CN116078385B - Porous nano flake NiCo1.48Fe0.52O4Electrocatalyst, preparation and use thereof - Google Patents
Porous nano flake NiCo1.48Fe0.52O4Electrocatalyst, preparation and use thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002060 nanoflake Substances 0.000 title description 6
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 85
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 52
- 239000002135 nanosheet Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000006260 foam Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 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 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 238000012360 testing method Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 239000012085 test solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000001566 impedance spectroscopy Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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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
- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst, a preparation method and an application thereof. The electrocatalyst enables porous nano sheet NiCo 1.48Fe0.52O4 to be loaded on foam nickel through a hydrothermal method and a thermal annealing method; wherein the thickness of the electrocatalyst is 20-60 nm, the diameter is 400-800 nm, and holes with the aperture of 10-60 nm are distributed on the surface. The OER performance of the electrocatalyst is optimal by adjusting the feeding proportion of the Co source and the Fe source in the raw materials, the thermal annealing is further carried out in a reducing atmosphere, the surface pore forming of the nano sheet NiCo 1.48Fe0.52O4 is realized, a large number of pore structures with different sizes are formed, the pore structures are favorable for exposing active sites in the electrocatalyst, meanwhile, charge transmission between the electrocatalyst and a solution is favorable for accelerating the chemical reaction kinetics rate through further electrochemical activation treatment, and the electrocatalyst is subjected to electrocatalytic oxidation water oxygen evolution in a three-electrode electrochemical system under the combined action of the structures, so that the efficient oxygen evolution capability is shown, and the electrocatalyst is hopefully widely applied to the field of electrocatalyst.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst, a preparation method and an application thereof.
Background
In order to achieve the aim of dual carbon, there is an urgent need to reduce the dependence on fossil raw materials and develop a clean energy source. The hydrogen energy is used as a clean energy source, has high heat value and no pollution, and is considered as one of the most promising energy sources. But at present, more than 96% of hydrogen is sourced from coal-based hydrogen production and industrial byproduct hydrogen production, and only less than 4% of hydrogen is sourced from electrochemical decomposition water. The raw material for hydrogen production by electrochemical water decomposition is water, and the product is pollution-free and meets the requirement of sustainable development. The complete water splitting reaction consists of two half reactions, the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER). However, OER kinetics are slow and overpotential is high, which becomes the bottleneck of the water-splitting reaction.
The OER electrocatalytic performance of the current commercial electrode RuO 2/IrO2 is excellent, but its scarcity, high cost and low stability prevent its large-scale application. Therefore, development of an efficient and low-cost electrocatalyst is urgently required to improve the catalytic activity and stability of the electrocatalyst, and realize large-scale commercialization. In recent years, transition metal oxides such as Fe, co, ni and the like have better electrocatalytic activity, and as a transition metal oxide catalyst with adjustable coordination environment, the transition metal oxide catalyst has become an electrocatalyst with wide application prospect. However, most of these exposed metal oxide active sites are limited, and are trapped in closed spaces or difficult-to-access areas that do not typically participate in the electrocatalytic reaction, resulting in unsatisfactory electrocatalytic performance, and thus, there is still a gap in their electrocatalytic performance compared to commercial electrodes.
To address this problem, optimizing the electrocatalyst feed ratio, structuring pores on the electrocatalyst surface, and electrochemical treatments are effective approaches to improve the electrocatalyst performance of the materials. A porous structure can expose the active site in the electrocatalyst to the maximum extent, and further electrochemical treatment can accelerate the charge transfer rate between the electrocatalyst and the solution and the chemical reaction kinetics, so that the electrocatalytic activity of the electrocatalyst is obviously improved.
Therefore, the invention provides a porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst capable of exposing the internal active site of a material and improving the structural stability of the material, a preparation method thereof and application thereof in OER.
Disclosure of Invention
In view of the foregoing problems of the prior art, a first object of the present invention is to provide a porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst. The porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst grows on a foam nickel substrate, has the advantages of multiple active sites, strong catalytic capability, good structural stability and the like, and is an electrocatalyst with excellent performance.
It is a second object of the present invention to provide a process for preparing an electrocatalyst as described above. The preparation method is simple, low in cost and good in repeatability.
A third object of the present invention is to provide the use of an electrocatalyst as described above in an electrochemical oxygen evolution reaction. The electrocatalyst shows excellent catalytic performance in OER, and is expected to be widely applied to the field of electrocatalysis.
In order to achieve the first object, the present invention adopts the technical scheme that:
The invention discloses a porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst, which enables porous nano sheet NiCo 1.48Fe0.52O4 to be loaded on foam nickel by a hydrothermal method and a thermal annealing method;
wherein the thickness of the electrocatalyst is 20-60 nm, the diameter is 400-800 nm, and holes with the aperture of 10-60 nm are distributed on the surface.
In the technical scheme of the invention, the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst is prepared by firstly preparing nano sheet NiCo 1.48Fe0.52O4 loaded on a foam nickel substrate by adopting a hydrothermal method and a thermal annealing method, and then pore-forming on the surface of the nano sheet by the thermal annealing process under a reducing atmosphere to obtain the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst, wherein pores with different sizes are distributed on the surface of the electrocatalyst.
Compared with the prior art, when the Co source and the Fe source are added in a molar ratio of 3:1, the porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst grows on the foam nickel substrate after Ar/H 2 thermal annealing, has a rough porous morphology, is favorable for charge transmission between the electrocatalyst and a solution, has the advantages of multiple active sites, good conductivity, high electrochemical activity and the like, and can effectively improve the catalytic performance of the electrocatalyst.
In order to achieve the second object, the present invention adopts the technical scheme that:
The invention discloses a method for preparing a porous nano platy NiCo 1.48Fe0.52O4 electrocatalyst, which comprises the following steps:
S1, sequentially dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate, ammonium fluoride and urea in a molar ratio of 1:1.5:0.5:6.5:1.5 in a reaction kettle filled with deionized water, adding cleaned foam nickel, keeping the temperature in an oven for a period of time to obtain a precursor, then placing the precursor in a tubular furnace, heating and reacting for a certain time in an inert atmosphere, and naturally cooling to room temperature after the reaction is finished to obtain nano-sheet NiCo 1.48Fe0.52O4 loaded on the foam nickel;
S2, placing the nano sheet-shaped NiCo 1.48Fe0.52O4 obtained in the S1 into a tube furnace, continuously introducing reducing gas for roasting, preserving heat for a period of time, and cooling to room temperature to obtain the porous nano sheet-shaped NiCo 1.48Fe0.52O4 electrocatalyst.
In the step S1, the heat preservation temperature of the oven is 110-150 ℃ and the heat preservation time is 5-12 h.
Further, in the steps S1 and S2, the temperature rising rate in the tube furnace is 6-15 ℃/min, the reaction temperature is 280-400 ℃, and the heat preservation time is 1.5-4 h.
Further, the reducing gas is a mixed gas of hydrogen and one selected from nitrogen, helium and argon.
Further, the flow rate of the inert gas in the step S1 is 30-100 sccm.
Further, in the step S2, the flow rate of the mixed gas is 80-200 sccm; preferably, the volume ratio of the inert gas to the reducing gas in the mixed gas is 85:15.
In order to achieve the third object, the present invention adopts the technical scheme that:
The invention discloses an application of an electrocatalyst prepared by the method or the electrocatalyst in the electrochemical oxygen evolution reaction.
In a three-electrode system, a porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst is used as a working electrode, a graphite rod is used as a counter electrode, hg/HgO is used as a reference electrode, and the electrocatalytic oxidation water oxygen evolution reaction is carried out.
Further, before the electrochemical oxygen evolution reaction, the electrocatalyst is subjected to an activation treatment in advance, and the specific steps are as follows:
The porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst is used as a working electrode, a graphite rod is used as a counter electrode, hg/HgO is used as a reference electrode, and cyclic voltammetry is used for carrying out activation treatment within the range of 0-0.7V (vs Hg/HgO).
Further, the activation treatment solution is 1M KOH or 1M NaOH.
Further, the scanning rate of the activation treatment is 10 to 100mV/s.
Further, the number of scanning turns of the activation treatment is 150 to 300.
The invention has the beneficial effects that:
The invention provides a porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst. According to the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst, the OER performance of the electrocatalyst is optimal by preparing the feeding ratio of a Co source and an Fe source in raw materials, thermal annealing is further carried out in a reducing atmosphere, holes are formed on the surface of nano sheet NiCo 1.48Fe0.52O4, a large number of pore structures with different sizes are formed, the pore structures are favorable for exposing active sites in the electrocatalyst, when the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst is used, charge transmission between the electrocatalyst and a solution is facilitated through further electrochemical activation treatment, the chemical reaction kinetic rate is accelerated, and under the combined action of the structures, the electrocatalyst performs electrocatalytic oxidation water oxygen evolution in a three-electrode electrochemical system, so that the high-efficiency oxygen evolution capability is shown, and the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst is expected to be widely applied to the field of electrocatalyst.
Drawings
Fig. 1 shows SEM images of samples prepared in example 1 of the present invention.
Fig. 2 shows an SEM image of porous nanoplatelets NiCo 1.48Fe0.52O4 in example 2 of the present invention.
Fig. 3 shows an SEM image of porous nanoplatelets NiCo 1.48Fe0.52O4 after electrochemical activation treatment according to example 3 of the present invention.
Fig. 4 shows the linear sweep voltammetry test curves for the samples prepared in example 1, comparative example 2, comparative example 3 and comparative example 4 according to the present invention.
Fig. 5 shows HRTEM images of samples prepared in example 1 of the present invention.
Fig. 6 shows HRTEM images of samples prepared in example 3 of the present invention.
Fig. 7 shows EDS patterns of samples prepared in example 3 of the present invention.
FIG. 8 shows XPS patterns of samples prepared in example 1 of the present invention.
Fig. 9 shows XPS profile of a sample prepared in example 3 of the present invention.
Fig. 10 shows the linear sweep voltammetry test curves for samples prepared in examples 1 and 3 of the present invention.
FIG. 11 shows the linear sweep voltammetry test curves for samples prepared in inventive example 3, comparative example 5, comparative example 6, comparative example 7 and comparative example 8.
Fig. 12 shows electrochemical impedance spectrum test curves of samples prepared in examples 1 and 3 of the present invention.
Fig. 13 shows tafel slope patterns of samples prepared in examples 1 and 3 of the present invention.
Figure 14 shows the stability test of the sample prepared in example 3 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. It should be understood that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are commercially available from the public unless otherwise specified, and the units M are mol/L unless otherwise specified.
Example 1
7.7mg Ni(NO3)2·6H2O、11.8mg Co(NO3)2·6H2O、5.4mg Fe(NO3)3·9H2O、6.2mg NH4F And 22.5mg of urea were weighed, dissolved in sequence in a Teflon (Teflon) lined stainless steel autoclave filled with 15mL of deionized water, and put into a foam nickel (area 2.5 cm. Times.2.5 cm) which was ultrasonically cleaned with 3M hydrochloric acid, absolute ethanol and deionized water, respectively, for 15 min. And (3) placing the reaction kettle in a baking oven at 120 ℃ for heat preservation for 6 hours, naturally cooling to room temperature, repeatedly flushing with deionized water, and drying with N 2 to obtain a precursor loaded on the foam nickel. And then placing the precursor in a tube furnace, vacuumizing, introducing high-purity Ar at a rate of 50sccm, heating to 350 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nano sheet NiCo 1.48Fe0.52O4 loaded on the foam nickel. As shown in the SEM picture of fig. 1, the morphology is a nano-platelet structure.
Example 2
Placing the foam nickel loaded with nano flake NiCo 1.48Fe0.52O4 obtained in the example 1 in a tube furnace, vacuumizing, introducing Ar/H 2 (the volume ratio of Ar to H 2 is 85%: 15%) at a rate of 100sccm, heating to 350 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the porous nano flake NiCo 1.48Fe0.52O4 electrocatalyst, wherein the morphology of the porous nano flake NiCo 1.48Fe0.52O4 electrocatalyst is a porous nano flake structure, the thickness of the nano flake is 20-60 nm, and the diameter is 400-800 nm as shown in an SEM picture of FIG. 2; the surface of the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst is distributed with holes with the aperture of 10-60 nm.
Example 3
The electrocatalyst prepared in example 2 was used as a working electrode, a graphite rod as a counter electrode, hg/HgO as a reference electrode, and the electrocatalyst was activated by running 200 cycles in 1M KOH solution with a cyclic voltammetry at a scan rate of 50mV/s between 0 and 0.7V (vs Hg/HgO) for use in the subsequent electrocatalytic reaction. As shown in the SEM picture of fig. 3, the appearance of the nano-plate is a porous nano-plate structure, the thickness of the nano-plate is 20-60 nm, and the diameter is 400-800 nm; the pores on the surface of the electrocatalyst remain, but the surface becomes rougher.
Comparative example 1
7.7mg Ni(NO3)2·6H2O、15.6mg Co(NO3)2·6H2O、6.2mg NH4F And 22.5mg of urea were weighed, dissolved in sequence in a Teflon (Teflon) lined stainless steel autoclave filled with 15mL of deionized water, and put into a foam nickel (area 2.5 cm. Times.2.5 cm) which was ultrasonically cleaned with 3M hydrochloric acid, absolute ethanol and deionized water, respectively, for 15 min. And (3) placing the reaction kettle in a baking oven at 120 ℃ for heat preservation for 6 hours, naturally cooling to room temperature, repeatedly flushing with deionized water, and drying with N 2 to obtain a precursor loaded on the foam nickel. And then placing the precursor in a tube furnace, vacuumizing, introducing high-purity Ar at a rate of 50sccm, heating to 350 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nano sheet NiCo 2O4 loaded on the foam nickel.
Comparative example 2
7.7mg Ni(NO3)2·6H2O、7.9mg Co(NO3)2·6H2O、10.7mg Fe(NO3)3·9H2O、6.2mg NH4F And 22.5mg of urea were weighed, dissolved in sequence in a Teflon (Teflon) lined stainless steel autoclave filled with 15mL of deionized water, and put into a foam nickel (area 2.5 cm. Times.2.5 cm) which was ultrasonically cleaned with 3M hydrochloric acid, absolute ethanol and deionized water, respectively, for 15 min. And (3) placing the reaction kettle in a baking oven at 120 ℃ for heat preservation for 6 hours, naturally cooling to room temperature, repeatedly flushing with deionized water, and drying with N 2 to obtain a precursor loaded on the foam nickel. And then placing the precursor in a tube furnace, vacuumizing, introducing high-purity Ar at a rate of 50sccm, heating to 350 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nano-sheet NiCoFeO 4 loaded on the foam nickel.
Comparative example 3
7.7mg Ni(NO3)2·6H2O、3.9mg Co(NO3)2·6H2O、16.1mg Fe(NO3)3·9H2O、6.2mg NH4F And 22.5mg of urea were weighed, dissolved in sequence in a Teflon (Teflon) lined stainless steel autoclave filled with 15mL of deionized water, and put into a foam nickel (area 2.5 cm. Times.2.5 cm) which was ultrasonically cleaned with 3M hydrochloric acid, absolute ethanol and deionized water, respectively, for 15 min. And (3) placing the reaction kettle in a baking oven at 120 ℃ for heat preservation for 6 hours, naturally cooling to room temperature, repeatedly flushing with deionized water, and drying with N 2 to obtain a precursor loaded on the foam nickel. And then placing the precursor in a tube furnace, vacuumizing, introducing high-purity Ar at a rate of 50sccm, heating to 350 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nano sheet NiCo 0.5Fe1.5O4 loaded on the foam nickel.
Comparative example 4
7.7mg Ni(NO3)2·6H2O、21.4mg Fe(NO3)3·9H2O、6.2mg NH4F And 22.5mg of urea were weighed, dissolved in sequence in a Teflon (Teflon) lined stainless steel autoclave filled with 15mL of deionized water, and put into a foam nickel (area 2.5 cm. Times.2.5 cm) which was ultrasonically cleaned with 3M hydrochloric acid, absolute ethanol and deionized water, respectively, for 15 min. And (3) placing the reaction kettle in a baking oven at 120 ℃ for heat preservation for 6 hours, naturally cooling to room temperature, repeatedly flushing with deionized water, and drying with N 2 to obtain a precursor loaded on the foam nickel. And then placing the precursor in a tube furnace, vacuumizing, introducing high-purity Ar at a rate of 50sccm, heating to 350 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the nano sheet NiFe 2O4 electrocatalyst loaded on the foam nickel.
Comparative example 5
The nano sheet-shaped NiCo 2O4 loaded on the foam nickel obtained in the comparative example 1 is placed in a tube furnace, vacuumized, introduced with Ar/H 2 (the volume ratio of Ar to H 2 is 85 percent to 15 percent) at a rate of 100sccm, heated to 350 ℃ at a heating rate of 10 ℃/min, kept for 2 hours, and naturally cooled to room temperature, thus obtaining the porous nano sheet-shaped NiCo 2O4 electrocatalyst. And then using the obtained electrocatalyst as a working electrode, using a graphite rod as a counter electrode and Hg/HgO as a reference electrode, and using a cyclic voltammetry to run for 200 circles in a 1M KOH solution at a scanning rate of 50mV/s between 0 and 0.7V (vs Hg/HgO), so as to activate the electrocatalyst for subsequent electrocatalytic reactions.
Comparative example 6
The nano sheet NiCoFeO 4 loaded on the foam nickel obtained in the comparative example 2 is placed in a tube furnace to be vacuumized, ar/H 2 (the volume ratio of Ar to H 2 is 85 percent to 15 percent) is introduced at the speed of 100sccm, the temperature is increased to 350 ℃ at the heating speed of 10 ℃/min, the temperature is kept for 2 hours, and the porous nano sheet NiCoFeO 4 electrocatalyst is obtained after natural cooling to the room temperature. And then using the obtained electrocatalyst as a working electrode, using a graphite rod as a counter electrode and Hg/HgO as a reference electrode, and using a cyclic voltammetry to run for 200 circles in a 1M KOH solution at a scanning rate of 50mV/s between 0 and 0.7V (vs Hg/HgO), so as to activate the electrocatalyst for subsequent electrocatalytic reactions.
Comparative example 7
The nano sheet-shaped NiCo 0.5Fe1.5O4 loaded on the foam nickel obtained in the comparative example 3 is placed in a tube furnace, vacuumized, introduced with Ar/H 2 (the volume ratio of Ar to H 2 is 85 percent to 15 percent) at a rate of 100sccm, heated to 350 ℃ at a heating rate of 10 ℃/min, kept for 2 hours, and naturally cooled to room temperature, thus obtaining the porous nano sheet-shaped NiCo 0.5Fe1.5O4 electrocatalyst. And then using the obtained electrocatalyst as a working electrode, using a graphite rod as a counter electrode and Hg/HgO as a reference electrode, and using a cyclic voltammetry to run for 200 circles in a 1M KOH solution at a scanning rate of 50mV/s between 0 and 0.7V (vs Hg/HgO), so as to activate the electrocatalyst for subsequent electrocatalytic reactions.
Comparative example 8
The nano sheet-shaped NiFe 2O4 loaded on the foam nickel obtained in the comparative example 4 is placed in a tube furnace, vacuumized, ar/H 2 (the volume ratio of Ar to H 2 is 85 percent to 15 percent) is introduced at the rate of 100sccm, the temperature is increased to 350 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2 hours, and the porous nano sheet-shaped NiFe 2O4 electrocatalyst is obtained after natural cooling to the room temperature. And then using the obtained electrocatalyst as a working electrode, using a graphite rod as a counter electrode and Hg/HgO as a reference electrode, and using a cyclic voltammetry to run for 200 circles in a 1M KOH solution at a scanning rate of 50mV/s between 0 and 0.7V (vs Hg/HgO), so as to activate the electrocatalyst for subsequent electrocatalytic reactions.
Test example 1
In a three-electrode electrochemical system, the samples prepared in example 1, comparative example 2, comparative example 3 and comparative example 4 were used as working electrodes, hg/HgO electrodes were used as reference electrodes, and graphite electrodes were used as counter electrodes, respectively, to perform electrocatalytic oxidation water test. The test solution is 1M KOH solution, and the electrochemical scanning is carried out within the range of 0-0.7V (vs. Hg/HgO) by adopting a linear scanning voltammetry, as shown in FIG. 4, the OER performance of the obtained electrocatalyst is optimal when the molar ratio of Co to Fe is 3:1, and the overpotential is only 260mV at the minimum when the current density reaches 10mA/cm 2. The ratio of the raw materials is explained as the relatively optimum ratio.
Test example 2
The samples prepared in example 1 and experimental example 3 were subjected to HRTEM test, and the results are shown in fig. 5 to 6. As can be seen from the figure, the samples of example 1 and experimental example 3 each have a lattice structure corresponding to the cubic system of NiCo 1.48Fe0.52O4, indicating that NiCo 1.48Fe0.52O4 has been successfully prepared.
Test example 3
The samples prepared in example 3 were subjected to EDS spectroscopy and the results are shown in fig. 7. As can be seen from the figure, the sample contains four elements of Ni, co, fe and O.
Test example 4
XPS test was performed on the samples prepared in example 1 and example 3, and the results are shown in FIGS. 8 to 9. As can be seen from the figure, ni exists mainly in +2 valence, co exists mainly in +3 valence with Fe in nano-sheet NiCo 1.48Fe0.52O4 after pore formation and electrochemical treatment under reducing gas, oxygen is converted from lattice oxygen to oxygen defect form mainly, and defect state is often the active center of catalyst, so that the sample in example 3 is more beneficial to electrocatalysis.
Test example 5
In a three-electrode electrochemical system, the samples prepared in example 1 and example 3 were used as working electrodes, hg/HgO electrodes were used as reference electrodes, and graphite electrodes were used as counter electrodes, respectively, for the electrocatalytic oxidation water test. The test solution is 1MKOH solution, and the linear sweep voltammetry is adopted to carry out electrochemical scanning within the range of 0-0.7V (vs. Hg/HgO), as shown in figure 10, when the OER current density of the porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst obtained after Ar/H 2 reduction and electrochemical treatment reaches 10mA/cm 2, the overpotential is only 220mV, which indicates that the Ar/H 2 reduction pore-forming and electrochemical treatment can obviously improve the electrocatalytic OER performance.
Test example 6
In a three-electrode electrochemical system, the samples prepared in example 3, comparative example 5, comparative example 6, comparative example 7 and comparative example 8 were used as working electrodes, hg/HgO electrodes were used as reference electrodes, and graphite electrodes were used as counter electrodes, respectively, to perform electrocatalytic oxidation water test. The test solution is 1M KOH solution, and the electrochemical scanning is carried out within the range of 0-0.7V (vs. Hg/HgO) by adopting a linear scanning voltammetry, as shown in FIG. 11, the performance is optimal when Co is still in a feed ratio of Fe=3:1 in the porous nano sheet-like electrocatalyst obtained after Ar/H 2 reduction and electrochemical treatment.
Test example 7
In a three-electrode electrochemical system, the samples prepared in example 1 and example 3 were used as working electrodes, hg/HgO electrodes were used as reference electrodes, and graphite electrodes were used as counter electrodes, respectively, for the electrocatalytic impedance spectroscopy test. The test solution is 1MKOH solution, and electrochemical impedance spectrum test is carried out in the potential range of 0-0.7V (vs. Hg/HgO), as shown in FIG. 12, the result is that the impedance of the porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst obtained after Ar/H 2 reduction and electrochemical treatment is smaller, which indicates that the charge transmission rate between the catalyst and the solution is faster.
Test example 8
In a three-electrode electrochemical system, the samples prepared in example 1 and example 3 were used as working electrodes, hg/HgO electrodes were used as reference electrodes, and graphite electrodes were used as counter electrodes, respectively, for the electrocatalytic impedance spectroscopy test. The test solution is 1MKOH solution, and electrochemical Tafil slope test is carried out in the potential range of 0-0.7V (vs. Hg/HgO), as shown in FIG. 13, and the result shows that the Tafil slope of the porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst obtained after Ar/H 2 reduction and electrochemical treatment is minimum, which indicates that the chemical reaction kinetic rate is the fastest in the OER process.
Test example 9
In a three-electrode electrochemical system, the sample prepared in example 3 was used as a working electrode, an Hg/HgO electrode was used as a reference electrode, and a graphite electrode was used as a counter electrode for a chronoamperometric test. The test solution is 1M KOH solution, the initial current density is 10mA/cm 2, the test is carried out for 10 hours, and as shown in figure 14, the current density fluctuates up and down at 10mA/cm 2 after the stability test for 10 hours, which proves that the prepared porous nano flaky NiCo 1.48Fe0.52O4 electrocatalyst has excellent electrochemical stability.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (11)
1. The application of the porous nano sheet NiCo 1.48Fe0.52O4 electrocatalyst in electrochemical oxygen evolution reaction is characterized in that the electrocatalyst enables the porous nano sheet NiCo 1.48Fe0.52O4 to be loaded on foam nickel by a hydrothermal method and a thermal annealing method;
wherein the thickness of the electrocatalyst is 20-60 nm, the diameter is 400-800 nm, and holes with the aperture of 10-60 nm are distributed on the surface of the electrocatalyst;
The electrocatalyst is prepared by the following steps:
S1, sequentially dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate, ammonium fluoride and urea in a molar ratio of 1:1.5:0.5:6.5:1.5 in a reaction kettle filled with deionized water, adding cleaned foam nickel, keeping the temperature in an oven for a period of time to obtain a precursor, then placing the precursor in a tubular furnace, heating and reacting for a certain time in an inert atmosphere, and naturally cooling to room temperature after the reaction is finished to obtain nano-sheet NiCo 1.48Fe0.52O4 loaded on the foam nickel;
s2, placing the nano sheet-shaped NiCo 1.48Fe0.52O4 obtained in the S1 into a tube furnace, continuously introducing reducing gas for roasting, preserving heat for a period of time, and cooling to room temperature to obtain the porous nano sheet-shaped NiCo 1.48Fe0.52O4 electrocatalyst;
The application is as follows: in a three-electrode system, an electrocatalytic oxidation water oxygen evolution reaction is carried out by taking a porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst as a working electrode, a graphite rod as a counter electrode and Hg/HgO as a reference electrode.
2. The use according to claim 1, wherein in step S1, the oven is kept at a temperature of 110 to 150 ℃ for a period of 5 to 12 hours.
3. The use according to claim 1, wherein in steps S1 and S2, the heating rate in the tube furnace is 6-15 ℃/min, the reaction temperature is 280-400 ℃, and the holding time is 1.5-4 h.
4. The use according to claim 1, wherein the reducing gas is a mixture of one selected from nitrogen, helium and argon in combination with hydrogen.
5. The use according to claim 1, wherein the inert gas flow rate in step S1 is 30-100 sccm.
6. The method according to claim 4, wherein the flow rate of the mixture in step S2 is 80-200 sccm.
7. The method according to claim 4, wherein the volume ratio of inert gas to reducing gas in the mixture is 85:15.
8. The use according to claim 1, characterized in that the electrocatalyst is pre-activated prior to the electrochemical oxygen evolution reaction, comprising the following specific steps:
The porous nano-sheet NiCo 1.48Fe0.52O4 electrocatalyst is used as a working electrode, a graphite rod is used as a counter electrode, hg/HgO is used as a reference electrode, and cyclic voltammetry is used for carrying out activation treatment within the range of 0-0.7V (vs Hg/HgO).
9. The use according to claim 8, wherein the activation treated solution is 1M KOH or 1M noh.
10. The use according to claim 8, wherein the scanning rate of the activation treatment is 10 to 100mV/s.
11. The use according to claim 8, wherein the number of turns of the activation treatment is 150-300.
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| CN110284153A (en) * | 2018-03-19 | 2019-09-27 | 天津大学 | A kind of cobalt/cobalt protoxide porous nano-sheet array composite material and its preparation method and application |
| CN111495417A (en) * | 2020-05-26 | 2020-08-07 | 盐城工学院 | Foam nickel loaded iron-cobalt-nickel metal nano catalyst and preparation method and application thereof |
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| CN109794247A (en) * | 2019-01-16 | 2019-05-24 | 北京工业大学 | A kind of amorphous iron-doped nickel oxide nano-sheet electrocatalysis material and its preparation and application |
| CN111495417A (en) * | 2020-05-26 | 2020-08-07 | 盐城工学院 | Foam nickel loaded iron-cobalt-nickel metal nano catalyst and preparation method and application thereof |
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