CN110387559B - Preparation method of electrocatalytic oxygen production film electrode material, product and application thereof - Google Patents
Preparation method of electrocatalytic oxygen production film electrode material, product and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of an electrocatalytic oxygen production film electrode material, and a product and application thereof. The Prussian blue analogue film is grown on the foamed nickel by adopting a liquid phase epitaxial growth method, and then is calcined in the air for oxidation treatment to obtain the oxide film. The method has the advantages of high synthesis speed, high preparation efficiency, controllable film area, controllable film thickness, environmental protection, low cost, simple operation and the like, and provides a convenient method for large-scale preparation. The prepared electro-catalytic oxygen production thin-film electrode material can be directly used for a working electrode for electro-catalytic oxygen production, has good conductivity, and solves the problems that a glassy carbon electrode is poor in performance as a current collector, an active substance on the surface of the electrode material is poor in adhesion, easy to fall off and the like in the field of electro-catalytic oxygen production in the prior art, so that the electro-catalytic oxygen production thin-film electrode material has good application prospect in the field of electro-catalytic oxygen production (OER).
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of an electrocatalytic oxygen production film electrode material, and a product and application thereof.
Background
The rapid development of economy has an increasing demand for energy, the reserves of traditional fossil fuels are limited, and the environmental problems caused by the large consumption of fossil fuels are becoming more serious, so that the development of clean and efficient energy materials is important. Hydrogen is an energy source material with abundant reserves, cleanness, high efficiency and sustainable utilization, the preparation of hydrogen by water electrolysis is an important source of hydrogen, and the anodic half-reaction and oxygen production reaction (OER) of water electrolysis need to overcome higher overpotential and consume higher energy, so the development of an OER catalyst with high efficiency, low price and high stability is one of the hot problems concerned by scientists at present.
Studies have shown that noble metal oxides, such as ruthenium dioxide and iridium dioxide, are highly effective OER catalysts, but their practical application is limited due to their high price and limited reserves. At present, transition metal oxides, sulfides and phosphides of some powder are widely researched, but most of researches are carried out on the basis of being loaded on a glassy carbon electrode, and the requirements of practical application cannot be met.
Therefore, a simple, economical and large-scale preparation method of the electrocatalytic oxygen production electrode is urgently needed at present, so that the prepared electrode material has lower cost and can be applied to catalyzing the oxygen production half reaction in actual electrolyzed water.
Disclosure of Invention
The invention aims to reduce the cost for preparing an electrocatalytic oxygen production material on one hand and provide an efficient and stable oxide thin film electrode as well as a preparation method and application thereof on the other hand. The Prussian Blue analogue (PBAs for short) is grown on the foamed nickel by adopting a liquid phase epitaxial growth method, and then the Prussian Blue analogue is converted into the metal oxide by adopting a method of carrying out oxidation treatment by high-temperature calcination, so that the prepared oxide film material electrode can be directly used as a working electrode for electrocatalytic oxygen generation. The method can prepare uniform and compact PBAs film precursors, the oxide film formed after heat treatment can still be attached to the foamed nickel substrate, and the PBAs film precursors have high-efficiency oxygen generation reaction (OER) catalytic performance.
The technical scheme adopted by the invention is as follows:
a preparation method of an electrocatalytic oxygen production film electrode material comprises the following steps:
1) growing Prussian Blue Analogue (PBAs) films on the foamed nickel by adopting a liquid phase epitaxial growth method;
2) calcining the material obtained in the step 1) at high temperature to obtain the electrocatalytic oxygen production film electrode material, wherein the material comprises foamed nickel and a metal oxide film attached to the foamed nickel.
According to the invention, the main component of the metal oxide thin film is MM'2O4Wherein M is selected from divalent metal ionsAnd M' is selected from trivalent metal ions.
For example, M is selected from Co2+、Fe2+、Zn2+、Mn2+、Ni2+、Cd2+Or Cu2+(ii) a M' is selected from Co3+、Al3+、Fe3+、Ni3+、Mn3+、Cr3+、Ln3+Etc., wherein Ln3+Is a rare earth ion selected from La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+、Y3+Or Sc3+。
According to the invention, the metals of M and M' may be the same or different.
Specifically, the main component of the metal oxide thin film is CoFe2O4、ZnFe2O4、MnFe2O4、FeMn2O4、NiFe2O4、CdFe2O4、CuFe2O4、FeCo2O4、Co3O4、ZnCo2O4、MnCo2O4、NiCo2O4、CdCo2O4、CuCo2O4、MnAl2O4、FeAl2O4、CoAl2O4、NiAl2O4、CuAl2O4、ZnAl2O4、ZnNi2O4、CoNi2O4、MnNi2O4、CoCr2O4、NiCr2O4、FeCr2O4、FeLn2O4、CoLn2O4、NiLn2O4Wherein Ln is a rare earth element selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
According to the invention, the PBAs are combined with M-containing metal ionsSubstances and K3[M’(CN)6]Or compounds containing M' metal ions with K4[M(CN)6]The complex with a certain space structure is formed.
Preferably, the M metal ion-containing compound is selected from M (CH)3COO)2、MSO4、M(NO3)2Or MCl2And the like.
Preferably, the M 'metal ion containing compound is selected from M' (CH)3COO)3、M’2(SO4)3、M’(NO3)3Or M' Cl3And the like.
According to the invention, the PBAs are preferably compounds containing M metal ions with K3[M’(CN)6]The complex with a certain space structure is formed.
For example, the PBAs may be the reaction product of potassium ferricyanide and cobalt acetate: co3[Fe(CN)6]2Abbreviated PBA (Co-Fe).
According to the invention, the preparation method of the electrocatalytic oxygen production film electrode material can specifically comprise the following steps:
s1, preparing solution of compound containing M metal ions and K3[M’(CN)6]Or preparing a solution of a compound containing M' metal ions and K4[M(CN)6]The solution of (1);
s2, cleaning the foamed nickel substrate;
s3, soaking the foam nickel in a solution of a compound containing M metal ions and K3[M’(CN)6]Or soaking the foamed nickel in a solution of a compound containing M' metal ions and K4[M(CN)6]Forming a thin film layer of PBAs by a liquid phase epitaxial growth method;
s4, repeating the step S3 to obtain a PBAs film growing on the foamed nickel;
and S5, calcining at high temperature to obtain the electrocatalytic oxygen production film electrode material.
According to the present invention, in step S1, the solvent of the solution may be water.
In step S1, the concentration of the M metal ion-containing compound or the M' metal ion-containing compound in the solution may be 2 to 10mmol/L, preferably 3 mmol/L.
In step S1, K in the solution3[M’(CN)6]Or K4[M(CN)6]The concentration of (B) may be 2 to 10mmol/L, preferably 2 mmol/L.
According to the present invention, in step S2, the cleaning may be: and ultrasonically cleaning the foamed nickel by using a dilute hydrochloric acid solution, then ultrasonically cleaning the foamed nickel in distilled water for several times, and airing the foamed nickel.
According to the present invention, in step S3, the reaction is preferably performed by a manual soaking method.
In step S3, the reaction may be performed in an apparatus for liquid phase epitaxial growth.
In step S3, the method for preparing PBAs films on nickel foam, for example, includes the following steps: in a solution containing M metal ions and K3[M’(CN)6]Sequentially soaking foamed nickel in the solution to form a PBAs film on the foamed nickel; or, in a solution containing M' metal ions and K4[M(CN)6]The solution of (a) is sequentially soaked in the foamed nickel to form a PBAs film on the foamed nickel.
Wherein, the solution of the M metal ion-containing compound and K3[M’(CN)6]The amount of the solution of (a) may be the same or different, and the solution is preferably used without foaming nickel; or, a solution of the M' metal ion-containing compound and K4[M(CN)6]The amount of the solution of (a) may be the same or different, and the solution is preferably used without foaming nickel.
Wherein the temperature of the soaking may be the same or different, and is selected independently from 25-80 ℃, such as 50-80 ℃;
preferably, the soaking process may be performed under water bath conditions.
Wherein the soaking times may be the same or different and are independently selected from 15 to 60 minutes, preferably 20 to 25 minutes.
Preferably, after soaking the solution of the M metal ion-containing compound and K3[M’(CN)6]After the solution of (A), or after soaking the solution of the M' metal ion-containing compound and K4[M(CN)6]Further comprising the step of allowing each of them to stand to sufficiently react. The time of standing may be 3 to 5 minutes.
Further preferably, the method further comprises the step of removing residual reaction raw materials by using distilled water after the standing reaction.
Preferably, the sequential soaking sequence is as follows: solution of M metal ion-containing compound → distilled water → K3[M’(CN)6]Solution of (a) → distilled water, or solution of a compound containing M' metal ion → distilled water → K4[M(CN)6]Solution of → distilled water.
According to the invention, in step S4, the number of repetitions is 10 or more, for example 15.
According to the present invention, in step S5, the reaction may be performed in a muffle furnace.
In step S5, the temperature of the calcination may be 200-500 deg.C, such as 250 deg.C, 350 deg.C or 450 deg.C.
In step S5, the calcination time may be 1 to 5 hours, preferably 2 hours.
In step S5, the calcination may be performed in air.
According to the invention, the preparation method of the electrocatalytic oxygen production film electrode material can specifically comprise the following steps:
s1, preparing a cobalt acetate solution and a potassium ferricyanide solution;
s2, cleaning the foamed nickel substrate;
s3, soaking the foamed nickel in a cobalt acetate solution and a potassium ferricyanide solution, and forming a film layer of PBAs by a liquid phase epitaxial growth method;
s4, repeating the step S3 to obtain a PBAs film growing on the foamed nickel;
and S5, calcining at high temperature to obtain the electrocatalytic oxygen production film electrode material.
The method according to the invention for preparing PBAs films on nickel foam comprises, for example, the following steps: sequentially soaking foamed nickel in a cobalt acetate solution and a potassium ferricyanide solution to form a PBA (Co-Fe) film on the foamed nickel: PBA (Co-Fe)/NF.
Preferably, the sequential soaking sequence is as follows: cobalt acetate solution → distilled water → potassium ferricyanide solution → distilled water.
According to the invention, the thickness of the PBAs film can be controlled by controlling the repeated operation times, so that different PBAs film thicknesses can be prepared according to different use requirements.
According to the invention, in order to obtain electrode materials with different areas, the nickel foam with different areas can be selected according to the use requirement.
The invention also provides the following scheme:
the electrocatalytic oxygen production thin film electrode material is prepared by the preparation method of the electrocatalytic oxygen production thin film electrode material, and comprises foamed nickel and a metal oxide thin film attached to the foamed nickel.
Preferably, the main component of the metal oxide thin film is MM'2O4Wherein M is selected from divalent metal ions and M' is selected from trivalent metal ions.
For example, M is selected from Co2+、Fe2+、Zn2+、Mn2+、Ni2+、Cd2+Or Cu2+(ii) a M' is selected from Co3+、Al3+、Fe3+、Ni3+、Mn3+、Cr3+、Ln3+Etc., wherein Ln3+Is a rare earth ion selected from La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+、Y3+Or Sc3+。
According to the invention, the metals of M and M' may be the same or different.
Specifically, the main component of the metal oxide thin film is CoFe2O4、ZnFe2O4、MnFe2O4、FeMn2O4、NiFe2O4、CdFe2O4、CuFe2O4、FeCo2O4、Co3O4、ZnCo2O4、MnCo2O4、NiCo2O4、CdCo2O4、CuCo2O4、MnAl2O4、FeAl2O4、CoAl2O4、NiAl2O4、CuAl2O4、ZnAl2O4、ZnNi2O4、CoNi2O4、MnNi2O4、CoCr2O4、NiCr2O4、FeCr2O4、FeLn2O4、CoLn2O4、NiLn2O4Wherein Ln is a rare earth element selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
The invention also provides application of the electro-catalytic oxygen production film electrode material as a working electrode, preferably an anode working electrode for water electrolysis, for OER catalytic reaction.
In the preparation method of the present invention, the oxide thin film prepared by the high-temperature calcination method can be directly used for the OER catalytic reaction as an electrode material. Therefore, the membrane material prepared by the method effectively combines the active substance and the current collector together, and can be directly used as a working electrode for OER catalytic reaction.
The invention has the advantages of
The invention provides a preparation method of a film material with electrocatalytic oxygen production performance, which comprises the steps of growing a PBAs film on the surface of foamed nickel by adopting a liquid phase epitaxial growth method, for example, taking cobalt acetate and potassium ferricyanide as raw materials, and sequentially assembling the raw materials layer by using a soaking method, thereby preparing the foamed nickel embedded with the PBAs film. The method can accurately control the thickness and the area of the PBAs film in the preparation process, and has high preparation efficiency. And the thickness of the PBAs film can be controlled by controlling the number of operations. The thickness of the PBAs film can control the amount of the calcined loaded substance, and the uniformity of the PBAs film can ensure that the calcined loaded substance is more uniformly attached to the foamed nickel substrate.
The invention adopts a high-temperature calcination method to calcine the foamed nickel embedded with the PBAs film, so as to obtain the electrocatalytic oxygen production electrode material containing the metal oxide film. The method has the advantages of simple operation, high efficiency, high synthesis speed, environmental protection and low cost. Therefore, the invention provides a large-scale and convenient preparation method.
The electrocatalytic oxygen production film electrode material prepared by the invention has better conductivity, is convenient for diffusion and transmission of electrons, and solves the problems that in the electrocatalytic oxygen production field in the prior art, a glassy carbon electrode is poor in performance as a current collector, and active substances on the surface of the electrode material are poor in adhesive force and easy to fall off, so that the electrocatalytic oxygen production film electrode material has wide prospect in the electrocatalytic oxygen production field and other electrochemical fields.
Drawings
FIG. 1 is a powder diffraction pattern (including experimental values, theoretical values and base nickel foam) of the electrocatalytic oxygen generating thin film electrode material prepared in example 1.
FIG. 2 is a physical diagram of the electrocatalytic oxygen-producing thin film electrode material prepared in example 1.
Fig. 3 is an SEM image of the electrocatalytic oxygen-generating thin film electrode material prepared in example 1.
FIG. 4 is a LSV curve of the electrocatalytic oxygen generating thin film electrode material prepared in example 1 in a 1.0mol/L KOH electrolyte.
FIG. 5 shows the electrocatalytic oxygen-generating thin film electrode material prepared in example 1 at a current density of about 10mA/cm2And (4) testing the stability of the test piece.
Detailed Description
The invention provides a method for preparing an oxide film electrode material with OER catalytic performance by growing a PBAs film on foamed nickel and further calcining at high temperature. Specifically, a PBAs film is grown on the foamed nickel by adopting a liquid phase epitaxial growth method, and then the PBAs film is calcined for oxidation treatment to obtain the oxide film electrode material with OER catalytic performance. The invention adopts a liquid phase epitaxial growth method, namely two reactants are prepared into solution with a certain proportion, preferably aqueous solution, then PBAs films are assembled layer by a manual soaking method, and then the oxide film electrode material with OER catalytic performance is obtained by a high-temperature calcination method.
In the preparation process, in order to enable the PBAs film to grow well, the invention also carries out acid cleaning on the foamed nickel, thereby providing a good growth template for the preparation of the film. According to the present invention, after the foamed nickel is washed and dried, it is placed in an apparatus for liquid phase epitaxial growth. And soaking the cleaned foamed nickel in the raw material solution according to a certain sequence by using a manual injection method, and controlling the reaction time to perform epitaxial growth on the foamed nickel.
The concentration distribution of the raw material solution is controlled within the range, the factors such as reaction speed, surface morphology control and the like are mainly considered, and the effects of controllable thickness and smooth and flat surface can be achieved within the numerical range.
The technical solution of the present invention is explained in detail by the exemplary embodiments below. These examples should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the examples are all commercially available products or can be prepared by known methods.
Example 1
1) Preparation of PBA (Co-Fe)/NF Prussian blue analogue film
Cobalt acetate and potassium ferricyanide were weighed and dissolved in distilled water to prepare 500ml solutions having concentrations of 3mmol/L and 2mmol/L, respectively.
Pouring the prepared 3mmol/L cobalt acetate aqueous solution into a brown bottle, putting the cleaned foam nickel into the brown bottle, putting the bottle into a 50 ℃ water bath kettle for standing for a period of time, taking out the foam nickel, rinsing the foam nickel with distilled water, taking the prepared 2mmol/L potassium ferricyanide aqueous solution, pouring the foam nickel into the brown bottle, putting the bottle into the 50 ℃ water bath kettle for standing for a period of time, taking out the foam nickel, rinsing the foam nickel with distilled water, and completing a complete manual soaking cycle.
Wherein the soaking amount of the cobalt acetate solution is preferably 20 minutes, the soaking time is 20 minutes, the standing reaction time is 3 minutes after soaking, and the residual reaction raw materials are removed by rinsing with distilled water after reaction. And then soaking the potassium ferricyanide solution for 25 minutes until the potassium ferricyanide solution is immersed in the foamed nickel, standing for reaction for 3 minutes after soaking, and rinsing with distilled water after reaction to remove residual reaction raw materials. And then repeating the raw material soaking step for 15 times to obtain the PBA (Co-Fe)/NF Prussian blue analogue film material with the corresponding thickness.
2) Preparation of electrocatalytic oxygen production film electrode material
And finally, placing the foamed nickel with the PBA (Co-Fe) film in a crucible, placing the crucible in a muffle furnace, calcining for 2 hours at 350 ℃ in the air atmosphere, and then cooling to room temperature to obtain the oxide film material.
And (3) performing powder diffraction characterization and scanning electron microscope characterization on the sample obtained in the step 1) and the step 2), wherein the results are shown in fig. 1 and fig. 3. As can be seen from the powder diffraction spectrum in FIG. 1, the Prussian blue analog PBA (Co-Fe) film successfully grows on the foamed nickel, and CoFe is formed after 2 hours of heat treatment at 350 DEG C2O4A film. The change in color of the base foam nickel, from gray to black, can be seen in fig. 2. As can be seen from the scanning electron micrograph of fig. 3, the oxide film obtained after oxidation treatment of the PBAs film prepared in example 1 uniformly grew on the nickel foam.
3) Electrocatalytic oxygen production performance test
The film material obtained in the step 2) is directly used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and the electrocatalytic oxygen production performance is tested in a KOH solution of 1mol/L, and the result is shown in figure 4.
From FIG. 4, the change in current density with voltage can be seen, at a current density of 10mA/cm2The overpotential is 269mv, and the OER performance is better. From FIG. 5, it can be seen that the current density is dependent on timeAt a current density of about 10mA/cm2Meanwhile, the prepared oxide film electrode can continuously work for 20 hours, and the current density is not obviously attenuated, so that the oxide film electrode has high stability.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The preparation method of the electrocatalytic oxygen production film electrode material is characterized by comprising the following steps:
s1, preparing solution of compound containing M metal ions and K3[M’(CN)6]Or preparing a solution of a compound containing M' metal ions and K4[M(CN)6]The solution of (1);
s2, cleaning the foamed nickel substrate;
s3, soaking the foam nickel in a solution of a compound containing M metal ions and K3[M’(CN)6]Or soaking the foamed nickel in a solution of a compound containing M' metal ions and K4[M(CN)6]Forming a thin film layer of PBAs by a liquid phase epitaxial growth method;
the specific soaking steps are as follows: solution of M metal ion-containing compound → distilled water → K3[M’(CN)6]Solution of (a) → distilled water, or solution of a compound containing M' metal ion → distilled water → K4[M(CN)6]Solution of → distilled water;
s4, repeating the step S3 to obtain a PBAs film growing on the foamed nickel;
s5, calcining at high temperature to obtain the electrocatalytic oxygen production film electrode material; the material comprises foamed nickel and a metal oxide film attached to the foamed nickel; the main component of the metal oxide film is MM'2O4Wherein M is selected from Co2+、Fe2+、Zn2+、Mn2 +、Ni2+、Cd2+Or Cu2+(ii) a M' is selected from Co3+、Al3+ 、Fe3+、Ni3+、Mn3+、Cr3+Or Ln3+Wherein, Ln3+Is a rare earth ion selected from La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+、Y3+Or Sc3+；
The M metal ion-containing compound is selected from M (CH)3COO)2、MSO4、M(NO3)2Or MCl2；
The M 'metal ion-containing compound is selected from M' (CH)3COO)3、M’2(SO4)3、M’(NO3)3Or M' Cl3；
In step S1, the concentration of the M metal ion-containing compound or the M' metal ion-containing compound in the solution is 2 to 10 mmol/L;
in step S1, K in the solution3[M’(CN)6]Or K4[M(CN)6]The concentration of (A) is 2 to 10 mmol/L;
in step S5, the temperature of the calcination is 200-500 ℃.
2. The method according to claim 1, wherein the metals of M and M' are the same or different.
3. The production method according to claim 1, wherein the main component of the metal oxide thin film is CoFe2O4、ZnFe2O4、MnFe2O4、FeMn2O4、NiFe2O4、CdFe2O4、CuFe2O4、FeCo2O4、Co3O4、ZnCo2O4、MnCo2O4、NiCo2O4、CdCo2O4、CuCo2O4、MnAl2O4、FeAl2O4、CoAl2O4、NiAl2O4、CuAl2O4、ZnAl2O4、ZnNi2O4、CoNi2O4、MnNi2O4、CoCr2O4、NiCr2O4、FeCr2O4、FeLn2O4、CoLn2O4Or NiLn2O4Wherein Ln is a rare earth element selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
4. The method of claim 1, wherein the PBAs are the reaction product of potassium ferricyanide and cobalt acetate: co3[Fe(CN)6]2。
5. The method according to claim 1, wherein in step S1, the solvent of the solution is water.
6. The method according to claim 1, wherein in step S2, the cleaning is: and ultrasonically cleaning the foamed nickel by using a dilute hydrochloric acid solution, then ultrasonically cleaning the foamed nickel in distilled water for several times, and airing the foamed nickel.
7. The method according to claim 1, wherein the solution of the M metal ion-containing compound and K are mixed in step S33[M’(CN)6]The dosage of the solution is the same or different, and the dosage of the solution is the amount of the foam nickel; or, a solution of the M' metal ion-containing compound and K4[M(CN)6]The amount of the solution of (a) is the same or different, and the solution is used without foaming nickel.
8. The method for preparing the compound of claim 1, wherein the soaking temperature is the same or different and is selected from 25-80 ℃ independently from each other in step S3;
the soaking times are the same or different and are independently selected from 15 to 60 minutes.
9. The method according to claim 1, wherein the M metal ion-containing compound is soaked in the solution and K in step S33[M’(CN)6]After the solution of (A), or after soaking the solution of the M' metal ion-containing compound and K4[M(CN)6]After the solution of (1), a step of allowing each of them to stand to sufficiently react; the standing time is 3-5 minutes.
10. The method according to claim 9, further comprising a step of soaking with distilled water after the standing reaction; the purpose of soaking with distilled water is to remove residual reaction raw materials.
11. The method according to claim 1, wherein the number of repetitions is 10 or more in step S4.
12. The method according to claim 1, wherein in step S5, the calcination is performed for 1 to 5 hours.
13. The production method according to any one of claims 1 to 12, characterized by being:
s1, preparing a cobalt acetate solution and a potassium ferricyanide solution;
s2, cleaning the foamed nickel substrate;
s3, soaking the foamed nickel in a cobalt acetate solution and a potassium ferricyanide solution, and forming a film layer of PBAs by a liquid phase epitaxial growth method;
s4, repeating the step S3 to obtain a PBAs film growing on the foamed nickel;
s5, calcining at high temperature to obtain the electrocatalytic oxygen production film electrode material;
step S3 specifically includes the following steps: sequentially soaking foamed nickel in a cobalt acetate solution and a potassium ferricyanide solution to form a PBA (Co-Fe) film on the foamed nickel: PBA (Co-Fe)/NF;
the sequential soaking sequence is as follows: cobalt acetate solution → distilled water → potassium ferricyanide solution → distilled water.
14. An electrocatalytic oxygen-producing thin film electrode material prepared by the method of any one of claims 1-13, the material comprising nickel foam and a thin film of metal oxide attached to the nickel foam.
15. Use of the electrocatalytic oxygen-producing thin film electrode material of claim 14 as an anode working electrode for water electrolysis for OER catalyzed reactions.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140531A (en) * | 2015-09-23 | 2015-12-09 | 太原理工大学 | Three-dimensional anode material for hydrogen production by water electrolysis and preparation method of three-dimensional anode material |
| CN105951123A (en) * | 2016-05-06 | 2016-09-21 | 湖北大学 | Preparation method for NiCoP nanowire electro-catalytic electrode |
| CN106966443A (en) * | 2017-03-24 | 2017-07-21 | 福州大学 | A kind of preparation method of transition metal oxide/sulfide nano composite material |
| CN107159293A (en) * | 2017-05-12 | 2017-09-15 | 华南理工大学 | A kind of NiFe3N/NF electrochemical catalysts and preparation method and application |
| CN107732206A (en) * | 2017-10-18 | 2018-02-23 | 安徽工业大学 | A kind of preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy |
-
2018
- 2018-04-16 CN CN201810339980.6A patent/CN110387559B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140531A (en) * | 2015-09-23 | 2015-12-09 | 太原理工大学 | Three-dimensional anode material for hydrogen production by water electrolysis and preparation method of three-dimensional anode material |
| CN105951123A (en) * | 2016-05-06 | 2016-09-21 | 湖北大学 | Preparation method for NiCoP nanowire electro-catalytic electrode |
| CN106966443A (en) * | 2017-03-24 | 2017-07-21 | 福州大学 | A kind of preparation method of transition metal oxide/sulfide nano composite material |
| CN107159293A (en) * | 2017-05-12 | 2017-09-15 | 华南理工大学 | A kind of NiFe3N/NF electrochemical catalysts and preparation method and application |
| CN107732206A (en) * | 2017-10-18 | 2018-02-23 | 安徽工业大学 | A kind of preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy |
Non-Patent Citations (1)
| Title |
|---|
| Mesoporous Ni一Fe oxide multi一composite hollownanocages for efficient electrocatalytic water oxidation reactions;Bong Kyun Kang等;《Journal of Materials Chemistry A》;20170130;第5卷;摘要，第4321页第1段 * |
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