CN114774968B - Foam nickel-loaded NiFe amorphous nano-array electrocatalytic electrode and preparation method thereof - Google Patents
Foam nickel-loaded NiFe amorphous nano-array electrocatalytic electrode and preparation method thereof Download PDFInfo
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- CN114774968B CN114774968B CN202210610800.XA CN202210610800A CN114774968B CN 114774968 B CN114774968 B CN 114774968B CN 202210610800 A CN202210610800 A CN 202210610800A CN 114774968 B CN114774968 B CN 114774968B
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Abstract
The invention discloses a nickel foam supported NiFe amorphous nano array electrocatalytic electrode and a preparation method thereof, wherein a piece of nickel foam with preset size is selected for pretreatment; coating the pretreated foam nickel to form a Ni-based coating on the surface; the nickel foam with Ni-based coating is subjected to secondary coating treatment to convert the surface Ni-based coating into NiFe-based coating, the multi-level combined porous composite structure of the NiFe multi-level porous amorphous nano-array provides fully exposed rich active sites and enhanced charge transport, and porous mass transfer channels can be used for high-efficiency ion and bubble transport, and the nickel foam-loaded NiFe multi-level porous amorphous nano-array exhibits excellent oxygen evolution electrocatalytic activity and ultra-high stability in alkaline electrolyte, near neutral electrolyte and alkaline seawater.
Description
Technical Field
The invention relates to the technical field of oxygen production by electrolyzed water, in particular to a nickel foam loaded NiFe amorphous nano array electrocatalytic electrode and a preparation method thereof.
Background
Since ancient times, energy is an important material basis and power source for human survival and development. With the continuing growth of the global population, the energy demands of the human society are increasing, and strong dependence on fossil fuels has been derived. Fossil energy is a limited non-renewable energy source that will face a dead environment in the foreseeable future, which undoubtedly presents a serious challenge for human survival and sustainable development of economic society. Through researches, the hydrogen energy, biomass energy, tidal energy, solar energy and wind energy are taken as alternative options of fossil energy, and the demand of human beings for green, environment-friendly and efficient renewable energy is greatly increased. The hydrogen energy has many advantages of high combustion heat value, large energy density, rich sources, cleanness, high efficiency and the like, and has long been regarded as ideal secondary energy. Compared with the traditional hydrogen production means such as fossil fuel pyrolysis hydrogen production, biomass hydrogen production and the like, the electrocatalytic decomposition water hydrogen production is a key technical means hopeful to realize the cyclic utilization of hydrogen energy. However, the current hydrogen production by electrolysis of water is only 3% of the total annual production, and the main reason is that the electrolysis of water needs to overcome the higher energy barrier of water decomposition, consumes a large amount of electric energy, and causes energy waste.
Secondly, the common electrocatalytic decomposition water reaction is carried out in an electrolyte environment prepared by pure water, pure water resources belong to rare resources on the earth, and the effective utilization of industrial wastewater and seawater is a key for solving the problem. To solve these key problems, the smart design of anode and cathode catalytic materials in an electrolytic cell is the most powerful means to reduce the water splitting reaction energy barrier. The water decomposition reaction can be divided into two half reactions, namely a Hydrogen Evolution Reaction (HER) and an Oxygen Evolution Reaction (OER), the research of electrode materials of the hydrogen evolution reaction is mature, the catalytic efficiency reaches a higher level under various conditions, but the oxygen evolution reaction electrocatalyst which can adapt to various electrolyte environments is not materially broken through at present, so the efficiency of the water decomposition is often reduced to be higher than that of the oxygen evolution reaction. Therefore, development of anode electrode materials with high catalytic activity for oxygen evolution reactions, which are suitable for various electrolyte environments, has become one of the key points for hydrogen production by water electrolysis.
However, the preparation method of the high-performance electrocatalytic oxygen evolution electrode material is more complicated and complex at present, and large-scale production is difficult to realize. A simple and efficient large-scale electrode material preparation method is developed, and the method is an effective method for effectively reducing the production difficulty and saving the cost. Currently, oxygen evolution electrocatalysts with higher catalytic activity are typically composed of noble metal materials (Ru/Ir). Precious metal materials are limited in their use on a large scale due to their high price and their low reserves. Therefore, development of a non-noble metal catalyst with high catalytic activity, strong stability and high price is imperative. Among them, transition metals (Fe, ni, etc.) are stored and enriched on earth, and oxygen evolution electrocatalysts with high catalytic activity prepared from them have the possibility of mass production.
Disclosure of Invention
The invention aims to provide a foam nickel-loaded NiFe amorphous nano array electrocatalytic electrode and a preparation method thereof, so as to solve or improve at least one of the technical problems.
In view of the above, a first aspect of the present invention is to provide a method for preparing a nickel foam supported NiFe amorphous nano-array electrocatalytic electrode.
The second aspect of the invention is to provide a nickel foam supported NiFe amorphous nano-array electrocatalytic electrode.
The third aspect of the invention is to provide an application of a nickel foam supported NiFe amorphous nano array electrocatalytic electrode.
The first aspect of the invention provides a preparation method of a nickel foam supported NiFe amorphous nano array electrocatalytic electrode, which comprises the following steps: s1, selecting foam nickel as a matrix, and preprocessing the foam nickel; s2, forming an amorphous Ni-based coating on the surface of the foam nickel matrix by adopting a continuous chemical deposition method; s3, forming an amorphous NiFe-based coating on the surface of the amorphous Ni-based coating by adopting a continuous chemical deposition method; s4, drying to obtain the nickel foam supported NiFe multi-level porous amorphous nano array electrocatalytic electrode.
According to the preparation method of the nickel foam supported NiFe amorphous nano array electrocatalytic electrode, provided by the invention, the NiFe-based coating is obtained by adopting the coating for two times, and the repeatability between the two operations is high, so that the preparation method is simple as a whole, the process is simple and easy to implement, and the industrial mass production and preparation can be realized.
The unique multilayer sheet structure is assembled layer by layer on the surface of the foam nickel by a multi-time coating method, and the foam nickel is a three-dimensional net-shaped material, so that the multilayer structure is compounded with the three-dimensional porous structure of the foam nickel, and the prepared catalyst has the unique multilayer sheet structure and the three-dimensional porous structure on the surface, so that the ultra-strong wettability with electrolyte in the catalytic process is ensured.
The foam nickel-assisted chemical deposition method of the bubble template ensures good structural stability of the oxygen evolution electrode, can bear a large amount of bubbles generated in the catalytic reaction process, and effectively improves the structural stability of the oxygen evolution electrocatalyst.
The multi-level combined porous composite structure of the NiFe multi-level porous amorphous nano-array provides fully exposed rich active sites and enhanced charge transport, and the porous mass transfer channels can be used for high-efficiency ion and bubble transport, and the nickel foam loaded NiFe multi-level porous amorphous nano-array exhibits excellent oxygen evolution electrocatalytic activity and ultra-high stability in alkaline electrolyte, near neutral electrolyte and alkaline seawater.
In addition, the technical scheme provided by the embodiment of the invention can also have the following additional technical characteristics:
in any of the above technical solutions, the step of preprocessing S1 specifically includes: sequentially placing a matrix in 5-7 mol/L hydrochloric acid, acetone and deionized water, and respectively carrying out ultrasonic treatment for 30-45 min; and then drying the matrix for 6-8 h in a vacuum environment with the temperature of 50-100 ℃.
In the technical scheme, the foam nickel needs to be subjected to a pretreatment process before the surface of the foam nickel is machined, so that the foam nickel is ensured to meet the expected production and machining state in the machining process, ultrasonic waves have energy, and operations such as washing and machining can be performed under the action of the ultrasonic waves. The nickel oxide layer and organic pollutants attached to the surface of the foam nickel and the inner wall of the hollow hole can be cleaned under the cooperation of various solutions, the influence on surface coating in subsequent experimental processing is avoided, the surface coating of the foam nickel is more uniform and complete, hydrochloric acid belongs to colorless liquid, the solution belongs to aqueous solution of hydrogen chloride, stubborn stains on the surface of the foam nickel can be corroded so as to fall off, substances can be dissolved by acetone cleaning, the substances can be kept in a state in the solution, residue is reduced, deionized water is in a pure water form for removing mineral ions (salt), and soluble ions and unattached sediments on the surface of the coating are removed.
In any of the above technical solutions, the S2 specifically includes: s2-1, immersing the substrate into a mixed aqueous solution of nickel chloride and sodium hypophosphite in a preset concentration range, and taking out after 0.5-1.5 min; s2-2, spraying an alkaline sodium borohydride aqueous solution with Ph being more than or equal to 9 by using a spray gun, and uniformly spraying the alkaline sodium borohydride aqueous solution onto the surface of the wetted substrate to form an amorphous Ni-based coating; s2-3, washing the substrate with the amorphous Ni-based coating by deionized water, and removing soluble ions and unattached sediments on the surface of the amorphous Ni-based coating; s2-4, returning to the step S2-1 until the foam nickel matrix is completely covered by the black amorphous Ni-based coating.
In the technical scheme, the pretreated foam nickel is immersed into the mixed aqueous solution of nickel chloride and sodium hypophosphite with preset concentration range, so that the surface of the foam nickel can carry the mixed solution, and the foam nickel is taken out after 0.5-1.5 min, so that the surface of the foam nickel and the inner wall of a hollow hole can be uniformly adhered with the mixed solution;
according to specific Ph value requirements, sodium hydroxide is dropwise added into an alkaline sodium borohydride aqueous solution to change the Ph value of the alkaline sodium borohydride aqueous solution (but Ph is more than or equal to 9), and then sodium hydroxide is dropwise added into the alkaline sodium borohydride aqueous solution to spray and shoot out through a spray gun in the prior art so as to spray the alkaline sodium borohydride aqueous solution on the surface of the foam nickel for reaction to form a Ni-based coating;
and then washing the foam nickel after the reaction by using ionized water to wash out soluble ions and unattached sediments on the surface of the Ni-based coating, so that the surface of the Ni-based coating is clean and the attachment of impurities is reduced.
In any of the above technical solutions, the step S3 specifically includes: s3-1, immersing the substrate with the Ni-based coating into a mixed aqueous solution of nickel chloride, ferrous sulfate and sodium hypophosphite with a preset concentration range, and taking out after 0.5-1.5 min; s3-2, spraying an alkaline sodium borohydride aqueous solution with Ph being more than or equal to 9 by using a spray gun, and uniformly spraying the aqueous solution onto the surface of the wetted amorphous Ni-based coating to form an amorphous NiFe-based coating; s3-3, washing the deposited substrate with deionized water to remove soluble ions and unattached sediments on the surface of the amorphous NiFe-based coating; s3-4, returning to the step S3-1 until the amorphous NiFe-based coating layer which is uniformly distributed is formed on the surface of the amorphous Ni-based coating layer of the matrix.
In the technical scheme, foam nickel with a Ni-based coating on the surface is immersed in a mixed aqueous solution of nickel chloride, ferrous sulfate and sodium hypophosphite with preset concentration ranges, so that the surface of the Ni-based coating can be provided with the mixed solution, and the foam nickel is taken out after 0.5-1.5 min, so that the Ni-based coatings at different positions of the foam nickel can be uniformly adhered with the mixed solution;
according to specific Ph value requirements, dropwise adding sodium hydroxide into an alkaline sodium borohydride aqueous solution to change the Ph value of the alkaline sodium borohydride aqueous solution (but the Ph is more than or equal to 9), and then dropwise adding sodium hydroxide into the alkaline sodium borohydride aqueous solution to spray and shoot out through a spray gun in the prior art so as to spray the alkaline sodium borohydride aqueous solution on the surface of the Ni-based coating for reaction to form a NiFe-based coating;
and then washing the foam nickel after the reaction by using ionized water to wash out soluble ions and unattached sediments on the surface of the NiFe-based coating, so that the surface of the NiFe-based coating is clean and the attachment of impurities is reduced.
In any of the above technical solutions, the drying process in S4 specifically includes: and (3) placing the substrate loaded with the amorphous NiFe-based coating in a vacuum oven at the temperature of 40-60 ℃ and drying for 3-6 h to obtain a final finished product.
In the technical scheme, as the surface with the NiFe-based coating is also provided with deionized water, if the surface is not removed in time, dust in the air is easy to adhere to the surface of the NiFe-based coating, the actual application is influenced, the deionized water can be slowly evaporated in a vacuum oven at 40-60 ℃, and the surface of the NiFe-based coating which can be foamed nickel can be dried completely after being dried for 3-6 hours.
In any of the above technical schemes, the concentration of the alkaline sodium borohydride is 2.5mol/L-3.5mol/L.
In the technical scheme, the concentration of the alkaline sodium borohydride is set to be between 2.5mol/L and 3.5mol/L, so that the concentration of the alkaline sodium borohydride can completely ensure the requirement of the processing procedure of the method, and meanwhile, the application of the excessive concentration can be avoided, so that the material waste is caused.
In any of the above technical schemes, the preset concentration range in S2-1 is: the concentration of the nickel chloride is 0.1mol/L-0.6mol/L, and the concentration of the sodium hypophosphite is 1.2mol/L-1.8mol/L; the preset concentration range in the step S3-1 is as follows: the concentration of the nickel chloride is 0.1mol/L-0.6mol/L, the concentration of the ferrous sulfate is 0.1mol/L-0.6mol/L, and the concentration of the sodium hypophosphite is 1.2mol/L-1.8mol/L.
In the technical scheme, in order to ensure the normal product output of the experiment, the concentration range of nickel chloride is set between 0.1mol/L and 0.6mol/L, the concentration range of ferrous sulfate is set between 0.1mol/L and 0.6mol/L, and the concentration range of sodium hypophosphite is set between 1.2mol/L and 1.8mol/L, so that the expected output of the experiment product is ensured, the waste caused by the overhigh setting of raw materials can be reduced, the random setting of the raw materials is avoided, and the smooth performance of the experiment processing is ensured.
The second aspect of the invention provides a nickel foam supported NiFe amorphous nano-array electrocatalytic electrode, which is prepared by the preparation method of the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode according to any one of the first aspect of the invention.
The nickel foam supported NiFe amorphous nano-array electrocatalytic electrode provided by the invention can be realized by the method steps of any one of the technical schemes, so that the electrocatalyst provided by the second aspect of the invention has all technical effects of the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode and is not described herein.
In a third aspect, the invention provides the use of a nickel foam supported NiFe amorphous nano array electrocatalytic electrode for electrocatalytic oxygen evolution reactions in alkaline, near neutral electrolytes and alkaline seawater.
The invention provides an application of a nickel foam supported NiFe amorphous nano array electrocatalytic electrode, which takes nickel foam with hollow bubbles as an auxiliary template, and prepares a NiFe multi-level porous amorphous nano array on the surface of nickel foam by a continuous chemical deposition method, wherein the nickel foam supported NiFe amorphous nano array has excellent electrocatalytic oxygen evolution performance in alkaline electrolyte, near-neutral electrolyte and alkaline seawater.
Additional aspects and advantages of embodiments according to the invention will be apparent from the description which follows, or may be learned by practice of embodiments according to the invention.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1 is a Scanning Electron Microscope (SEM) view of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the present invention;
FIG. 3 is a graph of oxygen evolution polarization of an electrocatalyst according to the invention in 1M KOH;
FIG. 4 is a graph of oxygen evolution polarization of the electrocatalyst of the invention in 1M KBi;
FIG. 5 is a graph showing the oxygen evolution polarization of the electrocatalyst of the invention in alkaline seawater.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
The embodiment of the first aspect of the invention provides a preparation method of a nickel foam supported NiFe amorphous nano-array electrocatalytic electrode, which comprises the following steps: s1, selecting foam nickel as a matrix, and preprocessing the foam nickel; s2, forming an amorphous Ni-based coating on the surface of the foam nickel matrix by adopting a continuous chemical deposition method; s3, forming an amorphous NiFe-based coating on the surface of the amorphous Ni-based coating by adopting a continuous chemical deposition method; s4, drying to obtain the nickel foam supported NiFe multi-level porous amorphous nano array electrocatalytic electrode.
According to the preparation method of the nickel foam supported NiFe amorphous nano array electrocatalytic electrode, provided by the invention, the NiFe-based coating is obtained by adopting the coating for two times, and the repeatability between the two operations is high, so that the preparation method is simple as a whole, the process is simple and easy to implement, and the industrial mass production and preparation can be realized.
The unique multilayer sheet structure is assembled layer by layer on the surface of the foam nickel by a multi-time coating method, and the foam nickel is a three-dimensional net-shaped material, so that the multilayer structure is compounded with the three-dimensional porous structure of the foam nickel, and the prepared catalyst has the unique multilayer sheet structure and the three-dimensional porous structure on the surface, so that the ultra-strong wettability with electrolyte in the catalytic process is ensured.
Further, by first forming an amorphous Ni-based plating layer on the surface of the nickel foam as a base body and then forming an amorphous NiFe-based plating layer again on the surface of the amorphous Ni-based plating layer, on the one hand, the connection tightness between the nickel foam as a base body and the upper load can be effectively enhanced, and the conductivity is better. On the other hand, the middle amorphous Ni-based coating exists, so that the connection is firmer, and the catalytic stability and the mechanical stability are better.
The foam nickel-assisted chemical deposition method of the bubble template ensures good structural stability of the oxygen evolution electrode, can bear a large amount of bubbles generated in the catalytic reaction process, and effectively improves the structural stability of the oxygen evolution electrocatalyst.
The multi-level combined porous composite structure of the NiFe multi-level porous amorphous nano-array provides fully exposed rich active sites and enhanced charge transport, and the porous mass transfer channels can be used for high-efficiency ion and bubble transport, and the nickel foam loaded NiFe multi-level porous amorphous nano-array exhibits excellent oxygen evolution electrocatalytic activity and ultra-high stability in alkaline electrolyte, near neutral electrolyte and alkaline seawater.
Further, the multi-layered structure can enhance the transport of substances (desorption of gaseous products) and charges during catalysis; the unique material structure synthesized by the bubble template method can ensure the catalytic stability of the gas product when the gas product is produced vigorously in the high-current density catalytic process.
Specifically, the nickel foam was cut into a sheet structure of 15cm×30cm in size prior to processing.
In any of the foregoing embodiments, the step of preprocessing S1 specifically includes: sequentially placing a matrix in 5-7 mol/L hydrochloric acid, acetone and deionized water, and respectively carrying out ultrasonic treatment for 30-45 min; and then drying the matrix for 6-8 h in a vacuum environment with the temperature of 50-100 ℃.
In this embodiment, the nickel foam is subjected to a pretreatment process before the surface treatment of the nickel foam is performed, so as to ensure that the nickel foam meets the expected production and processing state in the process, ultrasonic waves have energy, and operations such as washing and processing can be performed under the action of the ultrasonic waves. The nickel oxide layer and organic pollutants attached to the surface of the foam nickel and the inner wall of the hollow hole can be cleaned under the cooperation of various solutions, the influence on surface coating in subsequent experimental processing is avoided, the surface coating of the foam nickel is more uniform and complete, hydrochloric acid belongs to colorless liquid, the solution belongs to aqueous solution of hydrogen chloride, stubborn stains on the surface of the foam nickel can be corroded so as to fall off, substances can be dissolved by acetone cleaning, the substances can be kept in a state in the solution, residue is reduced, deionized water is in a pure water form for removing mineral ions (salt), and soluble ions and unattached sediments on the surface of the coating are removed.
In any of the foregoing embodiments, S2 specifically includes: s2-1, immersing the substrate in a mixed aqueous solution of nickel chloride and sodium hypophosphite in a preset concentration range, and taking out after 0.5-1.5 min; s2-2, spraying an alkaline sodium borohydride aqueous solution with Ph being more than or equal to 9 by using a spray gun, and uniformly spraying the alkaline sodium borohydride aqueous solution onto the surface of a wetted substrate to form an amorphous Ni-based coating; s2-3, washing the substrate with the amorphous Ni-based coating by deionized water to remove soluble ions and unattached sediments on the surface of the amorphous Ni-based coating; s2-4, returning to the step S2-1 until the foam nickel matrix is completely covered by the black amorphous Ni-based coating.
In the embodiment, the pretreated foam nickel is immersed in the mixed aqueous solution of nickel chloride and sodium hypophosphite with a preset concentration range, so that the surface of the foam nickel can carry the mixed solution, and the foam nickel is taken out after 0.5-1.5 min, so that the surface of the foam nickel and the inner wall of a hollow hole can be uniformly adhered with the mixed solution;
according to specific Ph value requirements, sodium hydroxide is dropwise added into an alkaline sodium borohydride aqueous solution to change the Ph value of the alkaline sodium borohydride aqueous solution (but Ph is more than or equal to 9), and then sodium hydroxide is dropwise added into the alkaline sodium borohydride aqueous solution to spray and shoot out through a spray gun in the prior art so as to spray the alkaline sodium borohydride aqueous solution on the surface of the foam nickel for reaction to form a Ni-based coating;
and then washing the foam nickel after the reaction by using ionized water to wash out soluble ions and unattached sediments on the surface of the Ni-based coating, so that the surface of the Ni-based coating is clean and the attachment of impurities is reduced.
In any of the foregoing embodiments, S3 specifically includes: s3-1, immersing the substrate with the Ni-based coating into a mixed aqueous solution of nickel chloride, ferrous sulfate and sodium hypophosphite with a preset concentration range, and taking out after 0.5-1.5 min; s3-2, spraying an alkaline sodium borohydride aqueous solution with Ph being more than or equal to 9 by using a spray gun, and uniformly spraying the alkaline sodium borohydride aqueous solution onto the surface of the wetted amorphous Ni-based coating to form an amorphous NiFe-based coating; s3-3, washing the deposited substrate with deionized water to remove soluble ions and unattached sediments on the surface of the amorphous NiFe-based coating; s3-4, returning to the step S3-1 until the amorphous NiFe-based coating layer which is uniformly distributed is formed on the surface of the amorphous Ni-based coating layer of the matrix.
In the embodiment, the foam nickel with the Ni-based coating on the surface is immersed in the mixed aqueous solution of nickel chloride, ferrous sulfate and sodium hypophosphite with preset concentration range, so that the surface of the Ni-based coating can carry the mixed solution, and the foam nickel is taken out after 0.5min-1.5min, so that the Ni-based coating at different positions of the foam nickel can be uniformly adhered with the mixed solution;
according to specific Ph value requirements, dropwise adding sodium hydroxide into an alkaline sodium borohydride aqueous solution to change the Ph value of the alkaline sodium borohydride aqueous solution (but the Ph is more than or equal to 9), and then dropwise adding sodium hydroxide into the alkaline sodium borohydride aqueous solution to spray and shoot out through a spray gun in the prior art so as to spray the alkaline sodium borohydride aqueous solution on the surface of the Ni-based coating for reaction to form a NiFe-based coating;
and then washing the foam nickel after the reaction by using ionized water to wash out soluble ions and unattached sediments on the surface of the NiFe-based coating, so that the surface of the NiFe-based coating is clean and the attachment of impurities is reduced.
Specifically, the amorphous NiFe-based coating is prepared by a simple continuous chemical deposition method at room temperature with the aid of a strong bubble template. A combination of sodium borohydride (NaBH 4) and sodium hypophosphite (NaH 2PO 2) in high concentrations was introduced as a strong reducing agent and a bubble generating agent to rapidly build and deposit the electrode material. During the reduction of the metal ions, the reducing agent itself releases a large number of metalloid atoms (B, P) incorporated into the metal matrix, resulting in a NiFe-based nanocomposite having a stable amorphous structure. In addition, the accelerated catalytic hydrolysis of excess sodium borohydride in continuous deposition results in severe hydrogen gas generation, which is mainly triggered by the massive protons released by sodium hypophosphite and the catalytic action of the in-situ deposited multi-component nickel-based amorphous coating.
In any of the above embodiments, the drying process in S4 specifically includes: and (3) placing the substrate loaded with the amorphous NiFe-based coating in a vacuum oven at the temperature of 40-60 ℃ and drying for 3-6 h to obtain a final product.
In this embodiment, since the surface with the NiFe-based coating is further provided with deionized water, if not removed in time, dust in the air is easy to adhere to and adhere to the surface of the NiFe-based coating, which affects practical application, the surface of the NiFe-based coating, which may be foamed nickel, is completely dried by slowly evaporating the deionized water in a vacuum oven at 40-60 ℃ and continuously drying for 3-6 hours.
In any of the above embodiments, the concentration of basic sodium borohydride is 2.5mol/L to 3.5mol/L.
In the embodiment, the concentration of the alkaline sodium borohydride is set to be between 2.5mol/L and 3.5mol/L, so that the concentration of the alkaline sodium borohydride can completely ensure the requirement of the processing procedure of the method, and meanwhile, the application of the excessive concentration can be avoided, so that the material waste is caused.
In any of the above embodiments, the predetermined concentration range in S2-1 is: the concentration of the nickel chloride is 0.1mol/L-0.6mol/L, and the concentration of the sodium hypophosphite is 1.2mol/L-1.8mol/L; the preset concentration range in step S3-1 is: the concentration of nickel chloride is 0.1mol/L-0.6mol/L, the concentration of ferrous sulfate is 0.1mol/L-0.6mol/L, and the concentration of sodium hypophosphite is 1.2mol/L-1.8mol/L.
In the embodiment, in order to ensure the normal product output of the experiment, the concentration range of nickel chloride is set between 0.1mol/L and 0.6mol/L, the concentration range of ferrous sulfate is set between 0.1mol/L and 0.6mol/L, and the concentration range of sodium hypophosphite is set between 1.2mol/L and 1.8mol/L, so that the expected output of the experiment product is ensured, the waste caused by the overhigh setting of raw materials can be reduced, the random setting of the raw materials is avoided, and the smooth performance of the experiment processing is ensured.
The second aspect of the invention provides a nickel foam supported NiFe amorphous nano-array electrocatalytic electrode, which is prepared by adopting the preparation method of the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode according to any one of the first aspect of the invention.
The nickel foam supported NiFe amorphous nano-array electrocatalytic electrode provided by the invention can be realized by the method steps of any one of the embodiments, so that the electrocatalyst provided by the second aspect of the invention has all technical effects of the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode and is not described herein.
The invention provides an application of a foam nickel-loaded NiFe amorphous nano array electrocatalytic electrode, which is used for electrocatalytic oxygen evolution reaction in alkaline and near-neutral electrolyte and alkaline seawater.
The invention provides an application of a nickel foam supported NiFe amorphous nano array electrocatalytic electrode, which takes nickel foam with hollow bubbles as an auxiliary template, and prepares a NiFe multi-level porous amorphous nano array on the surface of nickel foam by a continuous chemical deposition method, wherein the nickel foam supported NiFe amorphous nano array has excellent electrocatalytic oxygen evolution performance in alkaline electrolyte, near-neutral electrolyte and alkaline seawater.
Example 1
As shown in fig. 1 to 3, in the present embodiment, a large-sized nickel foam is used as a substrate, and an amorphous Ni-based plating layer is first chemically deposited on the nickel foam by a bubble template-assisted method at room temperature. And then, the amorphous NiFe multi-level porous amorphous nano array coating is chemically deposited on the foam nickel by a bubble template auxiliary method to prepare the high-performance oxygen evolution electrocatalyst.
The method for preparing the nickel foam supported NiFe multi-level porous amorphous nano array oxygen evolution electrocatalyst at room temperature in a large scale is carried out according to the following steps.
(1) A bulk foam nickel (15 cm x 30 cm) was first sonicated in 6M hydrochloric acid, acetone and water sequentially to remove the nickel oxide layer and organic contaminants.
(2) The nickel foam was immersed in a mixed aqueous solution of 0.6M nickel chloride and 1.5M sodium hypophosphite at a concentration for one minute and then removed to ensure that the nickel foam was completely filled with the solution.
(3) And (3) taking a newly prepared alkaline sodium borohydride aqueous solution (dropwise adding a proper amount of sodium hydroxide) with the pH value of more than or equal to 9 and the concentration of 3M, and uniformly spraying the aqueous solution onto the wet foam nickel matrix by using a spray gun to quickly form Ni-based black attachments.
(4) The deposited foam nickel is washed by deionized water, and the soluble ions and unattached sediments on the surface of the plating layer are removed.
(5) Repeating the steps (2) - (4) for 8 times until the foam nickel substrate is completely covered with the Ni-based black attachments.
(6) The foam nickel of the pre-deposited Ni-based black attachments was immersed in a mixed aqueous solution containing 0.4M nickel chloride and 0.2M ferrous sulfate and 1.5M sodium hypophosphite at a concentration for one minute and then removed to ensure that the foam nickel of the pre-deposited Ni-based black attachments was completely filled with the solution.
(7) And (3) taking newly prepared alkaline sodium borohydride aqueous solution with the pH value of more than or equal to 9 and the concentration of 3M (dropwise adding a proper amount of sodium hydroxide), and uniformly spraying the aqueous solution onto the foam nickel covered by the wetted Ni-based black attachments by using a spray gun to quickly form more NiFe-based black attachments.
(8) The deposited foam nickel is washed by deionized water, and the soluble ions and unattached sediments on the surface of the plating layer are removed.
(9) Repeating the steps (6) - (8) for 8 times until a uniformly distributed porous NiFe-based coating is obtained.
(10) The prepared material was dried in a vacuum oven at 45 ℃ for 5 hours.
(11) Taking the nickel foam supported NiFe multi-level porous amorphous nano-array electrocatalyst obtained in the embodiment as an example, the nickel foam coated by the nickel foam multi-level porous amorphous nano-array is in a uniform black shape as a whole. The black attachments carried on the surface of the nickel foam are scraped off, XRD analysis is carried out on the black attachments, as shown in figure 2, the NiFe multi-layer porous amorphous nano-array electrocatalyst prepared by the embodiment presents typical amorphous broad diffraction peaks, and the NiFe-based coating on the surface of the nickel foam is amorphous. From the SEM electron microscope image in fig. 1, it can be seen that the NiFe-based amorphous plating layer is uniformly distributed on the surface of the nickel foam and appears as a multi-layered and porous microstructure.
(12) The electrochemical test of this example was performed in a three-electrode cell at room temperature under normal pressure, the counter electrode was a Pt plate electrode, the reference electrode was a Hg/HgO electrode, the working electrode was a foam nickel-loaded NiFe multi-level porous amorphous nano array electrode prepared in this example, the electrochemical workstation was Shanghai Chen Hua CHI760I, the electrolyte was 1M KOH, and the electrode was 267mV overpotential at a current density of 500mA cm-2 as known from an oxygen evolution polarization graph (FIG. 3)
Example 2
As shown in fig. 4, in the present embodiment, a large piece of nickel foam is used as a substrate, and an amorphous Ni-based plating layer is first chemically deposited on the nickel foam by a bubble template assisted method at room temperature. And then, the amorphous NiFe multi-level porous amorphous nano array coating is chemically deposited on the foam nickel by a bubble template auxiliary method to prepare the high-performance oxygen evolution electrocatalyst.
(1) The preparation method of the foam nickel substrate and the preparation method of the electrocatalyst are exactly the same as the steps (1) to (10) of example 1.
(2) The electrochemical test of this example was performed in a three-electrode cell at room temperature under normal pressure, the counter electrode was a Pt plate electrode, the reference electrode was an Ag/AgCl electrode, the working electrode was a nickel foam-supported NiFe multi-level porous amorphous nano array electrode prepared in this example, the electrochemical workstation was Shanghai cinhua CHI760I, the electrolyte was 1M KBi (potassium tetraborate), and the electrode was 318mV overpotential at a current density of 100mA cm "2 as known from an oxygen evolution polarization graph (fig. 4).
Example 3
As shown in fig. 5, in the present embodiment, a large piece of nickel foam is used as a substrate, and an amorphous Ni-based plating layer is first chemically deposited on the nickel foam by a bubble template assisted method at room temperature. And then, the amorphous NiFe multi-level porous amorphous nano array coating is chemically deposited on the foam nickel by a bubble template auxiliary method to prepare the high-performance oxygen evolution electrocatalyst.
(1) The preparation method of the foam nickel substrate and the preparation method of the electrocatalyst are exactly the same as the steps (1) to (10) of example 1.
(2) The electrochemical test of this example was performed in a three-electrode cell at room temperature under normal pressure, the counter electrode was a Pt sheet electrode, the reference electrode was a Hg/HgO electrode, the working electrode was a nickel foam-supported NiFe multi-level porous amorphous nano-array electrode prepared in this example, the electrochemical workstation was Shanghai cinnabar CHI760I, the electrolyte was a 1M KOH natural seawater solution, and the electrode was 337mV overpotential at a current density of 500mA cm "2 as known from an oxygen evolution polarization graph (fig. 5).
In the description of the present invention, it should be understood that the terms "longitudinal," "transverse," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
The foregoing embodiments are merely illustrative of the preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but various modifications and improvements made by those skilled in the art to which the present invention pertains are made without departing from the spirit of the present invention, and all changes and modifications and improvements fall within the scope of the present invention as defined in the appended claims.
Claims (7)
1. The preparation method of the foam nickel-loaded NiFe amorphous nano array electrocatalytic electrode is characterized by comprising the following steps of:
s1, selecting foam nickel as a matrix, and preprocessing the foam nickel;
s2, forming an amorphous Ni-based coating on the surface of the foam nickel matrix by adopting a continuous chemical deposition method; the specific step of S2 comprises the following steps:
s2-1, immersing the substrate into a mixed aqueous solution of nickel chloride and sodium hypophosphite in a preset concentration range, and taking out after 0.5-1.5 min;
s2-2, spraying an alkaline sodium borohydride aqueous solution with Ph being more than or equal to 9 by using a spray gun, and uniformly spraying the alkaline sodium borohydride aqueous solution onto the surface of the wetted substrate to form an amorphous Ni-based coating;
s2-3, washing the substrate with the amorphous Ni-based coating by deionized water, and removing soluble ions and unattached sediments on the surface of the amorphous Ni-based coating;
s2-4, returning to the step S2-1 until the foam nickel matrix is completely covered by the black amorphous Ni-based coating;
s3, forming an amorphous NiFe-based coating on the surface of the amorphous Ni-based coating by adopting a continuous chemical deposition method; the step S3 specifically comprises the following steps:
s3-1, immersing the substrate with the Ni-based coating into a mixed aqueous solution of nickel chloride, ferrous sulfate and sodium hypophosphite with a preset concentration range, and taking out after 0.5-1.5 min;
s3-2, spraying an alkaline sodium borohydride aqueous solution with Ph being more than or equal to 9 by using a spray gun, and uniformly spraying the aqueous solution onto the surface of the wetted amorphous Ni-based coating to form an amorphous NiFe-based coating;
s3-3, washing the deposited substrate with deionized water to remove soluble ions and unattached sediments on the surface of the amorphous NiFe-based coating;
s3-4, returning to the step S3-1 until an amorphous NiFe-based coating layer which is uniformly distributed is formed on the surface of the amorphous Ni-based coating layer of the matrix;
s4, drying to obtain the nickel foam supported NiFe multi-level porous amorphous nano array electrocatalytic electrode.
2. The method for preparing the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode according to claim 1, wherein the step of S1 pretreatment specifically comprises:
sequentially placing a matrix in 5-7 mol/L hydrochloric acid, acetone and deionized water, and respectively carrying out ultrasonic treatment for 30-45 min;
and then drying the matrix for 6-8 h in a vacuum environment with the temperature of 50-100 ℃.
3. The method for preparing the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode according to claim 1, wherein the drying treatment in S4 specifically comprises:
and (3) placing the substrate loaded with the amorphous NiFe-based coating in a vacuum oven at the temperature of 40-60 ℃ and drying for 3-6 h to obtain a final finished product.
4. The method for preparing the nickel foam supported NiFe amorphous nano array electrocatalytic electrode according to claim 1, wherein the concentration of the alkaline sodium borohydride is 2.5mol/L-3.5mol/L.
5. The method for preparing the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode according to claim 1, wherein the preset concentration range in S2-1 is as follows: the concentration of the nickel chloride is 0.1mol/L-0.6mol/L, and the concentration of the sodium hypophosphite is 1.2mol/L-1.8mol/L;
the preset concentration range in the step S3-1 is as follows: the concentration of the nickel chloride is 0.1mol/L-0.6mol/L, the concentration of the ferrous sulfate is 0.1mol/L-0.6mol/L, and the concentration of the sodium hypophosphite is 1.2mol/L-1.8mol/L.
6. A nickel foam supported NiFe amorphous nano-array electrocatalytic electrode, characterized in that the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode is prepared by a preparation method according to any one of claims 1-5.
7. Use of the nickel foam supported NiFe amorphous nano-array electrocatalytic electrode of claim 6 for electrocatalytic oxygen evolution reactions in alkaline, near neutral electrolytes and alkaline seawater.
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| CN109794247A (en) * | 2019-01-16 | 2019-05-24 | 北京工业大学 | A kind of amorphous iron-doped nickel oxide nano-sheet electrocatalysis material and its preparation and application |
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| CN109794247A (en) * | 2019-01-16 | 2019-05-24 | 北京工业大学 | A kind of amorphous iron-doped nickel oxide nano-sheet electrocatalysis material and its preparation and application |
| WO2021030755A1 (en) * | 2019-08-15 | 2021-02-18 | University Of Houston System | Non-noble metal-nitride based electrocatalysts for high-performance seawater splitting |
| CA3176893A1 (en) * | 2020-04-28 | 2021-11-04 | Zhifeng Ren | Fast ambient-temperature synthesis of oer catalysts for water electrolysis |
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