CN115404490A - Nickel-doped molybdenum dioxide composite seawater electrocatalyst and preparation method and application thereof - Google Patents

Nickel-doped molybdenum dioxide composite seawater electrocatalyst and preparation method and application thereof Download PDF

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CN115404490A
CN115404490A CN202211064630.6A CN202211064630A CN115404490A CN 115404490 A CN115404490 A CN 115404490A CN 202211064630 A CN202211064630 A CN 202211064630A CN 115404490 A CN115404490 A CN 115404490A
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nickel
electrocatalyst
seawater
dioxide composite
molybdenum dioxide
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孟祥超
周岩
梁东东
孙建鹏
赵展
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Qingdao Zhongshi Daxin Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract

The invention discloses a nickel-doped molybdenum dioxide composite seawater electrocatalyst, a preparation method and application thereof, and relates to the technical field of catalysts. The preparation method comprises the following steps: preparing a transparent solution; (2) preparing a Ni-Mo-O precursor; (3) Ni-MoO 2 And (4) preparing an electrocatalyst. The invention also discloses application of the nickel-doped molybdenum dioxide composite electrocatalyst in the electro-catalytic cracking of seawater to produce hydrogen. The Ni-MoO provided by the invention 2 The electrocatalyst has the advantages of uniform size, regular appearance, large specific surface area, and high activity and stability. In addition, the preparation method has the advantages of mild preparation conditions, simple operation, strong repeatability and low requirements on instruments and equipment, and provides good technical basis and material guarantee for large-area application.

Description

Nickel-doped molybdenum dioxide composite seawater electrocatalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a nickel-doped molybdenum dioxide composite seawater electrocatalyst and a preparation method and application thereof.
Background
In recent years, hydrogen energy has attracted wide attention, and electrocatalysis cracking water for hydrogen production, especially electrocatalysis cracking seawater provides an effective means for solving energy crisis and developing new energy. But the electrocatalyst material is affected by the problems of high price, difficult synthesis, and scarce reserves, etc., so that it has not been developed rapidly.
In the traditional transition metal materials, transition metal oxides such as nickel oxide, cobalt oxide, manganese oxide and the like have attracted wide attention in the field of hydrogen production by electrocatalysis due to abundant reserves and low price. However, at present, the performance of the catalyst in the process of producing hydrogen by electrocatalytic cracking of water is limited due to poor conductivity and high adsorption energy of the catalyst. Meanwhile, in the prior art, reports about the rapid heating synthesis of the oxide electrocatalyst are less, the related test of the performance of the electrocatalytic cracking seawater is not carried out, and a large improvement space still exists in the aspects of synthesis methods, design strategies and the like.
Therefore, how to provide an economic and efficient electrocatalyst to promote the rapid development of oxide-based materials in the field of electrocatalytic cracking of seawater and finally realize the industrialization thereof is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nickel-doped molybdenum dioxide composite seawater electrocatalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) Respectively adding ammonium molybdate tetrahydrate and nickel chloride hexahydrate into deionized water, mixing, then putting foamed nickel into the obtained mixed solution, standing, heating, cooling to room temperature, washing, and drying in vacuum to obtain a Ni-Mo-O precursor;
2) And reacting the Ni-Mo-O precursor for 0.5-30min at the temperature of 400-800 ℃ in an inert atmosphere to obtain the nickel-doped molybdenum dioxide composite seawater electrocatalyst.
Further, in the step 1), the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1 (0.1-5.0).
Further, in the step 1), the standing time is 5-10min.
Further, in step 1), the parameters of the heat treatment are as follows: the temperature is 150-200 ℃, and the time is 5-10h.
Further, in step 1), the parameters of vacuum drying are as follows: the temperature is 5-100 ℃, the time is 8-72h, and the vacuum degree is 133-267Pa.
Further, in the step 2), the inert atmosphere refers to Ar/H 2 And (4) mixing the gases.
The invention also provides a nickel-doped molybdenum dioxide composite seawater electrocatalyst prepared by the preparation method of the nickel-doped molybdenum dioxide composite seawater electrocatalyst.
The invention also provides an application of the nickel-doped molybdenum dioxide composite seawater electrocatalyst in seawater hydrogen production through electrocatalytic cracking.
Further, the nickel-doped molybdenum dioxide composite seawater electrocatalyst is used as a working electrode, a calomel electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, and the electrolyte is alkaline seawater; the pH value of the electrolyte is 10-14.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, ammonium molybdate tetrahydrate is used as a molybdenum source, nickel chloride hexahydrate is used as a nickel source, the molybdenum source is loaded on a foamed nickel substrate, a precursor is prepared in a heating deposition manner, and then heating reaction is carried out in an inert atmosphere, so that the catalyst for producing hydrogen by electrocatalytic cracking of seawater is obtained. The electronic structure of the molybdenum dioxide material can be optimized by doping the metal, the synergistic effect is exerted, the transfer speed of electrons is accelerated, water molecules in seawater are adsorbed on the surface of the catalyst, the water molecules obtain electrons to generate hydrogen protons, and the two hydrogen protons are combined to generate hydrogen, so that the reaction process is accelerated.
Ni-MoO prepared by the invention 2 The electrocatalyst has the characteristics of large specific surface area, high activity and high stability, and has excellent hydrogen production performance in alkaline seawater. Further, ni-MoO in the present invention 2 The preparation of the electrocatalyst is short in time consumption, simple in operation,The repeatability is strong, and good technical basis and material guarantee are provided for large-area application.
Ni-MoO prepared by the invention 2 The electrocatalyst has a rod-shaped nano structure, can provide rich specific surface area, and further improves the catalytic activity of the electrocatalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows Ni-MoO prepared in example 1 2 Scanning electron micrographs of the electrocatalyst;
FIG. 2 shows Ni-MoO prepared in example 1 2 An X-ray diffraction pattern of the electrocatalyst;
FIG. 3 shows Ni-MoO prepared in example 1 2 The electro-catalyst is used for cracking the seawater hydrogen production performance diagram in the alkaline seawater.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The raw materials used in the embodiment of the invention are all purchased from the market.
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) Respectively adding ammonium molybdate tetrahydrate and nickel chloride hexahydrate into deionized water to obtain an ammonium molybdate tetrahydrate solution and a nickel chloride hexahydrate solution, dropwise adding the ammonium molybdate tetrahydrate solution into the nickel chloride hexahydrate solution, and continuously and uniformly stirring to obtain a mixed solution;
placing foamed nickel into the obtained mixed solution for standing, heating, cooling to room temperature, washing and vacuum-drying the obtained solid product to obtain a Ni-Mo-O precursor;
2) Reacting the Ni-Mo-O precursor for 0.5-30min at 400-800 ℃ in an inert atmosphere to obtain the nickel-doped molybdenum dioxide composite seawater electrocatalyst, namely Ni-MoO 2 An electrocatalyst. Preferably 500 deg.c.
In some preferred embodiments, in the step 1), the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1 (0.1-5.0). The concentration of the ammonium molybdate tetrahydrate solution is 0.02mol/L, and the concentration of the nickel chloride hexahydrate solution is 0.01-0.10mol/L.
In some preferred embodiments, in step 1), the time of standing is 5-10min.
In some preferred embodiments, in step 1), the parameters of the heat treatment are: the temperature is 150-200 ℃, and the time is 5-10h.
In some preferred embodiments, in step 1), the parameters of the vacuum drying are: the temperature is 5-100 ℃, the time is 8-72h, and the vacuum degree is 133-267Pa.
In some preferred embodiments, in step 1), the nickel foam has a thickness of 1.5mm and an area of 1-4cm 2 。
In some preferred embodiments, in step 2), the inert atmosphere refers to Ar/H 2 Mixed gas, the volume ratio of the two gases is 9:1.
the invention also provides a nickel-doped molybdenum dioxide composite seawater electrocatalyst prepared by the preparation method, namely Ni-MoO 2 Electrocatalyst with chemical composition of Ni-MoO 2 The structure is rod-shaped, and the length is 3 μm. The structure can provide abundant specific surface area, and further improve the catalytic activity of the catalyst.
The invention also provides an application of the nickel-doped molybdenum dioxide composite seawater electrocatalyst in seawater hydrogen production through electrocatalytic cracking.
In some preferred embodiments, the nickel-doped molybdenum dioxide composite seawater electrocatalyst is used as a working electrode, a calomel electrode is used as a reference electrode, a graphite electrode is used as a counter electrode, and an electrolyte is alkaline seawater; the pH value of the electrolyte is 10-14.
The seawater used in the embodiment of the invention is alkaline seawater which is taken from yellow sea of China, wherein the concentration of KOH is 1.0mol/L.
The term "room temperature" as used herein means 25 ℃.
Example 1
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1:1;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min (so that the transparent solution is completely immersed in the foamed nickel), transferring the foamed nickel into a reaction kettle, reacting for 6h at 150 ℃ to obtain a foamed nickel material, fully washing the foamed nickel material with deionized water and ethanol, and performing vacuum drying (at the temperature of 80 ℃, for 12h, and at the vacuum degree of 150 Pa) to obtain the foamed nickel material with the area of 2cm 2 The Ni-Mo-O precursor of (1);
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
FIG. 1 shows Ni-MoO prepared in example 1 2 Scanning electron micrograph of electrocatalyst, it can be seen that Ni-MoO prepared in this example 2 The electrocatalyst has a rod-like structure and grows on the nickel foam.
FIG. 2 shows Ni-MoO prepared in example 1 2 The X-ray diffraction spectrum of the electrocatalyst shows that the chemical composition of the prepared product is Ni-doped MoO 2 。
Example 2
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the ammonium molybdate tetrahydrate to the nickel chloride hexahydrate is 1:1;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting at 150 ℃ for 6h to obtain a foamed nickel material (Ni load: 13.4 mg/cm) -2 Mo loading amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (at 80 deg.C for 12 hr and vacuum degree of 150 Pa) to obtain a product with an area of 2cm 2 The Ni-Mo-O precursor of (1);
5) Setting the area obtained in the step (4) to be 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 400 ℃ in a mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 3
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1:1;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, reacting for 6h at 150 ℃ to obtain a foamed nickel material, fully washing with deionized water and ethanol, and performing vacuum drying(temperature 80 ℃, time 12h, vacuum degree 150 Pa) to obtain an area of 2cm 2 Ni-Mo-O precursor;
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 600 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 4
The difference from example 2 is that step 5) is: the area obtained in the step (4) is 2cm 2 Putting the Ni-Mo-O precursor into a molybdenum boat, transferring the molybdenum boat into a joule heating instrument, ar/H 2 Reacting for 0.5min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 5
The difference from example 2 is that step 5) is: the area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1.5min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 6
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the ammonium molybdate tetrahydrate to the nickel chloride hexahydrate is 1:2;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting at 150 ℃ for 6h to obtain foamNickel foam material (Ni load: 13.4 mg/cm) -2 Mo load amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (temperature 80 deg.C, time 12h, vacuum degree 150 Pa) to obtain a product with area of 2cm 2 Ni-Mo-O precursor;
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 7
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1:3;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting at 150 ℃ for 6h to obtain a foamed nickel material (Ni load: 13.4 mg/cm) -2 Mo loading amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (at 80 deg.C for 12 hr and vacuum degree of 150 Pa) to obtain a product with an area of 2cm 2 Ni-Mo-O precursor;
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 8
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1:4;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting at 150 ℃ for 6h to obtain a foamed nickel material (Ni load: 13.4 mg/cm) -2 Mo loading amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (at 80 deg.C for 12 hr and vacuum degree of 150 Pa) to obtain a product with an area of 2cm 2 The Ni-Mo-O precursor of (1);
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 9
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the ammonium molybdate tetrahydrate to the nickel chloride hexahydrate is 1:5;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting at 150 ℃ for 6h to obtain a foamed nickel material (Ni load: 13.4 mg/cm) -2 Mo loading amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (temperature 80 deg.C, time 12h, vacuum degree 150 Pa) to obtain a product with area of 2cm 2 The Ni-Mo-O precursor of (1);
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 10
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1:5;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting for 6h at 175 ℃ to obtain a foamed nickel material (Ni load: 13.4 mg/cm) -2 Mo loading amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (temperature 80 deg.C, time 12h, vacuum degree 150 Pa) to obtain a product with area of 2cm 2 Ni-Mo-O precursor of (2)；
5) The area obtained in the step (4) is 2cm 2 The Ni-Mo-O precursor is put into a molybdenum boat, the molybdenum boat is transferred into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Example 11
A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst comprises the following steps:
1) At room temperature, dispersing nickel chloride hexahydrate in deionized water to obtain a green and transparent nickel chloride hexahydrate solution with the concentration of 0.015 mol/L;
2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to obtain a colorless and transparent ammonium molybdate tetrahydrate solution with the concentration of 0.02 mol/L;
3) Dropwise adding the amine molybdate tetrahydrate solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1:5;
4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, and reacting at 200 ℃ for 6h to obtain a foamed nickel material (Ni load: 13.4 mg/cm) -2 Mo loading amount: 21.9mg/cm -2 ) Fully washing with deionized water and ethanol, and vacuum drying (temperature 80 deg.C, time 12h, vacuum degree 150 Pa) to obtain a product with area of 2cm 2 Ni-Mo-O precursor;
5) The area obtained in the step (4) is 2cm 2 Putting the Ni-Mo-O precursor into a molybdenum boat, transferring the molybdenum boat into a joule heating instrument, ar/H 2 Reacting for 1min at 500 ℃ in mixed atmosphere to obtain black Ni-MoO 2 An electrocatalyst.
Test example 1
The black Ni-MoO prepared in examples 1-5 2 The application of the electrocatalyst to the hydrogen production by cracking seawater specifically comprises the following steps: mixing Ni-MoO 2 The electrocatalyst is directly used as a working electrode, the calomel electrode is used as a reference electrode, and the graphite electrode is used as a reference electrodeFor the counter electrode, the electrolyte is alkaline seawater (KOH + real seawater, the real seawater is taken from Chinese yellow sea, and the concentration of KOH is 1.0 mol/L). The test results are shown in table 1. FIG. 3 shows Ni-MoO prepared in example 1 2 The electro-catalyst is used for cracking the seawater to produce hydrogen in the alkaline seawater.
TABLE 1Ni-MoO 2 Electrocatalytic performance of electrocatalyst
Figure BDA0003827801950000141
Figure BDA0003827801950000151
As can be seen from Table 1 and FIG. 3, the reaction is carried out for 6h at 150 ℃ under the condition that the mass ratio of ammonium molybdate tetrahydrate and nickel chloride hexahydrate is 1:1 to obtain Ni-Mo-O precursor, and the Ni-MoO precursor is prepared by reacting for 1min at 500 DEG C 2 The electrocatalyst has excellent performance of producing hydrogen by electrocatalysis cracking seawater.
Comparative example 1
The difference from example 2 is that in step 5), the reaction gas is argon.
Comparative example 2
The difference from example 2 is that in step 5), the reaction temperature was 800 ℃.
TABLE 2
Overpotential Overpotential
Comparative example 1 640mV@1Acm -2 200mV@10mAcm -2
Comparative example 2 509mV@1Acm -2 32mV@10mAcm -2
It can be seen that, at Ar/H 2 Black Ni-MoO obtained by reaction at 500 ℃ in mixed atmosphere 2 The electro-catalyst has the most excellent performance of producing hydrogen by electro-catalytically cracking seawater.
The above description is intended to be illustrative of the present invention and should not be taken as limiting the invention, as the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Claims (9)

1. A preparation method of a nickel-doped molybdenum dioxide composite seawater electrocatalyst is characterized by comprising the following steps:
1) Respectively adding ammonium molybdate tetrahydrate and nickel chloride hexahydrate into deionized water, mixing, then putting foamed nickel into the obtained mixed solution, standing, heating, cooling to room temperature, washing, and drying in vacuum to obtain a Ni-Mo-O precursor;
2) And reacting the Ni-Mo-O precursor for 0.5-30min at the temperature of 400-800 ℃ in an inert atmosphere to obtain the nickel-doped molybdenum dioxide composite seawater electrocatalyst.
2. The preparation method of the nickel-doped molybdenum dioxide composite seawater electrocatalyst according to claim 1, wherein in the step 1), the mass ratio of the amine molybdate tetrahydrate to the nickel chloride hexahydrate is 1 (0.1-5.0).
3. The preparation method of the nickel-doped molybdenum dioxide composite seawater electrocatalyst as claimed in claim 1, wherein in the step 1), the standing time is 5-10min.
4. The preparation method of the nickel-doped molybdenum dioxide composite seawater electrocatalyst according to claim 1, wherein in the step 1), the parameters of the heating treatment are as follows: the temperature is 150-200 ℃, and the time is 5-10h.
5. The preparation method of the nickel-doped molybdenum dioxide composite seawater electrocatalyst according to claim 1, wherein in the step 1), the parameters of vacuum drying are as follows: the temperature is 5-100 ℃, the time is 8-72h, and the vacuum degree is 133-267Pa.
6. The method for preparing the nickel-doped molybdenum dioxide composite seawater electrocatalyst according to claim 1, wherein in the step 2), the inert atmosphere refers to Ar/H 2 And (4) mixing the gases.
7. A nickel-doped molybdenum dioxide composite seawater electrocatalyst prepared by the preparation method of the nickel-doped molybdenum dioxide composite seawater electrocatalyst according to any one of claims 1 to 6.
8. The application of the nickel-doped molybdenum dioxide composite seawater electrocatalyst according to claim 7 in the production of hydrogen by electrocatalytic cracking of seawater.
9. The use of claim 8, wherein the nickel-doped molybdenum dioxide composite seawater electrocatalyst serves as a working electrode, a calomel electrode serves as a reference electrode, a graphite electrode serves as a counter electrode, and the electrolyte is alkaline seawater; the pH value of the electrolyte is 10-14.
CN202211064630.6A 2022-09-01 2022-09-01 Nickel-doped molybdenum dioxide composite seawater electrocatalyst and preparation method and application thereof Pending CN115404490A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116043267A (en) * 2023-01-31 2023-05-02 青岛中石大新能源科技有限公司 Ferronickel composite defect type molybdenum oxide electrocatalyst and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116043267A (en) * 2023-01-31 2023-05-02 青岛中石大新能源科技有限公司 Ferronickel composite defect type molybdenum oxide electrocatalyst and preparation method and application thereof
CN116043267B (en) * 2023-01-31 2023-08-29 青岛中石大新能源科技有限公司 Ferronickel composite defect type molybdenum oxide electrocatalyst and preparation method and application thereof

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