CN113355682A - Iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material, preparation method and application thereof - Google Patents
Iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, and a preparation method and application thereof. The preparation method comprises the following steps: reacting a liquid phase reaction system mainly composed of hydrogen fluoride, hydroxide, cobalt salt, ferrous salt and water under the protection of nitrogen to obtain the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material. The invention also discloses application of the electrocatalytic material as an oxygen evolution electrocatalyst in hydrogen production by water electrolysis. The preparation process of the electrocatalytic material is simple, the raw materials are cheap and easy to obtain, the oxygen evolution overpotential of the electrocatalytic material in a 1.0mol/LKOH solution is lower than that of an iridium noble metal electrode under the same condition, the oxygen evolution electrocatalytic performance and the electrocatalytic stability are both excellent, and the electrocatalytic material is expected to be applied to photovoltaic, wind power and hydroelectric hydrogen production in a large scale.
Description
Technical Field
The invention relates to an electrocatalytic oxygen evolution material, in particular to a preparation method of an iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material taking cobalt ions as coordination center ions and fluorine ions as ligands, and application thereof in electrocatalytic oxygen evolution in hydrogen production by water electrolysis, belonging to the technical field of renewable 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
In order to overcome the defects of the existing water electrolysis oxygen evolution electrocatalyst, reduce energy consumption and improve current efficiency, the invention aims to design a novel iron-doped trifluoro cobaltate oxygen evolution electrocatalyst material, a preparation method thereof and application in the aspect of water electrolysis hydrogen production.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, which comprises the following steps: reacting a uniform water-phase mixed reaction system mainly composed of hydrogen fluoride, hydroxide, cobalt salt, ferrous salt and water at the temperature of-2-99 ℃ for 0.5-2h under the protection of nitrogen to obtain the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, wherein the chemical formula of the material is MCo(1-x)FexF3M represents a charge-balancing ion, 0 < x < 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 ℃;
and mixing and grinding cobalt salt and ferrous salt, directly adding the mixture into the mixed solution, carrying out ultrasonic oscillation, heating to 85-99 ℃, and continuing to react for 0.5-2h to obtain the iron-doped trifluoro cobaltic acid oxygen evolution electrocatalytic material.
In some embodiments, the molar ratio of the ferrous salt to the cobalt salt is y: 1, wherein y > 0, preferably 0 < y < 1.
The embodiment of the invention also provides the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material prepared by the method, the crystal structure of the material is a perovskite type cubic crystal system, and the space group is Pm3mSpace group with chemical formula of MCo(1-x)FexF3M represents a charge-balancing ion, 0 < x < 1.
The embodiment of the invention also provides application of the iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material as an oxygen evolution electro-catalyst in the field of hydrogen production by water electrolysis.
Correspondingly, the embodiment of the invention also provides a method for producing hydrogen by electrolyzing water, which comprises the following steps:
preparing the iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material into an iron-doped trifluoro cobaltate electrode, wherein the iron-doped trifluoro cobaltate electrode comprises a carbon paste electrode, a nickel-based electrode, a titanium-based electrode or a stainless steel-based electrode;
and the iron-doped trifluoro cobaltate electrode is taken as an oxygen evolution electrode, nickel is taken as a hydrogen evolution electrode, the iron-doped trifluoro cobaltate electrode is matched with an alkaline aqueous solution to form a water electrolysis hydrogen production system, and the water electrolysis hydrogen production is realized by electrifying the oxygen evolution electrode and the hydrogen evolution electrode.
Compared with the prior art, the preparation method is simple in preparation process, the raw materials are cheap and easy to obtain, cobalt ions are used 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, the novel electrocatalytic oxygen evolution material is generated through coordination reaction of the cobalt ions and the ligands in a solvent, the oxygen evolution overpotential of the electrocatalytic material in a 1.0mol/LKOH solution is lower than that of an iridium noble metal electrode under the same condition, and the electrocatalytic material has excellent oxygen evolution performance and electrocatalytic stability and is expected to be applied to photovoltaic, wind power and hydroelectric hydrogen production in a large scale.
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.
FIG. 1 is a schematic diagram of a KFeF in an exemplary embodiment of the invention3、KCoF3、KCo0.75Fe0.25F3X-ray powder diffractogram of;
FIG. 2A is KCo in an exemplary embodiment of the invention0.75Fe0.25F3Transmission electron microscopy images of;
FIG. 2B is KCo in an exemplary embodiment of the invention0.75Fe0.25F3Electron diffraction pattern of (3);
FIG. 2C is KCo in an exemplary embodiment of the invention0.75Fe0.25F3High power transmission electron micrographs of;
FIG. 2D shows KCoF in an exemplary embodiment of the invention3Transmission electron microscopy images of;
FIG. 2E shows KCoF in an exemplary embodiment of the invention3Electron diffraction pattern of (3);
FIG. 2F is a KCoF 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. 3 is a diagram of graphite, KFeF in an exemplary embodiment of the invention3、IrO2、KCoF3、KCo(1-x)FexF3Linear scanning oxygen evolution voltammogram;
FIG. 4 is a KCo in an exemplary embodiment of the invention0.75Fe0.25F3Graph of oxygen evolution i-t.
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.
One aspect of the embodiment of the invention provides a preparation method of a novel iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material and application thereof in hydrogen production by water electrolysis. The preparation method adopts cobalt 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 cobalt ions and the ligands in a solvent.
In some exemplary embodiments, the preparation method comprises: reacting a uniform water-phase mixed reaction system mainly composed of hydrogen fluoride, hydroxide, cobalt salt, ferrous salt and water at the temperature of-2-99 ℃ for 0.5-2h under the protection of nitrogen to obtain the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, wherein the chemical formula of the material is MCo(1-x)FexF3M represents a charge-balancing ion, 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 uniform water phase mixed reaction system to remove oxygen for more than 20 minutes.
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 20 minutes, and controlling the temperature of the mixed solution to be below-2 ℃;
and grinding cobalt salt and ferrous salt, directly adding the ground cobalt salt and ferrous salt 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 the iron-doped trifluoro cobaltate 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 20 minutes, and controlling the temperature of the solution to be-2 ℃ in order 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 cobalt salt is y: 1, wherein y > 0, preferably 0 < y < 1.
In some exemplary embodiments, the cobalt salt includes, but is not limited to, cobalt sulfate (CoSO)4) Cobalt chloride (CoCl)2) Cobalt nitrate Co (NO)3)2And the like, or a combination of two or more thereof.
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: and after the reaction is finished, standing for layering, separating out solids, washing and drying to obtain the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material.
In some more specific exemplary embodiments, the preparation method of the iron-doped trifluoro cobaltate 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 cobalt salt is further taken to further increase KCoF3The oxygen evolution performance of (1) is that a certain amount of Fe (II) salt is added into cobalt salt, and the molar ratio of Fe (II) to Co can be (0-1): the molar amount of 1, even fe (ii), may be greater than the molar amount of Co. The XRD diffraction peak can shift 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 cobalt 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 cobaltate oxygen evolution electrocatalyst.
In another aspect, the present invention provides an iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material prepared by the method, wherein the crystal structure of the material is perovskite type cubic crystal system, and the space group is Pm3mSpace group with chemical formula of MCo(1-x)FexF3M represents a charge-balancing ion, 0 < x < 1.
Further, M includes potassium ion, sodium ion, etc., but is not limited thereto.
The embodiment of the invention also provides application of the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material as an oxygen evolution electrocatalyst in the field of hydrogen production by electrolyzing water.
Accordingly, another aspect of the embodiments of the present invention also provides a method for producing hydrogen by electrolyzing water, which includes:
preparing the iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material into an iron-doped trifluoro cobaltate electrode, wherein the iron-doped trifluoro cobaltate electrode comprises a carbon paste electrode, a nickel-based electrode, a titanium-based electrode or a stainless steel-based electrode;
and the iron-doped trifluoro cobaltate electrode is taken as an oxygen evolution electrode, nickel is taken as a hydrogen evolution electrode, the iron-doped trifluoro cobaltate electrode is matched with an alkaline aqueous solution to form a water electrolysis hydrogen production system, and the water electrolysis hydrogen production is realized by electrifying the oxygen evolution electrode and the hydrogen evolution electrode.
By the technical scheme, the preparation process is simple, raw materials are cheap and easy to obtain, cobalt ions are used 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, a novel electro-catalysis oxygen evolution material is generated through coordination reaction of the cobalt ions and the ligands in a solvent, the oxygen evolution overpotential of the electro-catalysis material in a 1.0mol/LKOH solution is lower than that of an iridium noble metal electrode under the same condition, and the electro-catalysis material has excellent oxygen evolution performance and electro-catalysis stability and is expected to be applied to photovoltaic, wind power and hydroelectric hydrogen production in a large scale.
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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the 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 trifluoro cobaltate KCoF3The 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 cobalt 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 KCoF3The X-ray powder diffraction spectrum is shown as curve a in figure 1 and is consistent with the diffraction pattern corresponding to the standard card number JCPDS 18-1006.
Comparative example 2
Similarly, potassium trifluoroacetate KFeF3As comparative example 2, the diffraction pattern obtained is shown in FIG. 1 as curve b.
Comparative example 3
Taking 0.15mmol of KF or NH4And F, grinding and mixing 0.05mol of cobalt chloride, 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 figure 1.
Example 1
KCo0.75Fe0.25F3Preparation of: taking 50mL of 3mol/L hydrofluoric acid, adding 55mL of 3mol/L KOH, introducing nitrogen, and deoxidizing for 20 minutes; then 0.0375mol of cobalt 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, thus obtaining the product. Standing for layering, separating out solids, washing and drying to obtain the oxygen evolution electrocatalyst KCo0.75Fe0.25F3The XRD diffractogram is shown as curve c in FIG. 1.
Example 2
KCo0.5Fe0.5F3The 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; then 0.025mol of cobalt chloride and 0.025mol of ammonium ferrous sulfate are taken, ground and directly added into the solution, and ultrasonically oscillated for 0.0 to 10.0 hours; then raising the temperature to 99 ℃, and continuing to react for 0.5h to obtain the product. Standing for layering, separating out solids, washing and drying to obtain the oxygen evolution electrocatalyst KCo0.5Fe0.5F3The XRD diffractogram is similar to curve c in FIG. 1.
Example 3
KCo0.6Fe0.4F3The 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 cobalt 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 solids, washing and drying to obtain the oxygen evolution electrocatalyst KCo0.6Fe0.4F3The XRD diffractogram is similar to curve c in FIG. 1.
Hereinafter, the present inventors also compared KCoF of comparative example 13KFeF of comparative example 23And KCo obtained in example 10.75Fe0.25F3The characterization and the test of each performance are carried out, and the results are as follows:
first, the embodiment 1 of the present invention is to proceedOne-step increase of KCoF3The oxygen evolution performance of (1) is that a certain amount of Fe (II) salt is added into cobalt salt, and the molar ratio of Fe (II) to Co can be (0-1): the molar amount of 1, even fe (ii), may be greater than the molar amount of Co. The XRD diffraction peak shifts depending on the content of Fe (II) added. Please refer to fig. 1, which shows KCoF3、KFeF3And KCo0.75Fe0.25F3XRD pattern of the sample. From the diffraction pattern, KCoF3The diffraction peaks of the electrocatalyst at 2 theta 21.842 deg., 31.064 deg., 38.285 deg. correspond to KCoF3Index of (100), (110) and (111) crystal planes of (JCPDS18-1006), 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 fluoride KCo0.75Fe0.25F3The diffraction angle and interplanar spacing at 2 theta of 21.722 deg., 30.864 deg., 38.025 deg. are both between the single metal fluoride KCoF3And KFeF3Indicating that the bimetal of Co, Fe changes the unit cell size.
Secondly, the inventors also compared KCoF of comparative example 13KFeF of comparative example 23And KCo obtained in example 10.75Fe0.25F3The results of transmission electron microscope tests show that KCo0.75Fe0.25F3，KCoF3And KFeF3The morphology, diffraction spots and interplanar spacings of (A) are shown in FIGS. 2A-2C, KCoF3The 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, the inventors also compared KCoF of comparative example 13KFeF of comparative example 23And KCo obtained in example 10.75Fe0.25F3The inventor synthesizes a series of KCo by performing oxygen evolution performance tests(1-x)FexF3Electrocatalyst, 0.15g KCo is weighed(1-x)FexF3The catalyst is made into a carbon paste electrode in 1.0mol/LKOHThe linear scanning curve is shown in FIG. 3, in which curve a represents graphite, curve b represents KFeF, and curve c represents IrO2Curve d represents KCoF and curve e represents KCo0.25Fe0.75F3Curve f represents KCo0.5Fe0.5F3Curve g represents KCo0.75Fe0.25F3。KCoF3And the oxygen evolution overpotential of the iron-doped potassium trifluoroacetate 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. KCo(1-x)FexF3(x<1.0) overpotential ratio of oxygen evolution of electrocatalyst noble metal Ir or IrO2Also 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
Fourth, the inventors also performed on the synthesized KCo0.75Fe0.25F3The stability of the electrocatalyst was tested
For testing KCo0.75Fe0.25F3I-t scans were performed at 0.6V (vs. sce), and fig. 4 is a plot of scan time over 6 hours. The initial current was 39mA/cm2The current density at the end of the electrode was approximately 44mA/cm2The current density is increased.
Example 4
Taking a series of KCo 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 carbon paste into 3mm diameter polytetrafluoroethylene tube, compacting, and forming KCo-containing copper wire(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, and oxygen can be observed at the anodeEvolution of hydrogen gas was observed at the cathode.
In conclusion, the novel electrocatalytic oxygen evolution material is generated by adopting cobalt ions as central ions, doping a certain amount of iron ions, adopting potassium ions or sodium ions as charge balance ions and adopting fluorine ions as ligands through the coordination reaction of the cobalt ions and the ligands in a solvent, and has excellent oxygen evolution performance 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. A preparation method of an iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material is characterized by comprising the following steps: reacting a uniform water-phase mixed reaction system mainly composed of hydrogen fluoride, hydroxide, cobalt salt, ferrous salt and water at the temperature of-2-99 ℃ for 0.5-2h under the protection of nitrogen to obtain the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, wherein the chemical formula of the material is MCo(1-x)FexF3M represents a charge-balancing ion, 0 < x < 1.
2. The production method according to claim 1, characterized by comprising: introducing nitrogen into the uniform water phase mixed reaction system to remove oxygen for more than 20 minutes; 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 ℃;
and mixing and grinding cobalt salt and ferrous salt, directly adding the mixture into the mixed solution, carrying out ultrasonic oscillation, heating to 85-99 ℃, and continuing to react for 0.5-2h to obtain the iron-doped trifluoro cobaltate 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 cobalt salt is y: 1, wherein y > 0, preferably 0 < y < 1; and/or the cobalt salt comprises any one or the combination of more than two of cobalt sulfate, cobalt chloride and cobalt nitrate; and/or, the ferrous salt comprises ferrous ammonium sulfate.
7. The method of claim 1, further comprising: and after the reaction is finished, standing for layering, separating out solids, washing and drying to obtain the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material.
8. The Fe-doped trifluoro cobaltate oxygen evolution electrocatalytic material prepared by the method of any one of claims 1 to 7, the crystal structure of which is perovskite type cubic crystal system, and the space group is Pm3mSpace group with chemical formula of MCo(1-x)FexF3M represents a charge-balancing ion, 0 < x < 1, preferably M comprises potassium and/or sodium ions.
9. The use of the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material as described in claim 8 as an oxygen evolution electrocatalyst in the field of hydrogen production from electrolysis of water.
10. A method for producing hydrogen by electrolyzing water is characterized by comprising the following steps:
preparing the iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material as described in claim 8 into an iron-doped trifluoro cobaltate electrode, wherein the iron-doped trifluoro cobaltate electrode comprises a carbon paste electrode, a nickel-based electrode, a titanium-based electrode or a stainless steel-based electrode;
and the iron-doped trifluoro cobaltate electrode is taken as an oxygen evolution electrode, nickel is taken as a hydrogen evolution electrode, the iron-doped trifluoro cobaltate electrode is matched with an alkaline aqueous solution to form a water electrolysis hydrogen production system, and the water electrolysis hydrogen production is realized by electrifying the oxygen evolution electrode and the hydrogen evolution electrode.
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