CN113355681A - MNi(1-x)FexF3Oxygen evolution electrocatalytic material, preparation method and application thereof - Google Patents

MNi(1-x)FexF3Oxygen evolution electrocatalytic material, preparation method and application thereof Download PDF

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CN113355681A
CN113355681A CN202110777940.1A CN202110777940A CN113355681A CN 113355681 A CN113355681 A CN 113355681A CN 202110777940 A CN202110777940 A CN 202110777940A CN 113355681 A CN113355681 A CN 113355681A
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mni
oxygen evolution
electrode
nickel
hydrogen
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CN113355681B (en
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刘守清
周漪雯
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Suzhou Sunshine Hydrogen Energy Material Technology Co ltd
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
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    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses MNi(1‑x)FexF3An oxygen evolution electrocatalytic material, a preparation method and an application thereof. The MNi(1‑x)FexF3The crystal structure of the catalytic material is a perovskite type cubic crystal system, and the space group is Pm3mSpace group, M is potassium or sodium ion, x is more than 0 and less than 1. The MNi(1‑x)FexF3The oxygen evolution electrocatalytic material can be obtained by mixing and reacting hydrogen fluoride, hydroxide, nickel salt and ferrous salt in a protective atmosphere. The MNi(1‑x)FexF3When the oxygen evolution electro-catalysis material is applied to hydrogen production by water electrolysis, the overpotential of oxygen evolution is lower than that of noble metal, the stability of oxygen evolution is high, and the oxygen evolution electro-catalysis material is applied to hydrogen production by photovoltaic water electrolysis, wind power hydrogen production and hydroelectric generationHas wide application prospect in hydrogen.

Description

MNi(1-x)FexF3Oxygen evolution electrocatalytic material, preparation method and application thereof
Technical Field
The invention relates to an oxygen evolution electrocatalytic material, in particular to MNi taking nickel ions as coordination center ions and fluorine ions as ligands(1-x)FexF3A preparation method of an oxygen evolution electro-catalysis material and application thereof in electro-catalysis oxygen evolution in water electrolysis hydrogen production, belonging to the technical field of hydrogen energy materials.
Background
Solar photovoltaic water electrolysis hydrogen production, wind energy water electrolysis hydrogen production or water conservancy power generation hydrogen production are important methods for obtaining clean hydrogen energy. The noble metals ruthenium and iridium and oxides thereof are well-known oxygen evolution electrocatalysts with excellent performance. The publication No. CN112853391A discloses a preparation method of ruthenium oxide supported double metal hydroxide and application in electrocatalytic oxygen evolution, and the publication No. CN112760677A discloses an iridium tungsten alloy nano material, a preparation method thereof and application as an acidic oxygen evolution reaction catalyst. The research on cheap and efficient non-noble metal catalysts is the key for realizing low-cost hydrogen production by water electrolysis and is an effective way for producing hydrogen by using renewable energy sources.
The complete reactions of electrolysis of water involve a cathodic hydrogen evolution reaction with 2 electron transfer and an anodic oxygen evolution reaction with 4 electron transfer.
2H++2e＝H2Cathode 2 electron transfer reaction
4OH--4e＝H2O+O2Anode 4 electron transfer reaction
Only when the energy consumption of the whole reaction is reduced, the current efficiency of water electrolysis can be really improved, and hydrogen production with low energy consumption and high efficiency is realized. From the reaction mechanism, the 4-electron transfer reaction is more complicated than the 2-electron transfer reaction, and the reaction resistance or the reaction energy barrier is also much larger. Therefore, the key to reducing the energy consumption in the hydrogen production reaction by electrolyzing water is to reduce the reaction energy barrier of the 4-electron oxygen evolution reaction.
Although some transition metal oxides or hydroxides are used as oxygen evolution electrocatalytic materials, their oxygen evolution overpotentials are still large and cannot meet the requirements of practical application. In particular, excess hydrogen ions generated by oxygen evolution can locally dissolve the transition metal oxide or hydroxide electrode, thereby affecting its electrolytic efficiency and service life.
Disclosure of Invention
Aiming at overcoming the defects of the existing water electrolysis oxygen evolution electrocatalyst, reducing the energy consumption and improving the currentEfficiency, an object of the present invention is to provide an MNi(1-x)FexF3A catalytic material, a preparation method thereof and application thereof in hydrogen production by water electrolysis.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides MNi(1-x)FexF3A method of preparing an oxygen evolution electrocatalytic material, comprising: reacting hydrogen fluoride, hydroxide, nickel salt and ferrous salt in a liquid phase reaction system at-2-99 ℃ for 0.5-2h in a protective atmosphere to obtain MNi(1-x)FexF3Oxygen evolution electrocatalytic material, wherein M represents charge balancing ions, and x is more than 0 and less than 1.
In some embodiments, the preparation method specifically comprises:
adding electrolyte into the mixed solution of hydrogen fluoride and hydroxide, and controlling the temperature of the mixed solution to be below-2 ℃;
mixing and grinding nickel salt and ferrous salt, directly adding the mixture into the mixed solution, carrying out ultrasonic oscillation, then heating to 85-99 ℃, and continuing to react for 0.5-2h to obtain MNi(1-x)FexF3An oxygen evolution electrocatalytic material.
In some embodiments, the molar ratio of the ferrous salt to the nickel salt is y: 1, wherein y is more than 0 and less than 1.
The embodiment of the invention also provides MNi prepared by the method(1-x)FexF3The oxygen evolution electrocatalytic material has a perovskite type cubic crystal system as a crystal structure and a space group of P m3mSpace group, M represents charge balancing ion, 0 < x < 1.
The embodiment of the invention also provides the MNi(1-x)FexF3The oxygen evolution electrocatalytic material is applied to hydrogen production by electrolyzing water as an oxygen evolution electrocatalyst.
Correspondingly, the embodiment of the invention also provides a method for producing hydrogen by electrolyzing water, which comprises the following steps: using the MNi(1-x)FexF3The oxygen evolution electrode is prepared from oxygen evolution electrocatalytic material and is arranged together with a nickel electrode as a hydrogen evolution electrodeAnd the alkaline aqueous solution is electrified between the oxygen evolution electrode and the hydrogen evolution electrode, so that hydrogen is produced by electrolysis.
Preferably, said oxygen evolving electrode comprises MNi(1-x)FexF3Carbon paste electrode, MNi(1-x)FexF3Nickel-based electrode, MNi(1-x)FexF3Titanium-based electrode, MNi(1-x)FexF3Stainless steel-based electrodes, and the like.
Compared with the prior art, the method adopts nickel ions as central ions, a certain amount of iron ions are doped, potassium ions or sodium ions are used as charge balance ions, fluorine ions are used as ligands, and novel MNi is generated through coordination reaction of the nickel ions and the ligands in a solvent(1-x)FexF3The oxygen evolution electro-catalysis material has excellent oxygen evolution performance and electro-catalysis stability, when the catalysis material is applied to hydrogen production by water electrolysis, the overpotential of oxygen evolution is lower than that of noble metal, the stability of oxygen evolution is high, and the catalysis material has wide application prospects in hydrogen production by water electrolysis of photovoltaic, hydrogen production by wind power and hydrogen production by hydroelectric power generation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1A and 1B are KFeF in an exemplary embodiment of the invention3、KNiF3、KNi0.75Fe0.25F3X-ray powder diffractogram of;
FIG. 2A illustrates KNi according to an exemplary embodiment of the invention0.75Fe0.25F3Transmission electron microscopy images of;
FIG. 2B illustrates KNi according to an exemplary embodiment of the invention0.75Fe0.25F3Electron diffraction pattern of (3);
FIG. 2C shows an exemplary embodiment of the present inventionKNi0.75Fe0.25F3High power transmission electron micrographs of;
FIG. 2D shows KNiF in an exemplary embodiment of the invention3Transmission electron microscopy images of;
FIG. 2E shows KNiF in an exemplary embodiment of the invention3Electron diffraction pattern of (3);
FIG. 2F shows KNiF in an exemplary embodiment of the invention3High power transmission electron micrographs of;
FIG. 2G is a KFeF in an exemplary embodiment of the invention3Transmission electron microscopy images of;
FIG. 2H is a schematic diagram of KFeF in an exemplary embodiment of the invention3Electron diffraction pattern of (3);
FIG. 2I is a schematic diagram of KFeF in an exemplary embodiment of the invention3High power transmission electron micrographs of;
FIG. 3A illustrates KNi in an exemplary embodiment of the invention0.75Fe0.25F3A full spectrum of (c);
FIG. 3B illustrates KNi in an exemplary embodiment of the invention0.75Fe0.25F3The atomic composition diagram of (1);
FIG. 3C illustrates KNi according to an exemplary embodiment of the invention0.75Fe0.25F3Fe 2p electron energy spectrum of (a);
FIG. 3D is a block diagram KNi of an exemplary embodiment of the invention0.75Fe0.25F3The electron energy spectrum of Ni 2 p;
FIG. 3E shows KNi in an exemplary embodiment of the invention0.75Fe0.25F3F1s electron energy spectrum of (a);
FIG. 3F illustrates KNi according to an exemplary embodiment of the invention0.75Fe0.25F3The K2 p electron energy spectrum of (1);
FIG. 4 shows a schematic diagram of a graphite KFeF in an exemplary embodiment of the invention3、KNiF3、Ir/IrO2、KNi0.25Fe0.75F3、 KNi0.5Fe0.5F3、KNi0.75Fe0.25F3Wherein curve a represents graphite and curve b represents KFeF3Curve c represents KNiF3The curve d represents Ir/IrO2Curve e represents KNi0.25Fe0.75F3Curve f represents KNi0.5Fe0.5F3Curve g represents KNi0.75Fe0.25F3；
FIG. 5 illustrates KNi according to an exemplary embodiment of the invention0.75Fe0.25F3I-t curve diagram of oxygen evolution stability.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps that are closely related to the solution according to the present invention are shown in the drawings, and other details that are not so relevant to the present invention are omitted.
An aspect of an embodiment of the present invention provides an MNi(1-x)FexF3A preparation method of oxygen evolution electrocatalytic material and application thereof in hydrogen production by water electrolysis. The preparation method adopts nickel ions as central ions, a certain amount of iron ions are doped, potassium ions or sodium ions are used as charge balance ions, fluorine ions are used as ligands, and the novel electro-catalytic oxygen evolution material is generated through the coordination reaction of the nickel ions and the ligands in a solvent.
In some exemplary embodiments, the MNi(1-x)FexF3The preparation method of the oxygen evolution electrocatalytic material comprises the following steps: reacting hydrogen fluoride, hydroxide, nickel salt and ferrous salt in a liquid phase reaction system at-2-99 ℃ for 0.5-2h in a protective atmosphere to obtain MNi(1-x)FexF3Catalytic material, M represents charge balancing ions, 0 < x < 1.
Further, M includes potassium ion, sodium ion, etc., but is not limited thereto.
In some exemplary embodiments, the preparation method further comprises: and introducing nitrogen into the liquid-phase reaction system to remove oxygen for more than 20min, and then carrying out the reaction.
In some exemplary embodiments, the preparation method specifically includes:
adding electrolyte into the mixed solution of hydrogen fluoride and hydroxide, introducing nitrogen to remove oxygen for more than 20min, and controlling the temperature of the mixed solution below-2 ℃;
grinding nickel salt and ferrous salt, directly adding into the mixed solution which is introduced with nitrogen and deoxidized, carrying out ultrasonic oscillation, then heating to 85-99 ℃, and continuing to react for 0.5-2h to obtain MNi(1-x)FexF3An oxygen evolution electrocatalytic material.
In other exemplary embodiments, the preparation method may further include: directly taking fluoride solution, introducing nitrogen to remove oxygen for more than 20min, and controlling the temperature of the solution at-2 ℃ to prevent metal ions from hydrolysis. To reach-2 ℃, electrolyte was added according to the principle of colligative properties.
Further, the fluoride used in the present invention includes potassium fluoride, sodium fluoride, etc., but is not limited thereto.
Further, the electrolyte includes any one or a combination of two or more of calcium chloride, potassium sulfate, sodium sulfate, potassium nitrate, sodium nitrate, potassium chloride, sodium chloride, glucose, and the like, but is not limited thereto.
Further, the time of the ultrasonic oscillation is below 10 h.
In some exemplary embodiments, the preparation method specifically includes: and mixing hydrofluoric acid and a hydroxide solution to prepare the fluoride solution, wherein the hydroxide solution comprises a potassium hydroxide solution and/or a sodium hydroxide solution and the like.
In some exemplary embodiments, the molar ratio of the ferrous salt to the nickel salt is y: 1, wherein y is more than 0 and less than 1.
In some exemplary embodiments, the nickel salt includes, but is not limited to, nickel sulfate (NiSO)4) Nickel chloride (NiCl)2) Ni (NO) nitrate3)2Etc. of any one or two or more kindsAnd (6) mixing.
In some exemplary embodiments, the ferrous salts include, but are not limited to, ferrous ammonium sulfate Fe (NH)4)2(SO4)2。
In some exemplary embodiments, the preparation method further comprises: after the reaction is finished, standing for layering, separating out solid, washing and drying to obtain MNi(1-x)FexF3An oxygen evolution electrocatalytic material.
Wherein, in some more specific exemplary embodiments, the MNi(1-x)FexF3The preparation method of the oxygen evolution electrocatalytic material specifically comprises the following steps:
(1) taking 50mL of 3mol/L KF, and controlling the temperature of the solution to be minus 2 ℃ below zero to prevent metal ions from being hydrolyzed;
(2) in order to reach-2 ℃, a certain amount of electrolyte is added according to the colligative principle, so that the temperature of the solution can be reduced to-2 ℃; 0.05mol of nickel salt is taken again to further increase KNiF3The oxygen evolution performance of (1) is that a certain amount of Fe (II) salt is added into nickel salt, the molar ratio of Fe (II) to Ni can be (0-1): 1, even the molar amount of Fe (II) can be more than that of Ni. The XRD diffraction peak is shifted according to the content of the added Fe (II);
(3) the electrolyte added according to the principle of colligative property includes, but is not limited to, calcium chloride, potassium sulfate, sodium sulfate, potassium nitrate, sodium nitrate, potassium chloride, sodium chloride, and even glucose and other substances with colligative property capable of reducing temperature;
(4) grinding nickel salt and Fe (II) salt, directly adding into the KF solution, and ultrasonically stirring for 0.0-10.0 h; and then raising the temperature to 85-99 ℃, and continuing to react to obtain a product. Standing for layering, separating out solid, washing and drying to obtain the iron-doped trifluoro nickelate oxygen evolution electrocatalyst.
Another aspect of an embodiment of the invention provides MNi prepared by the foregoing method(1-x)FexF3The oxygen evolution electrocatalytic material has a perovskite type cubic crystal system as a crystal structure and a space group of P m3mSpace group, M represents charge balancing ion, 0 < x < 1.
Further, M includes potassium ion, sodium ion, etc., but is not limited thereto.
Another aspect of an embodiment of the present invention provides the MNi(1-x)FexF3The oxygen evolution electrocatalytic material is applied to hydrogen production by electrolyzing water as an oxygen evolution electrocatalyst.
Accordingly, another aspect of the embodiments of the present invention also provides a method for producing hydrogen by electrolyzing water, which includes:
using the MNi(1-x)FexF3Preparing an oxygen evolution electrode from an oxygen evolution electrocatalytic material, wherein the oxygen evolution electrode comprises MNi(1-x)FexF3Carbon paste electrode, MNi(1-x)FexF3Nickel-based electrode, MNi(1-x)FexF3Titanium-based electrode, MNi(1-x)FexF3Stainless steel-based electrodes, etc.;
and the nickel electrode which is used as a hydrogen evolution electrode are put into alkaline aqueous solution and are connected with a photovoltaic power supply or a wind power supply, thereby realizing the hydrogen production by electrolysis.
By the technical scheme, the method adopts nickel ions as central ions, a certain amount of iron ions are doped, potassium ions or sodium ions are used as charge balance ions, fluorine ions are used as ligands, and novel MNi is generated through coordination reaction of the nickel ions and the ligands in a solvent(1-x)FexF3An oxygen evolution electrocatalytic material having excellent oxygen evolution performance and electrocatalytic stability; when the catalytic material is applied to hydrogen production by water electrolysis, the overpotential of oxygen evolution is lower than that of noble metal, and the stability of oxygen evolution is high, so that the catalytic material has wide application prospects in hydrogen production by photovoltaic water electrolysis, wind power hydrogen production and hydroelectric generation.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Comparative example 1
Potassium triflate KNiF3The preparation of (1): taking 50mL of 3mol/LKF, and controlling the temperature of the solution to be minus 2 ℃ below zero to prevent metal ions from being hydrolyzed. In order to reach-2 ℃, solid NaCl is added to saturate according to the colligative principle; taking 0.05mol of nickel salt, grinding, directly adding into the KF solution, and ultrasonically oscillating for 0.0-10.0 h; then keeping the heating rate at 1 ℃/min to 85 ℃, and continuing to react for 0.5 to 2 hours to obtain the product. Standing for layering, separating out solids, washing and drying to obtain the oxygen evolution electrocatalyst KNiF3The X-ray powder diffraction pattern is shown as curve a in FIG. 1A and is consistent with the diffraction pattern corresponding to the standard card number JCPDS 72-0112.
Comparative example 2
Similarly, potassium trifuorinated ferrite KFeF3As comparative example 2, the diffraction pattern obtained is shown in FIG. 1A as curve b.
Comparative example 3
Taking 0.15mmol of KF or NH4And F, taking 0.05mol of nickel chloride, grinding and mixing, putting the mixture into a tube furnace, heating the mixture to 350 ℃ under the protection of nitrogen airflow, keeping the temperature for 2-5 hours, collecting the obtained product, and measuring XRD diffraction data of the product, wherein the diffraction pattern of the product is similar to the curve a in the graph 1A.
Example 1
KNi0.75Fe0.25F3The preparation of (1): taking 50mL of 3mol/L hydrofluoric acid, adding 55mL of 3mol/L KOH, introducing nitrogen, and deoxidizing for 20 min; and then 0.0375mol of nickel sulfate and 0.0125mol of ammonium ferrous sulfate are mixed and ground, and then the mixture is directly added into the solution, and the temperature is kept at 95 ℃ under the ultrasonic oscillation condition, and the reaction is carried out for 1 hour to obtain the product. Standing for layering, separating out solid, washing and drying to obtain the oxygen evolution electrocatalyst KNi0.75Fe0.25F3The XRD diffractogram is shown as curve c in FIG. 1A. And KNi0.75Fe0.25F3Has a (110) plane diffraction angle of KNiF3And KFeF3Shows that Fe is doped in KNiF3Of the array of (1).
Example 2
KNi0.5Fe0.5F3The preparation of (1): taking 50mL of 3mol/L KF, introducing nitrogen to remove oxygen for 25 minutes; in order to prevent the metal ions from hydrolysis, the temperature of the solution is controlled at-2 ℃. In order to reach-2 ℃, solid NaCl is added to saturate according to the colligative principle; grinding 0.025mol of nickel chloride and 0.025mol of ammonium ferrous sulfate, directly adding into the solution, and ultrasonically oscillating for 0.0-10.0 h; then raising the temperature to 99 ℃, and continuing to react for 0.5h to obtain the product. Standing for layering, separating out solid, washing and drying to obtain the oxygen evolution electrocatalyst KNi0.5Fe0.5F3The XRD diffractogram is similar to curve c in FIG. 1A.
Example 3
KNi0.6Fe0.4F3The preparation of (1): taking 50mL of 3mol/L KF, introducing nitrogen to remove oxygen for 30 minutes; in order to prevent the metal ions from hydrolysis, the temperature of the solution is controlled at-2 ℃. In order to reach-2 ℃, solid NaCl is added to saturate according to the colligative principle; taking 0.03mol of nickel nitrate and 0.02mol of ammonium ferrous sulfate, grinding, directly adding into the solution, and ultrasonically oscillating for 0.0-10.0 h; then raising the temperature to 85 ℃, and continuing to react for 2h to obtain the product. Standing for layering, separating out solid, washing and drying to obtain the oxygen evolution electrocatalyst KNi0.6Fe0.4F3The XRD diffractogram is similar to curve c in FIG. 1A.
Hereinafter, the present inventors also compared KNiF of comparative example 13KFeF of comparative example 23KNi obtained in example 10.75Fe0.25F3The characterization and the test of each performance are carried out, and the results are as follows:
first, example 1 of the present invention is to further improve KNiF3The oxygen evolution performance of (1) is that a certain amount of Fe (II) salt is added into nickel salt, the molar ratio of Fe (II) to Ni can be (0-1): 1, even the molar amount of Fe (II) can be more than that of Ni. The XRD diffraction peak shifts depending on the content of Fe (II) added. Please refer to fig. 1A and 1B, which are KNiF3、KFeF3And KNi0.75Fe0.25F3XRD pattern of the sample. From the diffraction patterns, KNiF3The diffraction peaks of the electrocatalyst at 2 theta 22.143 deg., 31.484 deg., 38.806 deg. are respectively matched with KNiF3The (100), (110) and (111) indices of the crystal planes (JCPDS72-0112) correspond. KFeF3Diffraction peaks of the sample at 2 θ -21.724 °, 30.845 °, 38.001 ° correspond to KFeF, respectively3The (100), (110) and (111) crystal plane indices (JCPDS 20-0895). Iron doped fluorides KNi0.75Fe0.25F3The diffraction angles and interplanar spacings at 2 theta 22.067 DEG, 31.108 DEG, 38.457 DEG are all intermediate to that of the monometallic fluoride KNiF3And KFeF3It shows that the bimetal of Ni and Fe changes the unit cell size.
Secondly, the inventors also compared KNiF of comparative example 13KFeF of comparative example 23KNi obtained in example 10.75Fe0.25F3The transmission electron microscope test is carried out, and the result shows that KNi0.75Fe0.25F3，KNiF3And KFeF3The morphology, diffraction spots and interplanar spacings of (A) are shown in FIGS. 2A-2C, KNiF3The morphology, diffraction spots and interplanar spacings of (A) are shown in FIGS. 2D-2F, KFeF3The morphology, diffraction spots and interplanar spacings of (a) are shown in FIGS. 2G-2I. The results of the surface spacing were consistent with those of the powder diffraction, further showing that the resulting product was a perovskite fluoride.
Thirdly, KNi in fig. 3A-3F0.75Fe0.25F3Comparing the electron spectrum with the standard spectrum, KNi can be seen from the comparison0.75Fe0.25F3The product contains Fe, Ni, F and K elements. Wherein FIG. 3A is KNi0.75Fe0.25F3FIG. 3B is KNi0.75Fe0.25F3FIG. 3C is KNi0.75Fe0.25F3High resolution XPS of Fe 2p of (710.5 eV vs. Fe)2+2p3/2Characteristic peak of (713.6 eV) for Fe 2+2p1/2717.2eV is a satellite peak. KNi in FIG. 3D0.75Fe0.25F3High resolution electron spectrum of Ni 2pFIG. 1, in which Ni 2p is visible3/2And Ni 2p1/2Peaks were at 857.5 and 875.5eV, respectively, and two satellite peaks were at 864.0 and 881.5 eV. FIG. 3E shows KNi0.75Fe0.25F3The characteristic peak for F1s appears at 684.5 eV. FIG. 3F shows KNi0.75Fe0.25F3The characteristic peaks of medium K2 p3/2 and K2 p1/2 are at 292.7eV and 295.5eV, respectively.
Fourth, the inventors also compared KNiF of comparative example 13KFeF of comparative example 23KNi obtained in example 10.75Fe0.25F3After oxygen evolution performance tests, the inventor synthesizes a series of KNi(1-x)FexF3Electrocatalyst, 0.15g KNi was weighed(1-x)FexF3The linear scan curve of the catalyst prepared as a carbon paste electrode in 1.0mol/LKOH is shown in FIG. 4, wherein curve a represents graphite and curve b represents KFeF3Curve c represents KNiF3The curve d represents Ir/IrO2Curve e represents KNi0.25Fe0.75F3Curve f represents KNi0.5Fe0.5F3Curve g represents KNi0.75Fe0.25F3。KNiF3And the oxygen evolution overpotential of the iron-doped potassium trifluoronickelate is lower than that of the noble metal iridium. The oxygen evolution parameters for each electrode material at a current density of 10 milliamps per square centimeter are shown in table 1. KNi(1-x)FexF3(x is less than 1.0) overpotential ratio of oxygen evolution of electrocatalyst2Also has low cost, shows excellent oxygen evolution performance and can effectively reduce the energy consumption of the electrolyzed water.
TABLE 1 oxygen evolution Performance of a series of electrodes
Figure BDA0003156484190000081
Figure BDA0003156484190000091
*η30The current density is 30mV/cm2Overpotential of time
Fifth, the present inventors also synthesized KNi0.75Fe0.25F3The stability of the electrocatalyst was tested
To test KNi0.75Fe0.25F3I-t scans were performed at 0.6V (vs. sce), and fig. 5 is a 6-hour i-t plot. The initial current was 39mA/cm2The current density of the electrode at the end was approximately 43mA/cm2The current density is increased.
Example 4
Taking a series of KNi prepared by the invention(1-x)FexF30.15g of the raw materials are added into 0.45 g of graphite powder, the mixture is ground by a mortar, and a proper amount of silica gel oil is added and mixed evenly to obtain the carbon paste. Injecting the carbon paste into a 3mm diameter polytetrafluoroethylene tube, compacting the tube and forming a copper wire containing KNi(1-x)FexF3A carbon paste electrode of an oxygen evolution electrocatalyst. The carbon paste electrode is used as an oxygen evolution electrocatalyst, the nickel foam is used as a hydrogen evolution electrode, water is electrolyzed in 1.0mol/LKOH alkaline solution under the bath pressure of 1.6 volts, oxygen can be observed to be separated out at the anode, and hydrogen can be observed to be separated out at the cathode.
In summary, the invention adopts nickel ions as central ions, a certain amount of iron ions are doped, potassium ions or sodium ions are used as charge balance ions, fluorine ions are used as ligands, and novel MNi is generated through coordination reaction of the nickel ions and the ligands in a solvent(1-x)FexF3Catalytic material having excellent oxygen evolution properties and electrocatalytic stability.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. MNi(1-x)FexF3The preparation method of the oxygen evolution electrocatalytic material is characterized by comprising the following steps: reacting hydrogen fluoride, hydroxide, nickel salt and ferrous salt in a liquid phase reaction system at-2-99 ℃ for 0.5-2h in a protective atmosphere to obtain MNi(1-x)FexF3Oxygen evolution electrocatalytic material, wherein M represents a charge balancing ion, x is more than 0 and less than 1.
2. The production method according to claim 1, characterized by comprising: introducing nitrogen into the liquid phase reaction system to remove oxygen for more than 20min, and then carrying out the reaction; and/or, M comprises potassium and/or sodium ions.
3. The method according to claim 1, comprising:
adding electrolyte into the mixed solution of hydrogen fluoride and hydroxide, and controlling the temperature of the mixed solution to be below-2 ℃;
mixing and grinding nickel salt and ferrous salt, directly adding the mixture into the mixed solution, carrying out ultrasonic oscillation, then heating to 85-99 ℃, and continuing to react for 0.5-2h to obtain MNi(1-x)FexF3An oxygen evolution electrocatalytic material.
4. The method of claim 1, wherein: the electrolyte comprises any one or the combination of more than two of potassium sulfate, sodium sulfate, potassium nitrate, sodium nitrate, potassium chloride, sodium chloride, calcium chloride and glucose; and/or the time of the ultrasonic oscillation is less than 10 h.
5. The production method according to claim 3, characterized by comprising: the hydroxide comprises potassium hydroxide and/or sodium hydroxide.
6. The method of claim 1, wherein: the molar ratio of the ferrous salt to the nickel salt is y: 1, wherein y is more than 0 and less than 1; and/or the nickel salt comprises any one or the combination of more than two of nickel sulfate, nickel chloride and nickel nitrate; and/or, the ferrous salt comprises ferrous ammonium sulfate.
7. The method of claim 1, further comprising: after the reaction is finished, standing for layering, separating out solid, washing and drying to obtain MNi(1-x)FexF3An oxygen evolution electrocatalytic material.
8. MNi prepared by the method of any one of claims 1 to 7(1-x)FexF3The oxygen evolution electrocatalytic material has a perovskite type cubic crystal system as a crystal structure and a space group of Pm3mSpace group of chemical formula MNi(1-x)FexF3M represents a charge-balancing ion, 0 < x < 1, preferably M comprises potassium and/or sodium ions.
9. The MNi of claim 8(1-x)FexF3The oxygen evolution electrocatalytic material is applied to hydrogen production by electrolyzing water as an oxygen evolution electrocatalyst.
10. A method for producing hydrogen by electrolyzing water is characterized by comprising the following steps: using the MNi of claim 8(1-x)FexF3Preparing an oxygen evolution electrode by using an oxygen evolution electrocatalytic material, putting the oxygen evolution electrode and a nickel electrode serving as a hydrogen evolution electrode into an alkaline aqueous solution, and electrifying the oxygen evolution electrode and the hydrogen evolution electrode so as to realize electrolytic hydrogen production; preferably, said oxygen evolving electrode comprises MNi(1-x)FexF3Carbon paste electrode, MNi(1-x)FexF3Nickel-based electrode, MNi(1-x)FexF3Titanium-based electrodes or MNi(1-x)FexF3A stainless steel-based electrode.
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