of the activation treatment in the step (2) is-0.5V to-0.7V vs.
Preferably, the potential of the activation treatment of step (2) is-0.6V vs.
Further, the time of the activation treatment in the step (2) is 100-500 s.
Further, the drying mode in the step (2) is vacuum drying; the drying temperature is 50-60 ℃, and the drying time is 3-5 hours.
Preferably, the drying mode in the step (2) is vacuum drying; the drying temperature is 60 ℃, and the drying time is 5 hours.
Further, the transition metal salt solution in the step (3) is more than one of a nickel acetate solution and a ferrous sulfate solution. Namely, the transition metal salt solution in the step (3) is a nickel acetate solution, a ferrous sulfate solution or a mixed solution of the nickel acetate solution and the ferrous sulfate solution which are uniformly mixed.
Further, the concentration of the transition metal salt solution in the step (3) is 30-50 mM.
Further, the time of the ion adsorption treatment in the step (3) is 10s-20 min.
Preferably, the time of the ion adsorption treatment in the step (3) is 5min-20 min.
Further, the sweep rate of the cyclic voltammetry scanning method in the step (4) is 5mV-10 mV;
preferably, the sweep rate of the cyclic voltammetry scanning method in the step (4) is 10 mV.
Further, the number of cycles of the cyclic voltammetry scanning method in the step (4) is 5-10 cycles.
Preferably, the number of cycles of the cyclic voltammetry scan of step (4) is 5 cycles.
Further, the scanning range of the cyclic voltammetry scanning method in the step (4) is 0V-0.8V vs. Ag/AgCl.
Further, the alkaline solution in the step (4) is a potassium hydroxide solution; the concentration of the alkaline solution is 0.1M-1M.
The invention provides a Mo-doped transition metal hydroxide electrocatalyst which is prepared by the preparation method and is constructed by deep self-reconstruction.
The Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction provided by the invention can be applied to catalytic oxygen precipitation reaction.
The electrocatalyst has the advantages of simple preparation process, energy-saving preparation process, low preparation cost, strong universality of the preparation method, flexible and controllable preparation process, easy adjustment of the components of the obtained catalyst, high intrinsic activity and the like, and the deep self-reconstruction Mo-doped transition metal hydroxide electrocatalyst prepared under the optimal conditions has excellent catalytic activity of oxygen precipitation reaction.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction provided by the invention has the advantages of low raw material price, no need of high-temperature sintering, less energy consumption in the production process and low production cost;
(2) according to the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction, the preparation method adopts a transition metal ion adsorption strategy, the preparation process is simple, and the method is suitable for large-scale production;
(3) according to the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction, the preparation method adopts a metal ion adsorption strategy, is not influenced by ion species, can be used for easily preparing various transition metal compound catalysts according to requirements, and has universality;
(4) according to the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction, the preparation method adopts a metal ion adsorption strategy, can easily prepare composite catalysts with different transition metal ion ratios, and has a wide application range;
(5) the invention provides a Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction, and a preparation method thereof utilizes MoS2Is easy to be oxidized into MoOxAnd MoOxThe catalyst is easy to leach out in a KOH solution, the deep reconstruction of the catalyst is easily and quickly completed, the Mo-doped transition metal hydroxide is formed, and the obtained catalyst has full coverage of active species and high intrinsic activity.
(6) The deep self-reconstruction Mo-doped transition metal hydroxide electrocatalyst provided by the invention has good oxygen precipitation activity at 10mA/cm2The overpotential at the current density of (a) is 240-300mV, and the mass activity current density at the overpotential of 300mV is 55-1910A/g.
Drawings
FIG. 1 is a cyclic voltammogram obtained in example 1 for the catalytic test of an oxygen evolution reaction by deep self-reconfigurable construction of a Mo-doped transition metal hydroxide electrocatalyst;
FIG. 2 is a mass activity current density at 300mV overpotential for an oxygen evolution reaction catalysis test of a Mo doped transition metal hydroxide electrocatalyst constructed by deep self-reconfiguration as obtained in example 1;
FIG. 3 is a Tafel plot of Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction for catalysis testing of oxygen evolution reaction, obtained in example 1;
FIG. 4 is an AC impedance plot for the catalytic test of oxygen evolution reaction by deep self-reconfigurable construction of a Mo-doped transition metal hydroxide electrocatalyst obtained in example 1;
FIG. 5 is a cyclic voltammogram of the deep self-reconstituted Mo-doped transition metal hydroxide electrocatalyst obtained in example 2 for catalytic testing of oxygen evolution reaction;
FIG. 6 is the mass activity current density at 300mV overpotential for the oxygen evolution reaction catalysis test for the Mo doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction as obtained in example 2;
FIG. 7 is a Tafel plot of the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction for catalysis testing of the oxygen evolution reaction, obtained in example 2;
FIG. 8 is an AC impedance plot for the catalytic test of oxygen evolution reaction by the deep self-reconfigurable construction of a Mo-doped transition metal hydroxide electrocatalyst obtained in example 2;
FIG. 9 is a cyclic voltammogram obtained in example 3 by deep self-reconfigurable construction of a Mo-doped transition metal hydroxide electrocatalyst for catalytic testing of oxygen evolution reactions;
FIG. 10 is the mass activity current density at 300mV overpotential for the oxygen evolution reaction catalysis test by deep self-reconfigurable construction of a Mo-doped transition metal hydroxide electrocatalyst obtained in example 3;
FIG. 11 is a Tafel plot of Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction for catalysis testing of oxygen evolution reaction, obtained in example 3;
fig. 12 is an ac impedance plot for the catalytic test of oxygen evolution reaction by deep self-reconfigurable construction of Mo-doped transition metal hydroxide electrocatalysts as obtained in example 3.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
(1) Preparing a molybdenum disulfide nanosheet array on a carbon cloth substrate by a hydrothermal synthesis method;
(2) cleaning the molybdenum disulfide nanosheet array growing on the carbon cloth obtained in the step (1) for several times by using pure water, and drying for 5 hours at 50 ℃ in vacuum to obtain a dried molybdenum disulfide nanosheet array;
(3) activating the dried molybdenum disulfide nanosheet array obtained in the step (2) for 300s under-0.6V (vs. RHE) overpotential to obtain an activated molybdenum disulfide nanosheet;
(4) soaking the activated molybdenum disulfide nanosheets obtained in the step (3) in a nickel acetate solution with the concentration of 30mM for 5min, and using the molybdenum disulfide nanosheets as templates to carry out Ni reaction2+Carrying out adsorption to obtain a molybdenum disulfide/hydroxide composite material;
(5) and (3) soaking the molybdenum disulfide/hydroxide composite material obtained in the step (4) in a KOH solution (with the concentration of 0.1M), and then taking the molybdenum disulfide/hydroxide composite material as a working electrode to perform cyclic voltammetry scanning, wherein the scanning range is 0V-0.8V vs. Ag/AgCl, the scanning speed is 10mV/s, and the number of cyclic cycles is 5, so as to obtain the Mo-doped transition metal hydroxide electrocatalyst constructed through deep self-reconstruction in the embodiment.
This example performed an oxygen evolution electrocatalytic activity test on the resulting deep self-reconstituted Mo doped transition metal hydroxide electrocatalyst. Oxygen evolution activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is taken as a working electrode, saturated Ag/AgCl is taken as a reference electrode, a platinum net is taken as a counter electrode, and 1mol L of catalyst material is used-1The KOH solution is electrolyte, and the testing instrument is Shanghai Chenghua 660E electrochemical workstation. The cyclic voltammograms, tafel slopes and ac impedance profiles were tested at room temperature at 25 ℃. The cyclic voltammetry curve of the obtained deep self-reconstructed Mo-doped transition metal hydroxide electrocatalyst for the oxygen evolution reaction is shown as a solid line in FIG. 1, the mass activity at 300mV overpotential is shown as FIG. 2, the Tafel curve is shown as FIG. 3, and the AC impedance spectrum is shown as a solid line in FIG. 4.
The self-restructured Mo-doped nickel hydroxide in fig. 1-4 represents the deep self-restructured build-up of Mo-doped transition metal hydroxide electrocatalysts prepared by example 1.
Example 2
(1) Preparing a molybdenum disulfide nanosheet array on a carbon cloth substrate by a hydrothermal synthesis method;
(2) cleaning the molybdenum disulfide nanosheet array growing on the carbon cloth obtained in the step (1) for several times by using pure water, and drying for 3 hours at 60 ℃ in vacuum to obtain a dried molybdenum disulfide nanosheet array;
(3) activating the dried molybdenum disulfide nanosheet array obtained in the step (2) for 100s under-0.6V (vs. RHE) overpotential to obtain an activated molybdenum disulfide nanosheet;
(4) soaking the activated molybdenum disulfide nanosheets obtained in the step (3) in a ferrous sulfate solution with the concentration of 50mM for 10min, and carrying out Fe pairing by using the molybdenum disulfide nanosheets as templates2+Carrying out adsorption to obtain a molybdenum disulfide/hydroxide composite material;
(5) and (3) soaking the molybdenum disulfide/hydroxide composite material obtained in the step (4) in a KOH solution (with the concentration of 0.5M), and performing cyclic voltammetry scanning by using the molybdenum disulfide/hydroxide composite as a working electrode, wherein the scanning range is 0V-0.8V vs. Ag/AgCl, the scanning speed is 10mV/s, and the number of cyclic cycles is 5 cycles, so as to obtain the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction in the embodiment.
This example performed an oxygen evolution electrocatalytic activity test on the resulting deep self-reconstituted Mo doped transition metal hydroxide electrocatalyst. Oxygen evolution activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is taken as a working electrode, saturated Ag/AgCl is taken as a reference electrode, a platinum net is taken as a counter electrode, and 1mol L of catalyst material is used-1The KOH solution is electrolyte, and the testing instrument is Shanghai Chenghua 660E electrochemical workstation. The cyclic voltammograms, tafel slopes and ac impedance profiles were tested at room temperature at 25 ℃. The cyclic voltammogram of the obtained deep self-restructuring Mo-doped transition metal hydroxide electrocatalyst used for the oxygen evolution reaction is shown by a solid line in FIG. 5, the mass activity at 300mV overpotential is shown in FIG. 6, the Tafel curve is shown in FIG. 7, and the AC impedance spectrum is shown by a solid line in FIG. 8.
The self-reconfigurable Mo-doped iron hydroxide in fig. 5-8 represents the Mo-doped transition metal hydroxide electrocatalyst prepared by deep self-reconfigurable fabrication of example 2.
Example 3
(1) Preparing a molybdenum disulfide nanosheet array on a carbon cloth substrate by a hydrothermal synthesis method;
(2) cleaning the molybdenum disulfide nanosheet array growing on the carbon cloth obtained in the step (1) for several times by using pure water, and drying for 5 hours at 60 ℃ in vacuum to obtain a dried molybdenum disulfide nanosheet array;
(3) activating the dried molybdenum disulfide nanosheet array obtained in the step (2) for 500s under-0.6V (vs. RHE) overpotential to obtain an activated molybdenum disulfide nanosheet;
(4) soaking the activated molybdenum disulfide nanosheets obtained in the step (3) in a mixed solution of a nickel acetate solution and a ferrous sulfate solution (prepared from a 50mM nickel acetate solution and a 50mM ferrous sulfate solution according to a volume ratio of 3: 1), wherein the soaking time is 20min, and the molybdenum disulfide nanosheets are used as a template to carry out Ni reaction2+And Fe2+And adsorbing to obtain the molybdenum disulfide/hydroxide composite material.
(5) And (3) putting the molybdenum disulfide/hydroxide composite material obtained in the step (4) in a KOH solution (with the concentration of 1M), and then taking the molybdenum disulfide/hydroxide composite material as a working electrode to perform cyclic voltammetry scanning, wherein the scanning range is 0V-0.8V vs. Ag/AgCl, the scanning speed is 10mV/s, and the number of cyclic cycles is 5, so as to obtain the Mo-doped transition metal hydroxide electrocatalyst constructed by deep self-reconstruction in the embodiment.
This example performed an oxygen evolution electrocatalytic activity test on the resulting deep self-reconstituted Mo doped transition metal hydroxide electrocatalyst. Oxygen evolution activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is taken as a working electrode, saturated Ag/AgCl is taken as a reference electrode, a platinum net is taken as a counter electrode, and 1mol L of catalyst material is used-1The KOH solution is electrolyte, and the testing instrument is Shanghai Chenghua 660E electrochemical workstation. The cyclic voltammograms, tafel slopes and ac impedance profiles were tested at room temperature at 25 ℃. The cyclic voltammetry curve of the obtained deep self-reconstructed Mo-doped transition metal hydroxide electrocatalyst used for oxygen evolution reaction is shown as a solid line in FIG. 9, the mass activity under 300mV overpotential is shown as FIG. 10, the Tafel curve is shown as FIG. 11, and the AC impedance spectrumAs shown by the solid line in fig. 12.
The self-restructured Mo-doped nickel iron hydroxide in fig. 9-12 represents the construction of Mo-doped transition metal hydroxide electrocatalysts by deep self-restructuring prepared in example 3. The nickel iron hydroxide in fig. 9-12 represents iron doped nickel hydroxide with a molar ratio of nickel iron of 3: 1. the preparation of the nickel iron hydroxide comprises the following steps: 7.5mL of a 37.5mM nickel nitrate solution was mixed with 2.5mL of a 37.5mM iron nitrate solution, 20mL of a potassium nitrate solution (solvent 23% formamide and 77% water) was added, followed by heating and stirring at 80 ℃ for 30 minutes, followed by addition of a 0.25M KOH solution to adjust the pH to 10, followed by introduction of nitrogen into the resulting solution and natural cooling to room temperature, to obtain a precipitate by centrifugation, and the resulting precipitate was vacuum-dried at 60 ℃ for 12 hours to obtain ferronickel hydroxide.
Effect analysis
The results of fig. 9, in conjunction with fig. 1, 5, show that the Mo-doped transition metal hydroxide electrocatalyst fabricated by deep self-reconstruction, obtained in the example of the present invention, has excellent oxygen evolution reaction performance.
The results of fig. 10, in conjunction with fig. 2, 6, show that the Mo-doped transition metal hydroxide electrocatalyst fabricated by deep self-reconstruction, obtained in the example of the present invention, has higher mass activity, indicating higher intrinsic activity.
The results of fig. 3, 4, 7, 8, 11, 12, taken together, show that the resulting Mo-doped transition metal hydroxide electrocatalysts constructed by deep self-reconstruction in the examples of the present invention have faster kinetics of oxygen evolution reaction.
The results of fig. 9, 10, 11, and 12 show that the electrocatalysis prepared by simultaneously adsorbing multiple transition metal ions by using the transition metal ion adsorption strategy in the embodiment of the present invention can further improve the electrocatalysis activity of the oxygen evolution reaction, can simply and conveniently regulate and control the multi-component transition metal compound, and can realize the electrocatalysis of the high-efficiency oxygen evolution reaction through the synergistic effect between two or more transition metals.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method for constructing a Mo-doped transition metal hydroxide electrocatalyst through deep self-reconstruction is characterized by comprising the following steps of:
(1) preparing a molybdenum disulfide nanosheet array on a conductive substrate by a hydrothermal method;
(2) washing and drying the molybdenum disulfide nanosheet array obtained in the step (1), and then performing activation treatment under the condition of overpotential to obtain an activated molybdenum disulfide nanosheet array;
(3) soaking the activated molybdenum disulfide nanosheet array in the step (2) in a transition metal salt solution for ion adsorption treatment, and taking out to obtain a molybdenum disulfide/hydroxide complex;
(4) and (3) soaking the molybdenum disulfide/hydroxide complex in the step (3) in an alkaline solution, then taking the molybdenum disulfide/hydroxide complex as a working electrode, and carrying out deep self-reconstruction treatment by a cyclic voltammetry scanning method to obtain the Mo-doped transition metal hydroxide electrocatalyst constructed by the deep self-reconstruction.
2. The method for preparing the Mo-doped transition metal hydroxide electrocatalyst through deep self-reconstitution according to claim 1, wherein the conductive substrate in step (1) is one of carbon cloth and carbon paper.
3. The method for preparing a Mo-doped transition metal hydroxide electrocatalyst by deep self-reconstitution according to claim 1, wherein the potential of the activation treatment of step (2) is-0.5V to-0.7 vvs.rhe; the time of the activation treatment in the step (2) is 100-500 s.
4. The method for preparing a Mo-doped transition metal hydroxide electrocatalyst through deep self-reconstitution according to claim 1, wherein the drying manner of step (2) is vacuum drying; the drying temperature is 50-60 ℃, and the drying time is 3-5 hours.
5. The method for preparing a Mo-doped transition metal hydroxide electrocatalyst through deep self-reconstitution according to claim 1, wherein the transition metal salt solution in step (3) is one or more of a nickel acetate solution and a ferrous sulfate solution; the concentration of the transition metal salt solution is 30-50 mM.
6. The method for preparing a Mo-doped transition metal hydroxide electrocatalyst by deep self-reconstitution according to claim 1, wherein the time of the ion adsorption treatment in step (3) is 10s-20 min.
7. The method for preparing a Mo-doped transition metal hydroxide electrocatalyst through deep self-reconstitution according to claim 1, wherein the sweep rate of the cyclic voltammetry scan of step (4) is 5mV to 10 mV; the scanning range of the cyclic voltammetry scanning method is 0V-0.8V vs. Ag/AgCl; the number of cycles of the cyclic voltammetry scanning method is 5-10 cycles.
8. The method for preparing a Mo-doped transition metal hydroxide electrocatalyst by deep self-reconstitution according to claim 1, wherein the alkaline solution of step (4) is a potassium hydroxide solution; the concentration of the alkaline solution is 0.1M-1M.
9. A Mo-doped transition metal hydroxide electrocatalyst fabricated by deep self-restructuring made by the method of any one of claims 1 to 8.
10. Use of the Mo-doped transition metal hydroxide electrocatalyst fabricated by deep self-reconstitution according to claim 9 for catalyzing oxygen evolution reactions.
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