CN111036247B - Cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material and preparation method and application thereof - Google Patents
Cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001301 oxygen Substances 0.000 title claims abstract description 32
- KBYVKGITJVXLET-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Co+2].[O-2].[Fe+2].[Co+2] Chemical compound P(=O)([O-])([O-])[O-].[Co+2].[O-2].[Fe+2].[Co+2] KBYVKGITJVXLET-UHFFFAOYSA-K 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims abstract description 28
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims abstract description 28
- 239000006260 foam Substances 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- -1 cobalt ferricyanide Chemical compound 0.000 claims abstract description 25
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001308 synthesis method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HNKYLCMYAWLKMN-UHFFFAOYSA-N [Co](C#N)C#N.[Fe] Chemical compound [Co](C#N)C#N.[Fe] HNKYLCMYAWLKMN-UHFFFAOYSA-N 0.000 description 3
- 238000003491 array Methods 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YGLTVPURLVCOEV-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Co+3].O.O.O.O Chemical compound P(=O)([O-])([O-])[O-].[Co+3].O.O.O.O YGLTVPURLVCOEV-UHFFFAOYSA-K 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- B01J35/50—
-
- 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
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- 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
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material, a preparation method and application thereof, wherein the composite material is a composite material of cobalt-iron oxide nano squares and a cobalt phosphate nano array grown in situ on foam nickel, the expression of the composite material is CoFeO-CoPi@NF, and the composite material belongs to the technical field of new energy nano material synthesis. And taking the cobalt phosphate nano array growing on the foam nickel as a template and a cobalt source, forming cobalt ferricyanide nano squares on the cobalt phosphate nano array by introducing ferricyanide, and calcining at a high temperature in an air atmosphere to obtain the composite material of cobalt-iron oxide and cobalt phosphate. The synthesis method of the invention simply and effectively compounds the cobalt phosphate and the cobalt iron oxide, and enriches the synthesis method of the compound of the polymetallic oxide and the oxysalt. The material has excellent electrocatalytic oxygen evolution performance, and obvious morphology transformation after the electrocatalytic oxygen evolution, and is suitable for the field of new energy development.
Description
Technical Field
The invention belongs to the technical field of new energy nano material synthesis and electrochemistry, and in particular relates to synthesis and application of an efficient cobalt-iron oxide-cobalt phosphate composite material electrocatalytic oxygen evolution composite material.
Background
Energy crisis and environmental pollution are two major problems facing the current society. Hydrogen energy is an ideal substitute for fossil energy due to high energy density and no pollution. The water electrolysis hydrogen production technology is an ideal hydrogen production technology, but the expensive catalyst is the biggest obstacle restricting the development of the water electrolysis technology. The oxygen evolution reaction is a fast step of hydrogen production by water electrolysis due to the complex reaction process and slow kinetics. However, the existing electrocatalytic oxygen-evolving catalyst has the problems of high cost, low efficiency and the like, so that the development of the low-cost and high-efficiency electrocatalytic oxygen-evolving catalyst is a key for developing the water electrolysis hydrogen production technology.
Since phosphate is a good proton carrier and can effectively promote proton transport, transition metal phosphates are a good catalyst for electrocatalytic oxygen evolution. Meanwhile, the transition metal oxide also shows higher activity in electrocatalytic oxygen evolution due to good hydrophilicity. However, single materials still have certain limitations, for example, higher resistance, both phosphate and oxide, which also severely hampers further enhancement of electrocatalytic oxygen evolution activity. Therefore, through reasonable design, the two are compounded, the electronic structure of the catalyst is optimized, the electrocatalytic reaction path of the catalyst can be further optimized, and the activity of the catalytic reaction of the catalyst is further improved.
Disclosure of Invention
The invention provides a cobalt iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material, a synthesis method and application thereof, and solves the problem of effective recombination of transition metal oxide and transition metal phosphate.
Aiming at the problems that the existing transition metal oxide and transition metal phosphate are not thoroughly compounded, the morphology is difficult to control, the impurity concentration is high and the like, the invention provides the cobalt iron oxide and cobalt phosphate compounded nano material which is obtained by taking cobalt iron cyanide nano squares growing in a cobalt phosphate nano array as a template and calcining the cobalt iron cyanide nano squares in air at high temperature.
In order to solve the problems, the invention is realized by adopting the following technical scheme:
in one aspect, the invention provides a cobalt iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material, which is a nanocomposite formed by cobalt iron oxide nano squares and cobalt phosphate nano arrays, and has the expression of CoFeO-CoPi@NF.
On the other hand, the invention also provides a preparation method of the cobalt iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material, which comprises the following steps:
(1) Synthesizing a cobalt phosphate nano array precursor;
(2) Synthesizing a cobalt ferricyanide-cobalt phosphate precursor;
(3) High temperature calcination of cobalt ferricyanide-cobalt phosphate.
Further, the specific preparation method of the cobalt iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material comprises the following steps:
(1) The synthesis method of the cobalt phosphate nano array precursor comprises the following steps: the foam nickel (2 cm x 3 cm) is treated by ultrasonic treatment for 20 to 40 minutes in advance by using a mixed solution of acetone and hydrochloric acid so as to remove grease and an oxide layer on the surface. Cobalt nitrate hexahydrate and ammonium dihydrogen phosphate are dissolved in water and stirred for 20 to 40 minutes to prepare solution A. Pouring the solution A into a reaction kettle, putting the foam nickel which is treated in advance into the solution A, putting into a baking oven, reacting for 8-16 hours at 180 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the foam nickel, flushing the foam nickel with deionized water and absolute ethyl alcohol for 3-4 times, and baking the foam nickel in a vacuum baking oven at 50-70 ℃ for 10-15 hours to obtain a cobalt phosphate precursor which is marked as CoPi@NF.
(2) The synthesis method of the cobalt ferricyanide-cobalt phosphate precursor comprises the following steps: dissolving potassium ferricyanide in deionized water, and stirring for 20-40 minutes to obtain solution B. Transferring the solution B into a reaction kettle, then putting the prepared CoPi@NF into the solution B, putting the solution B into an oven, reacting for 10 to 15 hours at the temperature of 120 ℃, cooling the reaction kettle to the room temperature after the reaction is finished, taking out foam nickel, flushing the foam nickel with deionized water and absolute ethyl alcohol for 3 to 4 times, and baking the foam nickel in a vacuum oven at the temperature of 50 to 70 ℃ for 10 to 15 hours to obtain a cobalt ferricyanide-cobalt phosphate precursor which is denoted as PBA-CoPi@NF.
(3) The high temperature calcination method of cobalt ferricyanide-cobalt phosphate is as follows: and (3) placing the prepared PBA-CoPi@NF precursor into a porcelain boat, and heating to 350-450 ℃ at a heating rate of 2.5 ℃ per minute under an air atmosphere, and keeping for 1-3 hours to obtain the cobalt iron oxide-cobalt phosphate composite material, namely CoFeO-CoPi@NF.
The CoPi@NF precursor prepared in the step (1) is a nano array with the width of about 2 mu m; the PBA-CoPi@NF obtained in the step (2) is that cobalt ferricyanide nano squares with the side length of about 100 nanometers are grown on a cobalt phosphate nano array; coFeO-CoPi@NF obtained in the step (3) is similar to PBA-CoPi@NF, and cobalt iron oxide nano squares are grown on the cobalt phosphate nano array.
The cobalt-iron oxide-cobalt phosphate oxygen evolution composite material is applied to the aspect of electrocatalytic oxygen evolution.
The CoFeO-CoPi@NF of the cobalt-iron oxide-cobalt phosphate composite material is a nanocomposite formed by compositing cobalt-iron oxide nano squares and a cobalt phosphate nano array grown in situ on foam nickel. Through the effective recombination of cobalt phosphate and cobalt iron oxide, the electronic structure is optimized, the adsorption and the cracking of water on the surface of the cobalt iron oxide are effectively promoted, and the porous structure of cobalt iron cyanide is reserved, so that more active sites are exposed, and the cobalt iron oxide has excellent electrocatalytic oxygen evolution activity. In addition, the morphology of cobalt iron oxide and cobalt phosphate is obviously changed after the electrocatalytic oxygen evolution reaction, and the cobalt iron oxide and cobalt phosphate are changed from nano square blocks to nano sheets.
The method has the characteristics of simple process, strong controllability, good repeatability and the like, takes the cobalt phosphate nano-array and the cobalt ferricyanide as templates, provides a regular shape and porous framework structure, and obtains the composite material formed by the cobalt-iron oxide nano-square and the cobalt phosphate nano-array after calcining in the air under the high temperature condition. Can be expanded to the preparation of other transition metal phosphate and transition metal oxide composite materials, and can be used as an electrocatalytic oxygen evolution catalyst with controllable composition and morphology and high performance.
The CoFeO-CoPi@NF composite material with the specific morphology can be used in the field of electrocatalytic oxygen evolution.
The invention can be used for novel electrocatalytic oxygen evolution catalyst, and is a novel electrochemical catalytic material meeting the new energy requirement.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention uses the cobalt phosphate nano array and the cobalt ferricyanide nano square as templates, obtains the cobalt-iron oxide-cobalt phosphate composite nano catalyst through simple high-temperature calcination, and enriches the preparation and synthesis technology of transition metal oxide and phosphate by applying the cobalt oxide-cobalt phosphate composite nano catalyst to the field of electrocatalysis, thereby widening the practical application value of the cobalt oxide-cobalt phosphate composite nano catalyst.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1-1 is an X-ray powder diffraction pattern of the CoPi@NF precursor prepared in example 1;
FIGS. 1-2 are scanning electron microscope images of the CoPi@NF precursor prepared in example 1;
FIGS. 1-3 are X-ray powder diffraction patterns of the PBA-CoPi@NF precursor prepared in example 1;
FIGS. 1-4 are scanning electron microscope and transmission electron microscope images of the PBA-CoPi@NF precursor prepared in example 1;
FIGS. 1-5 are X-ray powder diffraction patterns of CoFeO-CoPi@NF composite materials prepared in example 1;
FIGS. 1-6 are scanning electron microscope and transmission electron microscope images of CoFeO-CoPi@NF composite material prepared in example 1;
FIGS. 1-7 are X-ray photoelectron spectra of CoFeO-CoPi@NF composite materials prepared in example 1;
FIG. 2-1 is a graph of electrocatalytic oxygen evolution data for CoFeO-CoPi@NF composite material prepared in example 1;
FIG. 2-2 is a scanning electron microscope and transmission electron microscope image of the CoFe-CoPi@NF composite material prepared in example 1 after electrocatalytic oxygen evolution.
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description.
Example 1:
(1) The synthesis method of the cobalt phosphate nano array precursor comprises the following steps: nickel foam (2 cm x 3 cm) was previously sonicated with a mixed solution of acetone and hydrochloric acid for 30 minutes to remove grease and oxide layers from the surface. Solution a was prepared by dissolving 0.44 g of cobalt nitrate hexahydrate and 0.115 g of ammonium dihydrogen phosphate in 30 ml of deionized water and stirring for 30 minutes. Pouring the solution A into a reaction kettle, putting the foam nickel which is treated in advance into the solution A, putting the solution A into an oven, reacting for 12 hours at 180 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the foam nickel, flushing the foam nickel with deionized water and absolute ethyl alcohol for 3-4 times, and baking the foam nickel in a vacuum oven at 60 ℃ for 12 hours to obtain a cobalt phosphate precursor which is marked as CoPi@NF.
(2) The synthesis method of the cobalt ferricyanide-cobalt phosphate precursor comprises the following steps: 0.33 g of potassium ferricyanide is dissolved in 30 ml of deionized water and stirred for 30 minutes to obtain solution B. Transferring the solution B into a reaction kettle, then putting the prepared CoPi@NF into the solution B, putting the solution B into an oven, reacting for 12 hours at 120 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out foam nickel, flushing the foam nickel with deionized water and absolute ethyl alcohol for 3-4 times, and baking the foam nickel in a vacuum oven at 60 ℃ for 12 hours to obtain a cobalt ferricyanide-cobalt phosphate precursor which is denoted as PBA-CoPi@NF.
(3) The high temperature calcination method of cobalt ferricyanide-cobalt phosphate is as follows: and (3) placing the prepared PBA-CoPi@NF precursor in a porcelain boat, heating to 350 ℃ at a heating rate of 2.5 ℃ per minute under an air atmosphere, and keeping for 2 hours to obtain the cobalt iron oxide-cobalt phosphate composite material, namely CoFeO-CoPi@NF.
FIG. 1-1 is an X-ray powder diffraction pattern of the CoPi@NF precursor prepared in example 1, which was compared with standard cards to confirm that the resultant product was cobalt phosphate tetrahydrate;
FIGS. 1-2 are scanning electron micrographs of the CoPi@NF precursor prepared in example 1, and it can be seen that the resulting product is a nanoarray about 2 microns wide;
FIGS. 1-3 are X-ray powder diffraction patterns of the PBA-CoPi@NF precursor prepared in example 1, which, by comparison with standard cards, confirm that the resulting product is a composite of cobalt phosphate tetrahydrate and cobalt ferricyanide;
FIGS. 1-4 (a) and (b) are scanning electron microscope and transmission electron microscope pictures, respectively, of the PBA-CoPi@NF precursor prepared in example 1, and it can be seen that nanocubes with morphology of about 100 nanometers on a side length are grown on a nanoarray;
FIGS. 1-5 are X-ray powder diffraction patterns of CoFeO-CoPi@NF composites prepared in example 1. By comparison with standard cards, the obtained product can be confirmed to be a composite material consisting of amorphous cobalt phosphate and cobalt iron oxide;
FIGS. 1-6 (a) and (b) are respectively a scanning electron microscope image and a transmission electron microscope image of the CoFeO-CoPi@NF composite material prepared in example 1, and can be seen to be a composite structure composed of nano square blocks and nano arrays, wherein the appearance of the nano square blocks and the nano arrays is similar to that of PBA-CoPi@NF;
FIGS. 1-7 are X-ray photoelectron spectra of the CoFeO-CoPi@NF composite material prepared in example 1, and confirm the existence of Co, fe, P and O, and confirm the rich valence state composition of cobalt and iron elements in the composite material.
Electrocatalytic oxygen evolution performance of cobalt-iron oxide-cobalt phosphate composite material
The CoFeO-copi@nf composite material obtained in example 1 was cut to a size of 1cm x 2cm, and used as a working electrode. In a standard three-electrode system, the electrocatalytic oxygen evolution performance was tested in 1M KOH aqueous solution with carbon rod and mercury/mercury oxide as counter and reference electrodes, respectively.
FIG. 2-1 is a graph of electrocatalytic oxygen evolution for CoFeO-CoPi@NF composites prepared in example 1. From the linear sweep voltammogram of FIG. 2-1 (a), it can be seen that the current density is 100mA cm -2 Its overpotential is only 235mV and its Tafil slope is only 56mV dec -1 The composite material as a whole exhibits very excellent electrocatalytic oxygen evolution activity. At a current density of 100mA cm -2 The faraday efficiency at the time of electrocatalytic oxygen evolution was tested under the conditions of (a) and found to be greater than 95%. As can be seen from the stability test in FIG. 2-1 (d), the stability test was performed under constant pressure conditionsThe current density did not decay significantly after 30 hours of testing, indicating superior cycling stability.
FIG. 2-2 is a graph showing the morphology of the CoFeO-CoPi@NF composite material prepared in example 1 after an electrocatalytic oxygen evolution test. By comparison, it was found that the nano-cubes on the surface were transformed into nano-platelet structures after electrocatalytic oxygen evolution.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (4)
1. The preparation method of the cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution material is characterized by comprising the following steps of:
(1) Preparing a cobalt phosphate nano array precursor;
(2) Preparing a cobalt ferricyanide-cobalt phosphate precursor;
(3) High temperature calcination of cobalt ferricyanide-cobalt phosphate.
2. The preparation method according to claim 1, characterized in that the preparation steps are as follows:
(1) The synthesis method of the cobalt phosphate nano array precursor comprises the following steps: ultrasonic treatment is carried out on the foam nickel in advance by using a mixed solution of acetone and hydrochloric acid for 20-40 minutes so as to remove grease and an oxide layer on the surface; dissolving cobalt nitrate hexahydrate and ammonium dihydrogen phosphate in water, and stirring for 20-40 minutes to prepare a solution A; pouring the solution A into a reaction kettle, putting the foam nickel which is treated in advance into the solution A, putting the solution A into an oven, reacting for 8-16 hours at the temperature of 180 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the foam nickel, flushing the foam nickel with deionized water and absolute ethyl alcohol for 3-4 times, and baking the foam nickel in a vacuum oven at the temperature of 50-70 ℃ for 10-15 hours to obtain a cobalt phosphate precursor which is marked as CoPi@NF;
(2) The synthesis method of the cobalt ferricyanide-cobalt phosphate precursor comprises the following steps: dissolving potassium ferricyanide in deionized water, and stirring for 20-40 minutes to obtain a solution B; transferring the solution B into a reaction kettle, then putting the prepared CoPi@NF into the solution B, putting the solution B into an oven, reacting for 10-15 hours at 120 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out foam nickel, flushing the foam nickel with deionized water and absolute ethyl alcohol for 3-4 times, and baking the foam nickel in a vacuum oven at 50-70 ℃ for 10-15 hours to obtain a cobalt ferricyanide-cobalt phosphate precursor which is denoted as PBA-CoPi@NF;
(3) The high temperature calcination method of cobalt ferricyanide-cobalt phosphate is as follows: and (3) placing the prepared PBA-CoPi@NF precursor in a porcelain boat, and heating to 350-450 ℃ at a heating rate of 2.5 ℃ per minute under an air atmosphere, and keeping for 1-3 hours to obtain the cobalt iron oxide-cobalt phosphate composite material, namely CoFeO-CoPi@NF.
3. The preparation method according to claim 2, characterized in that: the CoPi@NF precursor obtained in the step (1) is a nano array with the width of about 2 micrometers; the PBA-CoPi@NF obtained in the step (2) is that cobalt ferricyanide nano squares with the side length of about 100 nanometers are grown on a cobalt phosphate nano array; coFeO-CoPi@NF obtained in the step (3) is similar to PBA-CoPi@NF, and cobalt iron oxide nano squares are grown on the cobalt phosphate nano array.
4. Use of a composite material prepared by the method for preparing a cobalt iron oxide-cobalt phosphate composite material according to claim 1 for electrocatalytic oxygen evolution, wherein the morphology of the composite material is significantly changed after electrocatalytic oxygen evolution.
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