CN108425131B - Nickel-molybdenum-based alloy loaded on foamed nickel, amorphous carbon system, and preparation method and application thereof - Google Patents

Nickel-molybdenum-based alloy loaded on foamed nickel, amorphous carbon system, and preparation method and application thereof Download PDF

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CN108425131B
CN108425131B CN201810090565.1A CN201810090565A CN108425131B CN 108425131 B CN108425131 B CN 108425131B CN 201810090565 A CN201810090565 A CN 201810090565A CN 108425131 B CN108425131 B CN 108425131B
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nickel
molybdenum
amorphous carbon
based alloy
foamed
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CN108425131A (en
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杨化桂
俎梦杨
刘鹏飞
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East China University of Science and Technology
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Abstract

The invention discloses a nickel-molybdenum-based alloy loaded on foamed nickel, an amorphous carbon system, a preparation method and application thereof. The invention adopts nickel nitrate and ammonium molybdate as a nickel source and a molybdenum source respectively, and adopts glucose as a carbon source, and the bimetallic carbide Mo grows in situ on the surface of the foamed nickel by hydrothermal and high-temperature carburization methods6Ni6C is taken as a precursor, and Mo is subjected to an electrochemical oxidation process under certain conditions6Ni6C in situ conversion to MoNi3、MoNi4And an amorphous carbon three-substance mixed phase system. The nickel-molybdenum-based alloy and the amorphous carbon system loaded on the nickel foam can be directly used as a working electrode for electrocatalytic oxygen evolution, and can also be used in the fields of rechargeable metal air batteries, water electrolysis processes, regenerative fuel cells and the like.

Description

Nickel-molybdenum-based alloy loaded on foamed nickel, amorphous carbon system, and preparation method and application thereof
Technical Field
The material is prepared by preparing a precursor by a hydrothermal and high-temperature carburization method and then performing in-situ electrochemical oxidation, has excellent performance in the aspect of electrocatalytic oxygen evolution, and has potential application value in the fields of other energy development and environmental protection.
Background
With the rapid increase in energy demand, sustainable energy has received a great deal of attention, mainly including the design of new and effective energy storage devices and the development of natural energy. Among them, hydrogen, which is a clean energy having a very high combustion heat value, is considered as an ideal energy carrier, can be efficiently converted into available effective energy without causing environmental problems, and is applied to various renewable energy systems such as solar cells, metal-air cells, and water-splitting systems, etc. In view of cost and purity, hydrogen production by water electrolysis is one of the most promising and clean hydrogen production methods. However, the production efficiency of hydrogen is mainly affected by oxygen evolution half reaction (OER) at present, because the process of OER reaction needs to transfer four electrons, is a very slow kinetic process, needs to apply high overvoltage to drive the reaction to occur in the OER reaction, and the introduction of the catalyst helps to reduce overpotential, thereby improving the conversion efficiency of energy. Therefore, the development and research of the oxygen evolution electrode with high catalytic activity and low cost price have important theoretical significance and practical value.
The invention utilizes the hydrothermal and high-temperature carburization method to grow the nickel-molybdenum-based bimetallic carbide Mo on the surface of the foamed nickel in situ6Ni6C is used as a precursor and is converted into MoNi in situ through an electrochemical oxidation treatment process3，MoNi4And the amorphous carbon system is used as an electrochemical oxygen evolution catalyst, and during synthesis, the composite system has a simple and convenient process, low price of raw materials, no toxicity and very good oxygen evolution performance. In 1.0M KOH aqueous solution electrolyte, the current density can also reach 10mA cm when the overpotential is 190mV-2And can keep a stable working state for more than 100 hours, and is an oxygen evolution material with high catalytic activity and low cost.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a nickel-molybdenum-based alloy supported on nickel foam, an amorphous carbon system, a preparation method and applications thereof, wherein the preparation method is simple and the cost is low. The prepared nano material has lower oxygen evolution potential and excellent electrocatalytic oxygen evolution performance. No complex instrument is needed in the synthesis process, the operation is simple, and the method is beneficial to large-scale industrial application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nickel-molybdenum-based alloy with nickel loaded on foamed nickel and an amorphous carbon system are provided, wherein the molecular formula of the nickel-molybdenum-based alloy is MoNi3And MoNi4From the precursor Mo6Ni6C large crystal cells are formed by in-situ crushing and transformation, are mutually connected by amorphous carbon, are uniformly covered on the surface of the foamed nickel, keep the original shape of the precursor, and form rod-shaped clusters by nano particles, wherein the particle size is 30-100 nanometers, the shape is irregular spherical, and the scale of the rod-shaped clusters is 0.5-1.5 micrometers.
A hydrothermal and high-temperature carburization method for nickel-molybdenum-based alloy loaded on foamed nickel and an amorphous carbon system comprises the following steps:
(1) dispersing 0.2-0.6 g of nickel nitrate hexahydrate, 0.3-0.7 g of ammonium heptamolybdate tetrahydrate and 0.05-0.25 g of glucose in 10-50 mL of deionized water, placing the deionized water in a steel sleeve with a polytetrafluoroethylene lining, placing 1-5 pieces of foam nickel with a certain area, carrying out hydrothermal treatment for 2-10 hours in an oven at the temperature of 150-200 ℃, naturally cooling to room temperature, washing the foam nickel with deionized water, and placing the foam nickel in the oven at the temperature of 60 ℃ for drying for later use;
(2) putting 1-5 dried foamed nickel obtained in the step (1) into a quartz square boat in a tube furnace for 0.05-0.3L min-1Introducing fully mixed carrier gas, reacting for 60-180 min, and naturally cooling to room temperature;
the temperature of the tubular furnace is 500-900 ℃, and the carrier gas is a mixed gas of argon and hydrogen;
(3) taking out the quartz ark to obtain the nickel-molybdenum-based bimetallic carbide Mo6Ni6And C, belonging to a cubic system, uniformly covering the surface of the foamed nickel, and forming a rod-shaped cluster by using nano particles, wherein the particle size is 30-100 nanometers, the shape is irregular spherical, and the size of the rod-shaped cluster is 0.5-1.5 micrometers.
(4) Carrying out nickel molybdenum base carbide Mo loaded on the foamed nickel obtained in the step (3)6Ni6C, clamping a platinum electrode clamp as a working electrode, a silver-silver chloride electrode as a reference electrode, a graphite rod as a counter electrode, applying a positive potential to the three-electrode system in an alkaline electrolyte solution, taking off the foamed nickel after the treatment time is 10-50 min, washing the foamed nickel for multiple times by deionized water, and drying the foamed nickel in an argon atmosphere to obtain the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system3And MoNi4The nickel foam surface is uniformly covered with the amorphous carbon, and NiOOH and MoO are generated on the alloy surface in the in-situ electrochemical treatment processxAn oxidizing component as an active species for the OER reaction.
The alkaline electrolyte solution is 1.0M KOH, and the positive potential is 1.4-1.8V (vs. RHE).
The application of the nickel-molybdenum-based alloy and the amorphous carbon system is mainly in the aspect of electrocatalytic decomposition of water and oxygen evolution.
The application method comprises the following steps: 0.5-1.5 mol/L of potassium hydroxide aqueous solution is used as an electrolyte solution, the nickel-molybdenum-based alloy and amorphous carbon system growing on the surface of the foamed nickel is used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, a graphite rod electrode is used as a counter electrode, and the test temperature is 15-25 ℃; in an alkaline electrolyte solution, when the overpotential is 190mV, the current density can also reach 8-12 mA cm-2And can be kept in a stable working state for more than 100 hours.
The invention has the beneficial effects that:
(1) the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system are synthesized by adopting a simple hydrothermal and high-temperature carburization method and combining an electrochemical oxidation process, the synthesis method is simple, the operation is convenient and fast, the conditions are mild, the target product has high purity, and the method is safe and nontoxic and can be synthesized in a large scale;
(2) nickel-molybdenum base alloy loaded on foamed nickel and amorphous carbon system Mo6Ni6The result of the C serving as the oxygen evolution electrocatalyst shows that the C has better oxygen evolution performance and lower overpotential. In an alkaline electrolyte solution, when the overpotential is 190mV, the current density can reach 8-12 mA cm-2And can be kept in a stable working state for more than 100 hours;
(3) in the preparation process, all reagents are commercial products and do not need further treatment;
(4) the synthesis method is simple, and the obtained material is easy to apply, is beneficial to popularization and application in industrial production, and can be used as an oxygen evolution material in systems such as rechargeable air batteries, renewable fuel cells and electrochemical oxygen generation systems.
Drawings
FIG. 1 is a linear scan plot of oxygen evolution in alkaline electrolyte solution for nickel foam as a working electrode with nickel molybdenum base alloy prepared in example 1 and an amorphous carbon system supported on the nickel foam;
FIG. 2 shows that the current density of the nickel-molybdenum-based bimetal carbide supported on foamed nickel as the working electrode prepared in example 1 in the alkaline electrolyte solution is 10mA cm-2Time constant current profile;
FIG. 3 is an X-ray diffraction pattern of the nickel molybdenum-based alloy prepared in example 1 and an amorphous carbon system;
FIG. 4 is an X-ray photoelectron spectrum of the nickel element in the nickel-molybdenum-based alloy prepared in example 1 and in the amorphous carbon system and the precursor nickel-molybdenum-based bimetallic carbide;
FIG. 5 is an R-space spectrum of the nickel element in the nickel-molybdenum-based alloy prepared in example 1, as well as the amorphous carbon system and the precursor nickel-molybdenum-based bimetallic carbide;
FIG. 6 is an X-ray photoelectron spectrum of the molybdenum element in the nickel-molybdenum-based alloy prepared in example 1 and in the amorphous carbon system and the precursor nickel-molybdenum-based bimetallic carbide;
FIG. 7 is an in situ R space diagram of the molybdenum element in the nickel molybdenum based alloy and amorphous carbon system prepared in example 1;
FIG. 8 is a Raman spectrum of the nickel molybdenum based alloy supported on foamed nickel prepared in example 1 and the amorphous carbon system and precursor nickel molybdenum based bimetallic carbide;
FIG. 9 is an infrared spectrum of the nickel molybdenum based alloy supported on foamed nickel prepared in example 1 and the amorphous carbon system and precursor nickel molybdenum based bimetallic carbide;
fig. 10 is a scanning electron microscope image of the nickel molybdenum based alloy supported on nickel foam and amorphous carbon system prepared in example 1.
Detailed Description
The following detailed description of the present invention will be made with reference to the accompanying drawings and examples, but the scope of the present invention should not be limited thereby.
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum ranges 3, 4, and 5 are listed, the following ranges are all contemplated: 1-2, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers.
In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, if not specifically mentioned.
The preferred embodiments of the present invention will be described in detail with reference to the following examples, but it should be understood that those skilled in the art can reasonably change, modify and combine the examples to obtain new embodiments without departing from the scope defined by the claims, and that the new embodiments obtained by changing, modifying and combining the examples are also included in the protection scope of the present invention.
Example 1
Step one, preparation of nickel-molybdenum-based alloy loaded on foamed nickel and amorphous carbon system
0.4362g of Ni (NO)3)26H2O，0.5191g(NH4)6Mo7O24·4H2Adding O and 0.1g of glucose into 30mL of deionized water, performing ultrasonic treatment for 30 minutes to uniformly disperse, placing the obtained mixed solution into a steel sleeve with a polytetrafluoroethylene lining, adding 2 pieces of nickel foam with the thickness of 1 square centimeter, reacting in an oven at 150 ℃ for 6 hours, naturally cooling to room temperature, taking out the nickel foam, cleaning with deionized water, and drying in the oven at 60 ℃. The dried foam nickel filled stoneAn English square boat; pushing the quartz ark into the central hot area of the tube furnace, and sealing a flange plate; after hydrogen and argon are measured by a rotameter (hydrogen flow is 0.015L min)-1Argon flow of 0.085L min-1) Fully mixing and then entering a tube furnace; at 5 ℃ for min-1Heating the tube furnace to 700 ℃ at the speed of (1), and carrying out constant temperature treatment for 120 min; and then naturally cooling to room temperature, and taking out the quartz ark to obtain the nickel-molybdenum-based bimetallic carbide precursor loaded on the foamed nickel. The nickel-molybdenum-based bimetallic carbide loaded on the foamed nickel is directly used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, a graphite rod is used as a counter electrode, a 1.6V (vs. RHE) positive potential is applied to the three-electrode system in an alkaline electrolyte solution, namely 1.0M KOH, the foamed nickel is taken down after the treatment time is 30min, deionized water is used for washing for multiple times and is placed under the argon atmosphere for drying, and finally the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system are obtained.
Step two, performance characterization test
And directly taking the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system as working electrodes to perform electrochemical characterization tests. The obtained nickel-molybdenum-based alloy loaded on the nickel foam and the amorphous carbon system electrode are placed in a 1.0 mol/L potassium hydroxide aqueous solution through a CHI660 electrochemical workstation and a standard three-electrode system, and an oxygen evolution linear scanning test is carried out by adopting a conventional method.
Fig. 1 is a linear scan plot of oxygen evolution for the nickel molybdenum based alloy supported on nickel foam prepared in example 1 and an amorphous carbon system and a comparative experimental sample as a working electrode. Wherein: curve 1 is a linear scan curve under the test conditions of 25 ℃ of test temperature and 50 mv/sec of scan speed, in which the nickel-molybdenum-based alloy loaded on nickel foam prepared in example 1 and an amorphous carbon system are used as working electrodes, a silver-silver chloride electrode is used as a reference electrode, a graphite rod is used as a counter electrode, hydrogen saturated 1.0 mol/l potassium hydroxide solution is used as an electrolyte. Curve 2 is the commercial IrO in the comparative experiment2The nickel foam as the working electrode, the silver-silver chloride as the reference electrode, the graphite rod as the counter electrode, the hydrogen saturation of 1.0 mol/L potassium hydroxide solutionThe liquid is electrolyte, the testing temperature is 25 ℃, and the scanning speed is a linear scanning curve under the testing condition of 50 millivolts/second. Curve 3 is a linear scan curve under test conditions of a contrast experiment in which the hollow white nickel foam is used as a working electrode, the silver-silver chloride electrode is used as a reference electrode, the graphite rod is used as a counter electrode, hydrogen saturated sulfuric acid of 0.5 mol/l and potassium hydroxide solution of 1.0 mol/l are used as electrolytes, the test temperature is 25 ℃, and the scan speed is 50 mv/s.
As can be seen from FIG. 1, in a 1.0M KOH electrolyte solution, when the nickel-molybdenum-based alloy supported on nickel foam and the amorphous carbon system as the working electrode had an oxygen evolution overpotential of 190mV, the current density was 10mA cm-2The nickel-molybdenum-based alloy and the amorphous carbon system loaded on the foamed nickel are proved to have excellent electrocatalytic oxygen evolution activity. When the blank foam nickel is used as a working electrode, the current density can reach 10mA cm only when the oxygen evolution overpotential is 453mV-2This demonstrates that the electrocatalytic oxygen evolution activity is derived from the nickel molybdenum based alloy supported on foamed nickel prepared and the amorphous carbon system.
FIG. 2 is a graph showing a constant current curve measured on a CHI660 electrochemical workstation (Shanghai Chenghua instruments) for a nickel-molybdenum-based alloy supported on foamed nickel and an amorphous carbon system prepared in example 1. And (3) testing conditions are as follows: a three-electrode system, in which 1.0 mol/l of the solution is an electrolyte solution, the nickel-molybdenum-based alloy loaded on the nickel foam and the amorphous carbon system prepared in example 1 are working electrodes, a silver-silver chloride electrode is a reference electrode, a graphite rod is an auxiliary electrode, and the continuous current is 10mA cm-2The electrolysis was continued for 100 hours. As can be seen from the results of the graph shown in FIG. 2, the nickel-molybdenum-based alloy supported on nickel foam prepared by the present invention and the amorphous carbon system are used as the working electrode at a current density of 10mA cm-2The electrolysis is continued for 100 hours under constant current, and the oxygen evolution overpotential is maintained at about 220mV without obvious decline. The nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system prepared by the method are proved to have better stability when used as electrodes.
FIG. 3 is an X-ray diffraction pattern of the powder after drying from above the prepared nickel foam under ultrasound, identified as MoNi3、MoNi4And amorphous carbon. Wherein: the broader peak shown in dashed box 1 is the amorphous carbon peak; the series of sharper peaks shown in dashed box 2 is MoNi3And MoNi4The mixed phase of the two nickel-molybdenum-based alloys produces peaks. The scanning speed is 3 DEG min-1And the scanning range is 10-80 degrees.
FIG. 4 is an X-ray photoelectron spectrum of the nickel element in the product and the corresponding precursor. Wherein: curve 1 is the powder after drying with the nickel foam of the nickel molybdenum based alloy and amorphous carbon system prepared in example 1 under ultrasound, and curve 2 is the powder after drying with the nickel foam of the nickel molybdenum based bimetallic carbide precursor prepared in example 1 under ultrasound.
As can be seen from fig. 4, the valence of nickel element in the nickel-molybdenum-based alloy and amorphous carbon system is shifted to a higher position compared to the precursor nickel-molybdenum-based bimetallic carbide, which indicates the generation of high-valence nickel during the reaction, and the result is consistent with the subsequent raman result, which indicates that nickel oxyhydroxide having an oxidizing component on the surface of the nickel-molybdenum-based alloy is generated as an active species for the OER reaction.
FIG. 5 is an R-space spectrum of the nickel element in the product and the corresponding precursor, obtained by Fourier transform of the extended edge of the X-ray absorption fine structure spectrum, and capable of qualitatively analyzing microscopic coordination information of the product. Wherein: curve 1 is the powder after drying with the nickel foam of the nickel molybdenum based alloy and amorphous carbon system prepared in example 1 under ultrasound, and curve 2 is the powder after drying with the nickel foam of the nickel molybdenum based bimetallic carbide precursor prepared in example 1 under ultrasound.
By comparing the curves in FIG. 5, Mo is shown for the precursor dual metal carbide6Ni6C has a nickel element bonding similar to that of metallic nickel, and mainly has a nickel-nickel bond. The Fourier transform result of the extended edge of nickel element in Ni-Mo based alloy and amorphous carbon system is similar to that of nickel oxide
Figure BDA0001563578590000071
And
Figure BDA0001563578590000072
the peaks are clearly shown nearby, which indicates that nickel elements in the nickel-molybdenum-based alloy and the amorphous carbon system are similar to nickel monoxide, mainly have nickel-oxygen bonds, and are consistent with the subsequent raman result, which indicates that nickel oxyhydroxide with oxidized components on the surface of the nickel-molybdenum-based alloy is generated and used as an active species of the OER reaction.
FIG. 6 is an X-ray photoelectron spectrum of molybdenum in the product and the corresponding precursor. Wherein: curve 1 is the powder after drying with the nickel foam of the nickel molybdenum based alloy and amorphous carbon system prepared in example 1 under ultrasound, and curve 2 is the powder after drying with the nickel foam of the nickel molybdenum based bimetallic carbide precursor prepared in example 1 under ultrasound.
As can be seen from fig. 6, the valence of the molybdenum element in the nickel-molybdenum-based alloy and the amorphous carbon system is shifted to a higher position compared to the precursor nickel-molybdenum-based bimetallic carbide, which indicates the generation of high-valence molybdenum during the reaction, and is consistent with the subsequent infrared result, which indicates that the molybdenum oxide having an oxidized component on the surface of the nickel-molybdenum-based alloy is generated as the active species of the OER reaction.
FIG. 7 is an in-situ R-space spectrum of molybdenum in a product and a corresponding precursor, which is obtained by performing Fourier transform on an extended edge of an X-ray absorption fine structure spectrum and can qualitatively analyze microscopic coordination information of the product. Wherein: curve 1 is a plot of the open circuit voltage of the nickel molybdenum based alloy prepared in example 1 and an amorphous carbon system; curve 2 is the nickel molybdenum base alloy prepared in example 1 and the amorphous carbon system after applying a positive potential of 1.4V (vs. RHE); curve 3 is a plot of the nickel molybdenum base alloy prepared in example 1 and the amorphous carbon system after application of a positive potential of 1.45V (vs. RHE); curve 4 is the nickel molybdenum base alloy prepared in example 1 and the amorphous carbon system after applying a positive potential of 1.5V (vs. RHE); curve 5 is the nickel molybdenum based alloy prepared in example 1 and the amorphous carbon system after a longer 1.5V (vs. RHE) positive potential; curve 6 is the nickel molybdenum based alloy prepared in example 1 after reaction with an amorphous carbon system.
As can be seen from a comparison of the curves in fig. 7, after a positive potential is applied, the molybdenum-molybdenum bond in the original nickel-molybdenum-based bimetallic carbide precursor gradually disappears, and the molybdenum-oxygen bond gradually appears as the reaction proceeds. Consistent with the subsequent infrared results, it is demonstrated that molybdenum oxide having an oxidizing component on the surface of the nickel-molybdenum-based alloy is generated as an active species for the OER reaction.
Fig. 8 is a raman spectrum of the product and corresponding precursor, wherein: curve 1 is a curve in which the nickel-molybdenum-based alloy and the amorphous carbon system prepared in example 1 are supported on nickel foam, and curve 2 is a curve in which the nickel-molybdenum-based bimetal carbide precursor prepared in example 1 is supported on nickel foam. 470 and 550cm on Curve 1, compared to Curve 2-1The wave number shows a peak, which indicates that an oxidizing component NiOOH is generated on the surface of the nickel-molybdenum alloy and is used as an active species of an OER reaction.
Fig. 9 is an infrared spectrum of the product and corresponding precursor, wherein: curve 1 is a curve in which the nickel-molybdenum-based alloy and the amorphous carbon system prepared in example 1 are supported on nickel foam, and curve 2 is a curve in which the nickel-molybdenum-based bimetal carbide precursor prepared in example 1 is supported on nickel foam. 634 and 1385cm on Curve 1, compared to Curve 2-1The wave number shows a peak, which shows that the nickel-molybdenum alloy has an oxidizing component MoO on the surfacexGenerated as the active species for the OER reaction.
FIG. 10 is a scanning electron image of a product, and by observing the appearance of a sample, the material is uniformly covered on the surface of the foamed nickel, and the nano particles form a rod-shaped cluster, the particle size is 50 nanometers, the shape is irregular spherical, and the size of the rod-shaped cluster is 1.0 micrometer.
Compared with the existing preparation method of the electrocatalytic oxygen evolution material, the invention has the following advantages: the synthesis process is simple, the raw materials are widely selected, the cost is low, and the electrocatalytic oxygen evolution activity is high.
Example 2
0.2181g of Ni (NO)3)26H2O，0.5191g(NH4)6Mo7O24·4H2O and 0.1g of the mixture are dispersed in glucose and added into 30mL of deionized water, the mixture is evenly dispersed by ultrasonic treatment for 30 minutes, and the obtained mixed solution is placedPutting 2 pieces of foam nickel with the square centimeter inside a steel sleeve with a polytetrafluoroethylene lining, reacting in an oven at 150 ℃ for 6 hours, naturally cooling to room temperature, taking out the foam nickel, cleaning with deionized water, and drying in the oven at 60 ℃. Putting the dried foamed nickel into a quartz square boat; pushing the quartz ark into the central hot area of the tube furnace, and sealing a flange plate; after hydrogen and argon are measured by a rotameter (hydrogen flow is 0.015L min)-1Argon flow of 0.085L min-1) Fully mixing and then entering a tube furnace; at 5 ℃ for min-1Heating the tube furnace to 700 ℃ at the speed of (1), and carrying out constant temperature treatment for 120 min; and then naturally cooling to room temperature, taking out the quartz square boat, naturally cooling to room temperature, and taking out the quartz square boat to obtain the nickel-molybdenum-based bimetallic carbide precursor loaded on the foamed nickel. The nickel-molybdenum-based bimetallic carbide loaded on the foamed nickel is directly used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, a graphite rod is used as a counter electrode, a 1.6V (vs. RHE) positive potential is applied to the three-electrode system in an alkaline electrolyte solution, namely 1.0M KOH, the foamed nickel is taken down after the treatment time is 30min, deionized water is used for washing for multiple times and is placed under the argon atmosphere for drying, and finally the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system are obtained. The characteristics and properties are similar to those of example 1.
Example 3
0.8724g of Ni (NO)3)26H2O，0.5191g(NH4)6Mo7O24·4H2Dispersing O and 0.1g of the mixture in glucose, adding the mixture into 30mL of deionized water, ultrasonically dispersing the mixture uniformly for 30 minutes, placing the obtained mixed solution into a rigid sleeve with a polytetrafluoroethylene lining, placing 2 pieces of nickel foam with the thickness of 1 square centimeter, reacting the mixture for 6 hours in an oven at the temperature of 150 ℃, naturally cooling the mixture to room temperature, taking out the nickel foam, cleaning the nickel foam with the deionized water, and drying the nickel foam in the oven at the temperature of 60 ℃. Putting the dried foamed nickel into a quartz square boat; pushing the quartz ark into the central hot area of the tube furnace, and sealing a flange plate; after hydrogen and argon are measured by a rotameter (hydrogen flow is 0.015L min)-1Argon flow of 0.085L min-1) After fully mixingEntering a tube furnace; at 5 ℃ for min-1Heating the tube furnace to 700 ℃ at the speed of (1), and carrying out constant temperature treatment for 120 min; and then naturally cooling to room temperature, taking out the quartz square boat, naturally cooling to room temperature, and taking out the quartz square boat to obtain the nickel-molybdenum-based bimetallic carbide precursor loaded on the foamed nickel. The nickel-molybdenum-based bimetallic carbide loaded on the foamed nickel is directly used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, a graphite rod is used as a counter electrode, a 1.6V (vs. RHE) positive potential is applied to the three-electrode system in an alkaline electrolyte solution, namely 1.0M KOH, the foamed nickel is taken down after the treatment time is 30min, deionized water is used for washing for multiple times and is placed under the argon atmosphere for drying, and finally the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system are obtained. The characteristics and properties are similar to those of example 1.
The material obtained by the invention is applied to electrocatalytic oxygen evolution. The preparation of the nickel-molybdenum-based alloy loaded on the nickel foam and the application of the amorphous carbon system to a three-electrode test system for electrocatalytic oxygen evolution are carried out at normal temperature and normal pressure, wherein a silver-silver chloride electrode is used as a reference electrode, a graphite rod is used as a counter electrode, hydrogen saturated 1.0 mol/L potassium hydroxide solution is used as electrolyte, and the test temperature is 25 ℃. The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (3)

1. A preparation method of nickel-molybdenum-based alloy and amorphous carbon loaded on foamed nickel is characterized by comprising the following steps:
(1) dispersing 0.2-0.9 g of nickel nitrate hexahydrate, 0.3-0.7 g of ammonium heptamolybdate tetrahydrate and 0.05-0.25 g of glucose in 10-50 mL of deionized water, placing the deionized water in a steel sleeve with a polytetrafluoroethylene lining, placing 1-5 pieces of foam nickel with a certain area, carrying out hydrothermal treatment for 2-10 hours in an oven at the temperature of 150-200 ℃, naturally cooling to room temperature, washing the foam nickel with deionized water, and placing the foam nickel in the oven at the temperature of 60 ℃ for drying for later use;
(2) putting 1-5 dried foamed nickel sheets obtained in the step (1) into a quartz square boat in a tube furnace by 0.05-0.3Lmin-1Introducing fully mixed carrier gas, reacting for 60-180 min, and naturally cooling to room temperature;
the temperature of the tubular furnace is 500-900 ℃, and the carrier gas is a mixed gas of argon and hydrogen;
(3) taking out the quartz square boat to obtain nickel-molybdenum-based carbide Mo loaded on the foamed nickel6Ni6C, belonging to a cubic system, uniformly covering the surface of the foamed nickel, and forming a rod-shaped cluster by using nano particles, wherein the particle size is 30-100 nanometers, the shape is irregular spherical, and the size of the rod-shaped cluster is 0.5-1.5 micrometers;
(4) carrying out nickel molybdenum base carbide Mo loaded on the foamed nickel obtained in the step (3)6Ni6C, clamping a platinum electrode clamp as a working electrode, a silver-silver chloride electrode as a reference electrode, a graphite rod as a counter electrode, applying a positive potential to the three-electrode system in an alkaline electrolyte solution, taking off the foamed nickel after the treatment time is 10-50 min, washing the foamed nickel for multiple times by deionized water, and drying the foamed nickel in an argon atmosphere to obtain the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system, wherein the molecular formula of the nickel-molybdenum-based alloy is MoNi3And MoNi4The nickel foam surface is uniformly covered with the amorphous carbon, and NiOOH and MoO are generated on the alloy surface in the in-situ electrochemical treatment processxAn oxidizing component as an active species for the OER reaction; obtaining nickel-molybdenum-based alloy loaded on the foamed nickel and an amorphous carbon system;
the nickel-molybdenum-based alloy loaded on the foamed nickel and the amorphous carbon system are as follows: the molecular formula of the nickel-molybdenum-based alloy is MoNi3And MoNi4From the precursor Mo6Ni6C is formed by in-situ crushing and converting large crystal cells, the large crystal cells are connected with each other through amorphous carbon, the surface of the foamed nickel is uniformly covered, the original appearance of the precursor is kept, and the nano particles form rod-shaped clusters, the particle size is 30-100 nanometers, the shape is irregular spherical, and the size of the rod-shaped clusters is 0.5-1.5 micrometers; NiOOH and MoO are generated on the surface of the alloy in the in-situ electrochemical treatment processxAn oxidizing component as an active species for the OER reaction; obtaining the nickel-molybdenum-based alloy loaded on the foamed nickel and an amorphous carbon system.
2. Use of the nickel molybdenum based alloy supported on nickel foam and amorphous carbon system according to claim 1, characterized in that the nickel molybdenum based alloy supported on nickel foam and amorphous carbon system are used for electrocatalytic decomposition of water to oxygen.
3. The use according to claim 2, characterized in that the method of application is as follows: 0.5-1.5 mol/L of potassium hydroxide aqueous solution is used as electrolyte solution, and the nickel-molybdenum-based alloy MoNi growing on the surface of the foamed nickel is3、MoNi4The amorphous carbon system is used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, a graphite rod electrode is used as a counter electrode, and the testing temperature is 15-25 ℃; in an alkaline electrolyte solution, when the overpotential is 190mV, the current density can reach 8-12 mA cm-2And can be kept in a stable working state for more than 100 hours.
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