CN114108005A - Preparation method of nickel cobalt hydroxide nanosheet and prepared nickel cobalt hydroxide nanosheet - Google Patents
Preparation method of nickel cobalt hydroxide nanosheet and prepared nickel cobalt hydroxide nanosheet Download PDFInfo
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- CN114108005A CN114108005A CN202111435898.1A CN202111435898A CN114108005A CN 114108005 A CN114108005 A CN 114108005A CN 202111435898 A CN202111435898 A CN 202111435898A CN 114108005 A CN114108005 A CN 114108005A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 83
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002055 nanoplate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000010411 electrocatalyst Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910003266 NiCo Inorganic materials 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 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 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- -1 nickel-cobalt metal hydroxide Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 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 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
Abstract
The invention discloses a preparation method of a nickel-cobalt hydroxide nanosheet, which comprises the steps of respectively dissolving 2-methylimidazole and cobalt salt in water, mixing, adding nickel foam, stirring for reaction to obtain a Co-ZIF nanosheet, mixing the Co-ZIF nanosheet and the nickel salt in ethanol, and stirring at constant temperature to obtain a final product. The method is simple, convenient and environment-friendly, and the prepared hollow triangular nickel-cobalt hydroxide nanosheet is beneficial to contact between the electrolyte and the electrocatalytic material, and has good OER catalytic performance and high stability.
Description
Technical Field
The invention relates to the field of double-metal hydroxide nano materials, in particular to a preparation method of a hollow triangular nickel cobalt hydroxide nanosheet and a nickel cobalt hydroxide nanosheet prepared by the method.
Background
With the rapid development of society, the problems of energy crisis and climate change become more serious, and people are prompted to explore sustainable clean energy. Electrocatalytic water splitting is considered as the most promising strategy to achieve clean, sustainable energy, but is hampered by the slow kinetics of the anodic reaction, the Oxygen Evolution Reaction (OER), and therefore efficient, low cost catalysts need to be explored to better increase OER activity.
Currently, the common OER electrocatalysts include noble metal (Pt, Ir, Ru, etc.) based catalysts, but the large-scale application of the catalysts is further hindered due to the small storage amount and high price of the noble metals. Therefore, the development of a catalyst with high efficiency, low cost and strong stability to replace the noble metal-based catalyst is urgently needed. The transition metal, the transition metal oxide and the transition metal hydroxide are expected to be used as catalysts for replacing OER noble metals due to the advantages of low cost, good stability, easy preparation and the like. Among them, NiCo hydroxide has attracted great attention due to its adjustable structure and simple synthesis. Despite the great advances made in NiCo double metal hydroxide electrocatalysts, problems of poor conductivity and low catalytic activity are still encountered in terms of OER. Therefore, it is important to optimize the NiCo double hydroxide electrocatalyst for improved OER performance. The invention patent application CN 111921529A discloses a preparation method of a nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material, wherein the nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material is obtained by adopting urea, nickel salt, cobalt salt, terephthalic acid, N-dimethylformamide and the like, and then carrying out reaction kettle and centrifugal treatment, and the method is poor in environmental friendliness. The invention patent application CN 112299494A discloses a preparation method of a nickel-cobalt hydroxide material, wherein the nickel-cobalt hydroxide material is prepared by adopting nickel salt, cobalt salt, sodium hydroxide, ammonia water and the like and carrying out long-time reaction through coprecipitation. The preparation method of the catalyst uses strong alkali, and the reaction generally needs heating for dozens of hours, so that the time is long.
Disclosure of Invention
The invention aims to provide a preparation method of nickel cobalt hydroxide nanosheets, which is simple, convenient and environment-friendly, and the prepared nickel cobalt hydroxide nanosheets have rich active sites, good OER catalytic performance and high stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nickel cobalt hydroxide nanosheet comprises the following steps:
(a) respectively dissolving 2-methylimidazole and cobalt salt in water to obtain solutions, mixing the two solutions, adding foamed nickel, stirring, and taking out to obtain a Co-ZIF nanosheet loaded on the foamed nickel, wherein the loading capacity of the Co-ZIF nanosheet on the foamed nickel is 5-10 mg-cm-2；
(b) Mixing the Co-ZIF nanosheet loaded on the foamed nickel and the nickel salt in ethanol, stirring for 1-10 hours at a constant temperature of 20-80 ℃, and taking out to obtain the nickel-cobalt hydroxide nanosheet loaded on the foamed nickel, wherein the molar ratio of the cobalt salt to the nickel salt is 1: 1-10.
Preferably, the cobalt salt is selected from Co (NO)3)2·6H2O、CoCl2·6H2O、Co(NO3)2Or C4H6CoO4·4H2O; the nickel salt is selected from Ni (NO)3)2·6H2O、Ni(NO3)2、NiSO4Or NiCl2。
Preferably, the loading capacity of the Co-ZIF nanosheet on the foamed nickel is 6-7 mg-cm-2(ii) a The molar ratio of the cobalt salt to the nickel salt is 1: 7-8.
Preferably, the Co-ZIF nanosheets loaded on the foamed nickel are obtained after continuous stirring for 3 hours in the step (a); and mixing the Co-ZIF nanosheet loaded on the foamed nickel and the nickel salt in ethanol, and stirring for 1-2 hours at a constant temperature of 27 ℃ to obtain the nickel-cobalt hydroxide nanosheet loaded on the foamed nickel.
The invention also provides a nickel cobalt hydroxide nanosheet prepared by the method, wherein the nickel cobalt hydroxide nanosheet is of a hollow triangular structure.
In the preparation method, foam nickel is used as a substrate, and a Co-ZIF (ZIF refers to a zeolitic imidazolate framework compound) triangular nanosheet array rather than nanoparticles is prepared through a coordination reaction of cobalt ions and 2-methylimidazole. Then, Co-ZIF is used as a template, and the Co-ZIF and nickel salt are subjected to ion exchange reaction in ethanol to obtain the hollow triangular nickel-cobalt hydroxide nanosheet consisting of the nanosheets. The prepared catalyst has high specific surface area and roughness, is beneficial to the exposure of more active sites in the catalytic reaction process, simultaneously has a hollow structure, is beneficial to improving the mass transfer efficiency of reactants, and can provide a channel for the discharge of oxygen bubbles by an ordered array structure. In addition, the nickel is doped to effectively adjust the electronic structure of the material, so that excellent electrocatalytic performance is obtained. The hollow triangular nickel-cobalt hydroxide nanosheet catalyst prepared by the method does not need any binder, has good catalytic performance and strong stability in OER, and can obviously improve the kinetics of OER, thereby being beneficial to overcoming the bottleneck of slow kinetics of the anodic oxygen evolution reaction of electrolyzed water.
Drawings
Fig. 1 is an SEM spectrum of hollow triangular nickel cobalt hydroxide nanosheets prepared in example 1;
fig. 2 is a TEM spectrum of the hollow triangular nickel cobalt hydroxide nanosheets prepared in example 1;
FIG. 3 is X-ray photoelectron spectroscopy (XPS) of a hollow triangular nickel cobalt hydroxide nanosheet prepared in example 1, with graphs a and b corresponding to Ni and Co, respectively;
FIG. 4 shows the 2mVs of the materials prepared in example 1 and comparative examples 1, 2 and 3-1Polarization curve of scan rate in 1MKOH solution;
fig. 5 is a stability test curve of the hollow triangular nickel cobalt hydroxide nanosheets prepared in example 1 held at constant voltage for 10 hours;
fig. 6 is an X-ray diffraction spectrum (XRD) of the hollow triangular nickel cobalt hydroxide nanosheets prepared in example 1.
Detailed Description
The invention is further illustrated by the following preferred examples:
example 1: preparation of hollow triangular nickel cobalt hydroxide nanosheets example 1
1314mg of 2-methylimidazole (C)4H6N2) 582mg of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) are respectively dissolved in 40mL of ultrapure water, the two solutions are mixed and then added with clean foam nickel, and the mixture is continuously stirred for 3 hours to obtain Co-ZIF nano-sheets (Co in the stepThe loading amount of the-ZIF nano sheet on the foamed nickel is 7 mg-cm-2Namely, each square centimeter of the surface of the foam nickel is loaded with 7mgCo-ZIF nano-sheets).
Mixing the obtained Co-ZIF nano sheet loaded on the foamed nickel with nickel nitrate hexahydrate (Ni (NO)3)2·6H2O) in ethanol, cobalt nitrate hexahydrate (Co (NO) used in the above step3)2·6H2O) and nickel nitrate hexahydrate (Ni (NO) in the present step3)2·6H2O) is 1:8, and stirring is carried out for 1 hour at 27 ℃, thus finally obtaining the hollow triangular nickel cobalt hydroxide nanosheet material loaded on the foamed nickel.
SEM, TEM, XPS, and XRD spectra of the hollow triangular nickel cobalt hydroxide nanosheet material supported on nickel foam obtained in example 1 are shown in fig. 1, 2, 3, and 6, respectively. As can be seen from fig. 1, the morphology of the hollow nickel-cobalt hydroxide nanosheet is a triangular hollow nanosheet composed of nanosheets, and in the OER test process, the hollow structure can increase the contact area between the electrolyte and the electrocatalytic material, so that the flow of the electrolyte is facilitated, and the electrocatalytic activity of the catalyst is further enhanced; as can be seen from FIG. 2, the surface of the triangular hollow nanosheet is formed by an arrangement of a plurality of fine, mutually-interlaced nanoflakes. The above results confirmed that the material obtained in example 1 was a hollow nickel cobalt hydroxide nanosheet. From the surface valence analysis of FIG. 3, it can be seen that a is an XPS spectrum of Ni, and peaks at 855.9 and 873.7eV are oxidation state Ni2+. b is XPS spectrum of Co, with peaks at 781.6 and 796.9eV being Co2+. From the XRD pattern of FIG. 6, the material obtained in example 1 matches the nickel cobalt hydroxide of card number JCPDS No.33-0429, corresponding to the (003), (006), (012), (015), (018), (110) and (113) crystal planes (i.e. as evidenced by the cobalt nickel hydroxide). The above results confirm that the hollow triangular nickel cobalt hydroxide nanosheet material obtained in example 1 is successfully prepared, and the hollow structure is favorable for charge transfer and transmission in the OER process.
Example 2: preparation method of hollow triangular nickel cobalt hydroxide nanosheet example 2
1314mg of 2-methylimidazole (C)4H6N2) 476mg of cobalt chloride hexahydrate (CoCl)2·6H2O) are respectively dissolved in 45mL of ultrapure water, the two solutions are mixed and then added with clean nickel foam, and the mixture is continuously stirred for 6 hours to obtain Co-ZIF nano sheets loaded on the nickel foam (the loading amount of the Co-ZIF nano sheets in the step is 10mg cm)-2)。
Mixing the obtained Co-ZIF nano sheet loaded on the foamed nickel with nickel sulfate (NiSO)4) Mixing in ethanol, cobalt chloride hexahydrate (CoCl) as above2·6H2O) and nickel sulfate (NiSO)4) The molar ratio of the nickel-cobalt hydroxide is 1:1, the temperature is kept constant at 80 ℃, and the nickel-cobalt hydroxide nanosheet material is kept for 3 hours, and finally the hollow triangular nickel-cobalt hydroxide nanosheet material is obtained.
Example 3: preparation of hollow triangular nickel cobalt hydroxide nanosheets example 3
1314mg of 2-methylimidazole (C)4H6N2) 498mg of cobalt acetate tetrahydrate (C)4H6CoO4·4H2O) are respectively dissolved in 50mL of ultrapure water, the two solutions are mixed and then added with clean nickel foam, and the mixture is continuously stirred for 2 hours to obtain Co-ZIF nano sheets (the loading capacity of the Co-ZIF nano sheets in the step is 8mg cm)-2)。
Mixing the obtained Co-ZIF nano-sheet loaded on the foamed nickel with nickel chloride (NiCl)2) Mixing in ethanol, cobalt acetate tetrahydrate (C) used in the above step4H6CoO4·4H2O) and nickel chloride (NiCl)2) The molar ratio of the nickel-cobalt hydroxide is 1:10, the temperature is kept at 60 ℃ for 7 hours, and finally the hollow triangular nickel-cobalt hydroxide nanosheet material is obtained.
Example 4: preparation of hollow triangular Nickel cobalt hydroxide nanosheets EXAMPLE 4
1314mg of 2-methylimidazole (C)4H6N2) 366mg of cobalt nitrate (Co (NO)3)2) Respectively dissolving the two solutions in 60mL of ultrapure water, mixing the two solutions, adding clean nickel foam, and continuously stirring for 4 hours to obtain Co-ZIF nano sheets (the loading capacity of the Co-ZIF nano sheets in the step is 5mg cm)-2)。
Loading the obtained Co-ZIF sodium on foamed nickelRice flake and nickel nitrate (Ni (NO)3)2) Mixing in ethanol, cobalt nitrate (Co (NO) used in the previous step3)2) With nickel nitrate (Ni (NO)3)2) The molar ratio of the nickel-cobalt hydroxide is 1:4, the temperature is kept at 40 ℃, and the temperature is kept for 10 hours, so that the hollow triangular nickel-cobalt hydroxide nanosheet material is finally obtained.
SEM, TEM, XRD and XPS spectrums of the hollow triangular nickel cobalt hydroxide nanosheet materials prepared in the examples 2, 3 and 4 are respectively carried out, and the conclusion is basically the same as that of the example 1. The amplification experiments of the four examples show that multiple sheets of product can be made with comparable performance.
EXAMPLE 5 electrocatalytic Performance testing
Taking example 1 as an example, an electrocatalytic performance test was performed and compared with catalytic performance of several comparative examples as follows.
Comparative example 1: examples of ion exchange without nickel salt
(a) 1314mg of 2-methylimidazole (C)4H6N2) 582mg of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) are respectively dissolved in 40mL of ultrapure water, the two solutions are mixed and then added with clean foam nickel, and the mixture is continuously stirred for 3 hours to obtain the Co-ZIF nano sheet.
(b) And (3) putting the obtained Co-ZIF nanosheet into ethanol, and stirring for 1 hour at 27 ℃ to finally obtain the cobalt nanosheet material.
Comparative example 2:
commercial ruthenium dioxide was purchased, untreated.
Comparative example 3:
the foamed nickel was ultrasonically cleaned for 20 minutes using acetone, ethanol, 3M hydrochloric acid and ultrapure water in this order, and then left to dry at room temperature for use (the effective area of the foamed nickel was 1 x 1cm in the electrochemical test).
The test process comprises the following steps:
a catalyst slurry was prepared by dispersing 10mg of the material of comparative example 2 in a mixed solution of 980. mu.l of ethanol and 20. mu.l of Nafion; then 200 microliter of the catalyst slurry was dropped onto a clean nickel foam (1 x 1cm active area), dried to make the corresponding working electrode, and used for electrocatalytic comparative testing with the electrodes of example 1 and comparative examples 1 and 3.
In the electrocatalysis test, a platinum sheet and Hg/HgO are respectively used as a counter electrode and a reference electrode; potential reference Reversible Hydrogen Electrode (RHE): ERHE＝EHg/HgO+0.098+0.059 XpH (1M KOH solution). Calculating the overpotential (η) according to the equationRHE-1.23V. At 2 mV. s-1Linear Sweep Voltammetry (LSV) was recorded in 1M KOH solution at the scan rate to obtain a polarization curve, see fig. 4, where the electrode potential data was 90% iR compensated. The stability test was maintained at constant voltage for 10 hours, see fig. 5.
As can be seen from fig. 4, the application of the electrocatalyst of example 1 to the oxygen evolution reaction in an alkaline environment can significantly reduce the overpotential (relative to the cobalt nanosheets of comparative example 1, the commercial ruthenium dioxide of comparative example 2, and the blank nickel foam of comparative example 3). The current density of the electrocatalyst of example 1 is significantly increased compared to comparative example 3, indicating that the high activity originates from the electrocatalyst itself and not the substrate of the working electrode (blank nickel foam). Compared to comparative example 1, the electrocatalyst of example 1 exhibits a huge advantage of activity, indicating that its activity mainly derives from the doping and hollow structure of nickel. The electrocatalyst of example 1 has a higher current density and a lower potential compared to comparative example 2, indicating the potential of the catalyst for use as a replacement for commercial ruthenium dioxide. In addition, the electrocatalyst for example 1 was at 20 and 50mA cm-2The overpotential of the current density of (1) is only 285 mV and 313mV, and the excellent electrocatalytic oxygen generation activity is shown. Meanwhile, as can be seen from fig. 5, the prepared electrocatalyst has good stability in an alkaline electrolyte and is stable for 10 hours at a constant voltage, which indicates that the hollow triangular nickel-cobalt hydroxide nanosheet has strong structural stability. The hollow nano-sheet can effectively prevent catalytic aggregation, so that the high activity of catalytic sites of the hollow nano-sheet can be maintained in a long-time reaction process. The high activity of electrocatalytic oxygen generation mainly comes from the synergistic effect among the large active area, rich active sites and electrons of the hollow structure of the NiCo hydroxide triangular nanosheets. The preparation method of the catalyst is expected to be expanded to the synthesis of other metal hydroxide nanosheets, so that the method is applied to the synthesis of other metal hydroxide nanosheetsThe method has wide application prospect in the field of energy storage and conversion.
The above embodiments are merely illustrative of the concept and implementation of the present invention, and are not restrictive, and technical solutions that are not substantially changed under the concept of the present invention are still within the scope of protection.
Claims (6)
1. A preparation method of nickel cobalt hydroxide nanosheets is characterized by comprising the following steps:
(a) respectively dissolving 2-methylimidazole and cobalt salt in water to obtain solutions, mixing the two solutions, adding foamed nickel, stirring, and taking out to obtain a Co-ZIF nanosheet loaded on the foamed nickel, wherein the loading capacity of the Co-ZIF nanosheet on the foamed nickel is 5-10 mg-cm-2；
(b) Mixing the Co-ZIF nanosheet loaded on the foamed nickel and the nickel salt in ethanol, stirring for 1-10 hours at a constant temperature of 20-80 ℃, and taking out to obtain the nickel-cobalt hydroxide nanosheet loaded on the foamed nickel, wherein the molar ratio of the cobalt salt to the nickel salt is 1: 1-10.
2. The method of making nickel cobalt hydroxide nanoplates of claim 1, wherein the cobalt salt is selected from Co (NO)3)2·6H2O、CoCl2·6H2O、Co(NO3)2Or C4H6CoO4·4H2O; the nickel salt is selected from Ni (NO)3)2·6H2O、Ni(NO3)2、NiSO4Or NiCl2。
3. The method for preparing nickel cobalt hydroxide nanosheets as set forth in claim 1, wherein the Co-ZIF nanosheets have a loading of 6-7 mg-cm on the nickel foam-2(ii) a The molar ratio of the cobalt salt to the nickel salt is 1: 7-8.
4. The method for preparing nickel cobalt hydroxide nanosheets according to claim 1, wherein the Co-ZIF nanosheets supported on nickel foam are obtained after continuous stirring for 3 hours in step (a); and mixing the Co-ZIF nanosheet loaded on the foamed nickel and the nickel salt in ethanol, and stirring for 1-2 hours at a constant temperature of 27 ℃ to obtain the nickel-cobalt hydroxide nanosheet loaded on the foamed nickel.
5. A nickel cobalt hydroxide nanosheet characterized by being prepared by the method of preparing a nickel cobalt hydroxide nanosheet of any one of claims 1 to 4.
6. Nickel cobalt hydroxide nanoplatelets according to claim 5 wherein the nickel cobalt hydroxide nanoplatelets are hollow triangular structures.
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