CN111001414A - Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof - Google Patents
Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 239000002070 nanowire Substances 0.000 title claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000011258 core-shell material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000004744 fabric Substances 0.000 claims abstract description 30
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
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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
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- B01J35/30—
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- B01J35/33—
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- 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
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- 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
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
A structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method: dissolving cobalt nitrate, nickel nitrate and urea in an ethanol/water mixed solution, adding the treated carbon cloth, carrying out hydrothermal reaction, and washing, centrifuging and drying crystal lattices to obtain a nickel-cobalt precursor nanowire array uniformly grown on the carbon cloth; putting the nickel-cobalt precursor nano array into a potassium permanganate solution, carrying out hydrothermal reaction, washing, centrifuging and drying to obtain a nickel-cobalt-manganese mixed precursor array; and calcining the precursor in a nitrogen atmosphere to form the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material growing on the carbon cloth. And provides a preparation method of the structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material. The preparation method is simple in preparation process, the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material can be effectively prepared, and the prepared material has excellent performance of producing oxygen by electrolyzing water at normal temperature and normal pressure.
Description
(I) technical field
The invention relates to a structure-controllable hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material and a preparation method thereof, and the material can be applied to electrocatalytic water decomposition.
(II) background of the invention
In order to meet the increasing demand for energy, clean, sustainable energy sources have attracted considerable attention, such as hydrogen, solar energy, wind energy and tidal energy. Among these renewable energy sources, hydrogen has great potential as an energy carrier to replace fossil fuels. Electrocatalytic water decomposition provides a promising environmental protection method for large-scale hydrogen energy production. Generally, during the electrolysis of water, there is a significant loss of efficiency and overpotential due to the slow kinetics of the anodic Oxygen Evolution Reaction (OER). To overcome this critical problem, it is necessary to design and develop an efficient electrocatalyst to promote the kinetic process and reduce the overpotential during the oxygen evolution reaction. Conventional noble metal RuO2And IrO2Have higher OER activity, however, high cost and scarcity have hindered their practical application in commercial water electrolysis. Therefore, it is very important to develop a non-noble metal type OER electrocatalyst with low cost, high catalytic activity and high catalytic stability.
Transition metal (e.g., Ni, Co, Fe) materials are a promising OER electrocatalyst due to their high stability in alkaline electrolytes and their environmental friendliness. Among them, spinel-type cobalt-based oxides are attracting attention because of their high catalytic activity, convenient preparation, and low price. Co as a typical spinel type electrocatalyst3O4The OER process embodies high-efficiency catalytic activity and good corrosion resistance. In addition, other metal atoms are added to Co3O4In spinel structure, such as Ni, Zn, Fe, Co can be further increased3O4Electrocatalytic activity of (c). It is well known that nickel cobaltate (NiCo)2O4) Because of the special spinel structure, the catalyst can increase catalytic active sites and enhance conductivity (specific to Co)3 O 4100 times higher). In this structure, Co is distributed in the tetrahedral and octahedral positions,ni occupies the octahedral sites, forming different valence states. Therefore, due to these two redox couples (Co)3+/Co2+And Ni3+/Ni2+) Can obtain remarkable electrocatalytic active sites. Although NiCo2O4The catalyst has been developed to some extent, but in practical application, the catalytic performance of the catalyst still needs to be further improved. In recent years, ultra-thin manganese dioxide nanosheets have been extensively studied as a two-dimensional layered material in the field of OER electrocatalysts (a. the nuwara, e.cerkez, s.shumlas, n.attanayake, i.mckendry, l.frazer, e.borguet, q.kang, r.remsing and m.klein, Nickel confined in the interlayer region of the interface region of birnessite: an active electrochemical catalysis for water oxidation, angle.chem.int.ed, 2016,5510381). The two-dimensional layered MnO2MnO shared by edge6The octahedron has good electrocatalytic performance on OER due to the unique electronic structure characteristic. Ultra-thin MnO2The nanosheets provide sufficient active sites and have high conductivity, thereby having excellent OER catalytic performance. Therefore, NiCo is rationally bound2O4And MnO2Is to further improve NiCo2O4One promising strategy for the electrocatalytic performance of OERs.
In general, when a conventional catalytic electrode is manufactured, it is inevitable to add a polymer binder (such as Nafion or PTFE) to fix the catalyst on a current collector. However, the insulating polymer binder reduces the conductivity of the electrode. In addition, the diffusion of active sites and reactants of the electrocatalyst will be blocked and inhibited. Recent researches show that the three-dimensional nano-array catalytic electrode can promote efficient catalysis of OER (organic electroluminescent) and promote diffusion of electrolyte and O2And expose more active sites. Therefore, the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell hybrid nano-array is a promising OER catalytic material with high catalytic activity and stability.
Disclosure of the invention
In order to overcome the defects of the prior art, the invention aims to provide a hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material with a controllable structure and a preparation method thereof, the process is simple, the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material can be effectively prepared, and the prepared material has excellent performance of producing oxygen by electrolyzing water at normal temperature and pressure.
The technical scheme adopted by the invention is as follows:
a structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method:
(1) dissolving 0.1-0.6 g of cobalt nitrate, 0.05-0.3 g of nickel nitrate and 0.2-0.4 g of urea in 40mL of ethanol/water mixed solution, adding the treated carbon cloth, carrying out hydrothermal reaction at 80-120 ℃ for 8-24 h, washing, centrifuging and drying to obtain a nickel-cobalt precursor nanowire array uniformly grown on the carbon cloth;
(2) putting the nickel-cobalt precursor nano array into 0.4-1.6 mM potassium permanganate solution, carrying out hydrothermal reaction at 140-180 ℃ for 20-60 min, and finally washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) and calcining the precursor for 2-4 h at 300-400 ℃ in a nitrogen atmosphere to form the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material growing on the carbon cloth.
Furthermore, the selection of reaction conditions has an important influence on the preparation of the structure of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array. The pH value of the precursor solution can be adjusted by the hydrolysis of the urea, so that the alkaline nickel-cobalt precursor nano array can grow on the carbon cloth more easily. During the preparation process, the size, diameter and concentration of the nano array can be regulated and controlled by changing the concentration of the reactant.
A preparation method of a structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material comprises the following steps:
(1) dissolving 0.1-0.6 g of cobalt nitrate, 0.05-0.3 g of nickel nitrate and 0.2-0.4 g of urea in 40mL of ethanol/water mixed solution, adding the treated carbon cloth, carrying out hydrothermal reaction at 80-120 ℃ for 8-24 h, washing, centrifuging and drying to obtain a nickel-cobalt precursor nanowire array uniformly grown on the carbon cloth;
(2) putting the nickel-cobalt precursor nano array into 0.4-1.6 mM potassium permanganate solution, carrying out hydrothermal reaction at 140-180 ℃ for 20-60 min, and finally washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) and calcining the precursor for 2-4 h at 300-400 ℃ in a nitrogen atmosphere to form the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material growing on the carbon cloth.
Has good catalytic performance for electrolyzing water to generate oxygen at normal temperature and normal pressure. The specific operation process of the performance test is as follows:
(1) the prepared hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is cut into 1cm multiplied by 1cm and directly used as a working electrode. Meanwhile, a platinum wire electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system for oxygen evolution reaction test;
(2) before the test, 1M KOH solution was added to the cell, the test program of linear sweep cyclic voltammetry and chronoamperometry was selected, and the current at the working electrode at a sweep rate of 5mV/s was monitored by a computer. Finally, calculating 10mA/cm according to the measured data and a corresponding formula2And evaluating the oxygen reduction performance of the catalyst by overpotential and Tafel slope under current density.
The hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and the preparation method provided by the invention have the beneficial effects that:
(1) the two-step hydrothermal method is adopted, the synthesis is simple, and the core-shell nano array is uniformly grown on the carbon cloth with excellent conductivity and toughness.
(2) The shape and structure of the nano array can be controlled by changing the concentration of reactants and adjusting the reaction time.
(3) The hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material has excellent catalytic performance on oxygen production by electrolysis of water at normal temperature, and has a very high application prospect.
(IV) description of the drawings
Fig. 1 is an SEM image of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material according to embodiment 1 of the present invention.
Fig. 2 is a TEM image of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material according to embodiment 1 of the present invention.
Fig. 3 is an XRD chart of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material in embodiment 1 of the present invention.
Fig. 4 is an XPS diagram of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material according to embodiment 1 of the present invention.
Fig. 5 is a linear sweep voltammetry, tafel slope, linear sweep voltammetry curves before and after 5000 cycles, and a polarographic current-time curve of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material according to embodiment 1 of the present invention.
Fig. 6 is an SEM image of the nickel cobaltate nanowire array material according to embodiment 2 of the present invention.
Fig. 7 is a TEM image of a nickel cobaltate nanowire array material according to embodiment 2 of the present invention.
Fig. 8 is an XRD pattern of the nickel cobaltate nanowire array material according to embodiment 2 of the present invention.
Fig. 9 is a linear sweep voltammetry, tafel slope diagram of the nickel cobaltate nanowire array material according to embodiment 2 of the present invention.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
in this embodiment, the performance test of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material on the oxygen production from electrolyzed water at normal temperature is performed on a CHI 660 electrochemical workstation, and the specific operation process is as follows:
(1) the prepared hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is cut into 1cm multiplied by 1cm and directly used as a working electrode. Meanwhile, a platinum wire electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system for oxygen evolution reaction test;
(2) before testing, 1M KOH solution is added into an electrolytic cell, and the test procedures of linear sweep cyclic voltammetry and chronoamperometry are selected and usedThe computer monitors the current at the working electrode at a sweep rate of 5 mV/s. Finally, calculating 10mA/cm according to the measured data and a corresponding formula2And evaluating the oxygen reduction performance of the catalyst by overpotential and Tafel slope under current density.
Example 1:
a structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method:
(1) dissolving 0.29g of cobalt nitrate, 0.145g of nickel nitrate and 0.36g of urea in 40mL of ethanol/water mixed solution, adding the treated carbon cloth, carrying out hydrothermal reaction at 90 ℃ for 16h, washing, centrifuging and drying to obtain the nickel-cobalt precursor nanowire array uniformly grown on the carbon cloth;
(2) putting the obtained nickel-cobalt precursor nano array into 0.8mM potassium permanganate solution, carrying out hydrothermal reaction at 160 ℃ for 30min, and finally washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) calcining the nickel-cobalt-manganese mixed precursor array for 2 hours at 350 ℃ in a nitrogen atmosphere to form a hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material growing on the carbon cloth;
an SEM image of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material is obtained and is shown in figure 1, a TEM image of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material is obtained and is shown in figure 2, an XRD image of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material is obtained and is shown in figure 3, an XPS image of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material is obtained and is shown in figure 4, and linear scanning voltammetry, Tafel slope, linear scanning voltammetry curves before and after 5000 circles and polarographic current-time curves of the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material are obtained and are shown in figure 5.
As seen from the SEM image, the prepared hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array uniformly grows on the surface of the carbon cloth, and the surface of the nanowire forming the array has an obvious flaky structure. From the TEM image, it is seen that the nanowire is composed of a core having a hollow structure and a shell constructed by nanosheets. The synthesized nanowires were further confirmed to be composed of nickel cobaltate and manganese oxide by XRD and XPS analysis. Tong (Chinese character of 'tong')The linear sweep voltammetry shows that the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array is 10mA/cm2With a lower overpotential at current density. The tafel slope is 89mVdec calculated according to linear sweep voltammogram-1. From linear sweep voltammetry curves before and after 1000 circles and polarographic current time curves, the hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material has good stability.
Example 2:
a structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method:
(1) dissolving 0.29g of cobalt nitrate, 0.145g of nickel nitrate and 0.36g of urea in 40mL of ethanol/water mixed solution, adding the treated carbon cloth (2cm multiplied by 1cm), carrying out hydrothermal reaction at 90 ℃ for 16h, washing, centrifuging and drying,
(2) calcining the nickel-cobalt precursor array for 2h at 350 ℃ in a nitrogen atmosphere to form a nickel cobaltate nanowire array material growing on the carbon cloth;
SEM images of the obtained nickel cobaltate nanowire array material are shown in fig. 6, TEM images of the obtained nickel cobaltate nanowire array material are shown in fig. 7, XRD images of the obtained nickel cobaltate nanowire array material are shown in fig. 8, linear sweep voltammetry of the obtained nickel cobaltate nanowire array material is shown in fig. 9, and tafel slope diagram is shown in fig. 9.
As seen from the SEM image, the prepared nickel cobaltate nanowire array uniformly grows on the surface of the carbon cloth, and the surface of the nanowire forming the array has a rough structure. From the TEM images, nanowires are assembled from small nanoparticles. By XRD analysis, the synthesized nanowire was further confirmed to be nickel cobaltate. As can be seen by linearly scanning voltammetry curves, the nickel cobaltate nanowire array is 10mA/cm2The overpotential is large under the current density. The tafel slope is 156mVdec calculated according to the linear sweep voltammogram-1。
Example 3:
a structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method:
(1) dissolving 0.1g of cobalt nitrate, 0.05g of nickel nitrate and 0.2g of urea in 40mL of ethanol/water mixed solution, adding the treated carbon cloth (2cm multiplied by 1cm), carrying out hydrothermal reaction at 80 ℃ for 8h, washing, centrifuging and drying;
(2) putting the obtained nickel-cobalt precursor nano array into 0.4mM potassium permanganate solution, carrying out hydrothermal reaction at 140 ℃ for 20min, and finally washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) calcining the nickel-cobalt precursor array for 2h at 300 ℃ in a nitrogen atmosphere to form a nickel cobaltate nanowire array material growing on the carbon cloth;
good array catalysts cannot be grown due to too low precursor concentration. Meanwhile, the calcination temperature is low, and oxides cannot be formed well.
Example 4:
a structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method:
(1) dissolving 0.6g of cobalt nitrate, 0.3g of nickel nitrate and 0.4g of urea in 40mL of ethanol/water mixed solution, adding the treated carbon cloth (2cm multiplied by 1cm), carrying out hydrothermal reaction at 120 ℃ for 24h, washing, centrifuging and drying;
(2) putting the obtained nickel-cobalt precursor nano array into a 1.6mM potassium permanganate solution, carrying out hydrothermal reaction at 180 ℃ for 60min, and finally, washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) calcining the nickel-cobalt precursor array for 4 hours at 400 ℃ in a nitrogen atmosphere to form a nickel cobaltate nanowire array material growing on the carbon cloth;
due to the high concentration of the precursor, all the array materials formed on the surface of the carbon cloth are agglomerated together. Meanwhile, the calcination temperature is higher, and the calcination time is longer, so that the array catalyst is totally collapsed.
Claims (4)
1. A structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material is prepared by the following method:
(1) dissolving 0.1-0.6 g of cobalt nitrate, 0.05-0.3 g of nickel nitrate and 0.2-0.4 g of urea in 40mL of ethanol/water mixed solution, adding treated carbon cloth (2cm multiplied by 1cm), carrying out hydrothermal reaction at 80-120 ℃ for 8-24 h, washing, centrifuging and drying to obtain the nickel-cobalt precursor nanowire array uniformly grown on the carbon cloth;
(2) putting the nickel-cobalt precursor nano array into 0.4-1.6 mM potassium permanganate solution, carrying out hydrothermal reaction at 140-180 ℃ for 20-60 min, and finally washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) and calcining the nickel-cobalt-manganese mixed precursor array for 2-4 h at 300-400 ℃ in a nitrogen atmosphere to form the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material growing on the carbon cloth.
2. The hollow nickel cobaltate nanowire/sheet-shaped manganese oxide core-shell nanowire array material of claim 1, wherein the addition of urea adjusts the pH value of the precursor solution through hydrolysis thereof, so that the alkaline nickel cobalt precursor nanoarray can grow on carbon cloth more easily, and in the preparation process, the size, diameter and concentration of the nanoarray can be adjusted and controlled by changing the concentration of reactants.
3. The preparation method of the structure-controllable hollow nickel cobaltate nanowire/sheet manganese oxide core-shell array material according to claim 1, wherein the method comprises the following steps:
(1) dissolving 0.1-0.6 g of cobalt nitrate, 0.05-0.3 g of nickel nitrate and 0.2-0.4 g of urea in 40mL of ethanol/water mixed solution, adding treated carbon cloth (2cm multiplied by 1cm), carrying out hydrothermal reaction at 80-120 ℃ for 8-24 h, washing, centrifuging and drying to obtain the nickel-cobalt precursor nanowire array uniformly grown on the carbon cloth;
(2) putting the nickel-cobalt precursor nano array into 0.4-1.6 mM potassium permanganate solution, carrying out hydrothermal reaction at 140-180 ℃ for 20-60 min, and finally washing, centrifuging and drying the nickel-cobalt-manganese mixed precursor array;
(3) and calcining the nickel-cobalt-manganese mixed precursor array for 2-4 h at 300-400 ℃ in a nitrogen atmosphere to form the hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material growing on the carbon cloth.
4. The method of claim 3, wherein the concentration of cobalt nitrate, nickel nitrate, urea and potassium permanganate and the temperature and time of the hydrothermal reaction and heat treatment are controlled to regulate the shape and structure of the nanowire array.
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