CN112264018A - Nickel-cobalt oxide nanosheet tubular catalyst and preparation method and application thereof - Google Patents
Nickel-cobalt oxide nanosheet tubular catalyst and preparation method and application thereof Download PDFInfo
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- CN112264018A CN112264018A CN202011203422.0A CN202011203422A CN112264018A CN 112264018 A CN112264018 A CN 112264018A CN 202011203422 A CN202011203422 A CN 202011203422A CN 112264018 A CN112264018 A CN 112264018A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000002135 nanosheet Substances 0.000 title claims abstract description 48
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 46
- 239000002121 nanofiber Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000011258 core-shell material Substances 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000012924 metal-organic framework composite Substances 0.000 claims description 8
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000001588 bifunctional effect Effects 0.000 abstract description 8
- 239000010411 electrocatalyst Substances 0.000 abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
- B01J35/30—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
- 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
- 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
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a nickel cobalt oxide nanosheet tubular catalyst, and a preparation method and application thereof. The ultrathin nickel-cobalt oxide nanosheet tubular catalyst has a hollow nanofiber structure, the surface of the hollow nanofiber structure is of a rough lamellar structure, and meanwhile, the ultrathin nickel-cobalt oxide nanosheet tubular catalyst also has a metal-organic framework Material (MOF) structure. The catalyst provided by the invention provides more reaction active sites, and the tubular catalyst provides a more stable structure foundation, so that stacking agglomeration among the green sheets is not easy to occur, and the stability of the reaction for a longer time is facilitated. Therefore, the catalyst has excellent OER and ORR electrocatalytic activity and is a transition metal-based bifunctional electrocatalyst with great potential. The preparation method of the catalyst is simple to operate, does not need special experimental conditions, is low in cost and is easy for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of catalysts of electrochemistry and new energy, and particularly relates to a nickel-cobalt oxide nanosheet tubular catalyst, and a preparation method and application thereof.
Background
Establishing a global energy conversion system with sustainable development and protecting the environment which we rely on to live is one of the most important challenges facing today. In recent years, the problem of energy supply and climate change caused by the combustion of fossil fuels has attracted much attention. Therefore, in order to reduce the dependence of human social life on fossil fuels, a great deal of renewable clean energy sources (such as solar energy, wind energy, hydroelectric power, and the like) need to be developed to meet the human demand for energy.
The zinc-air battery has ideal energy density and power density, and is expected to be widely applied in the field of energy conversion and storage, so that the zinc-air battery draws high attention of researchers at home and abroad. Among them, the air electrode is the core area of the oxygen catalytic reaction, and is the focus of the whole zinc-air battery research. The electrochemical Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) play a crucial role in the performance of zinc air batteries. At present, in an alkaline medium, the noble metal Pt has the highest ORR catalytic activity, Ir, Ru and oxides thereof have excellent OER catalytic activity, but the high cost, scarcity and non-bifunctional catalytic activity of a single noble metal catalyst seriously restrict the commercial application of the single noble metal catalyst.
In recent years, non-noble metal bifunctional catalysts and electrodes thereof are gradually new catalyst candidates due to the characteristics of high activity, low cost, abundant varieties and the like, and the development of non-noble metal bifunctional catalysts with catalytic performance equivalent to that of noble metal catalysts is particularly important.
However, the structural defects of the existing non-noble metal bifunctional catalyst are limited by the blocky materials, the number of reaction active sites is small, and the electron mobility is influenced; and the problem that the single transition metal material has poor conductivity and influences the activity of the electrocatalytic reaction.
Disclosure of Invention
In view of the problems of the prior art, according to one aspect of the present invention, it is an object of the present invention to provide an ultra-thin nickel cobalt oxide nanosheet tubular catalyst, which comprises nickel cobalt oxide, and has both OER and ORR activities, and can be used as a novel bifunctional electrocatalyst.
The ultrathin nickel-cobalt oxide nanosheet tubular catalyst has a hollow nanofiber-shaped structure, the length of the catalyst is 1-10 microns, the hollow diameter of the catalyst is 10 nm-1 micron, the surface of the hollow nanofiber-shaped structure is a rough lamellar structure, the length of the lamellar structure is 1-10 microns, the thickness of the lamellar structure is 1-50 nm, and meanwhile, the bimetallic nickel-cobalt oxide of the catalyst also has a metal-organic framework (MOF) structure, wherein the molar ratio of metal nickel to cobalt is 1: 20-1: 0.05.
Preferably, the molar ratio of metallic nickel to cobalt in the catalyst is 1: 2.
According to another aspect of the invention, another object of the invention is to provide a preparation method of the ultrathin nickel cobalt oxide nanosheet tubular catalyst, which comprises the following steps:
1) dissolving ammonium molybdate in strong acid, uniformly dispersing by ultrasonic wave, transferring to a reaction kettle, carrying out hydrothermal reaction at 160-240 ℃ for 8-24 hours, cooling to room temperature, washing with water and alcohol, and drying at 60 ℃ to obtain white MoO3A nanofiber;
2) mixing terephthalic acid (PTA), polyvinylpyrrolidone (PVP-30) and NiCl2·6H2O and CoCl2·6H2Dissolving O in a mixed solution of water, ethanol and Dimethylformamide (DMF) in a volume ratio of 1:1:1 to prepare a NiCo-MOF precursor solution;
3) the MoO prepared in the step 1) is added3Uniformly dispersing the nano fibers in the NiCo-MOF precursor solution in the step 2), carrying out hydrothermal reaction at 120-180 ℃ for 4-12 hours, cooling to room temperature after the reaction is finished, centrifugally collecting, and carrying out vacuum drying at 70 ℃ to obtain the MoO with the core-shell structure3@ NiCo-MOF composite catalyst precursor wherein MoO3The concentration of the nano-fibers is 0.01-10 mg/mL;
4) the MoO obtained in the step 3) is treated3Adding the precursor of the @ NiCo-MOF composite catalyst into ammonia water for etching treatment to remove MoO3The nano-fiber contains 0.01-10M ammonia water and MoO3The concentration of the @ NiCo-MOF is 0.1-100 g/L, and the etching time is 10 min-5 h.
5) And (3) annealing the ultrathin nickel-cobalt oxide nanosheet tubular catalyst obtained in the step 4) in air at 200-400 ℃ for 1-4 hours.
Preferably, the strong acid in step 1) is selected from nitric acid or hydrochloric acid.
According to another aspect of the invention, another object of the invention is to provide the use of the ultrathin nickel cobalt oxide nanosheet tubular catalyst as an electrode material or catalyst in a battery, capacitor, electrolytic cell.
Preferably, according to the use of the ultrathin nickel cobalt oxide nanosheet tubular catalyst of the present invention, the battery is a zinc-air battery.
Advantageous effects
The shape of the ultrathin nickel-cobalt oxide nanosheet tubular catalyst is stable and controllable, the ultrathin flaky structure of the ultrathin nickel-cobalt oxide nanosheet tubular catalyst provides more reactive active sites, the tubular catalyst provides a more stable structural foundation, the stacking and agglomeration among the nanosheets are not easy to occur, and the reaction stability for a longer time is facilitated. Therefore, the catalyst has excellent OER and ORR electrocatalytic activity and is a transition metal-based bifunctional electrocatalyst with great potential. The preparation method of the catalyst is simple to operate, does not need special experimental conditions, is low in cost and is easy for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic flow chart of a preparation method of the ultrathin nickel cobalt oxide nanosheet tubular catalyst according to the invention.
FIG. 2 is a MoO prepared in example 13SEM image of nanofibers.
FIG. 3 is a MoO prepared in example 13SEM picture of @ NiCo-MOF.
Fig. 4 is an SEM image of the ultra-thin nickel cobalt hydroxide nanosheet tubular catalyst after etching in example 1.
Fig. 5 is an SEM image of the ultra-thin nickel cobalt oxide nanosheet tubular catalyst after annealing in example 1.
FIG. 6 is a MoO prepared in example 13Mapping graph of element distribution of @ NiCo-MOF.
Fig. 7(a) is an ORR test chart of ultra-thin nickel cobalt oxide nanosheet tubular catalysts prepared in examples 1 and 2 and comparative examples 1 to 3; fig. 7(b) is an OER test chart of the ultra-thin nickel cobalt oxide nanosheet tubular catalysts prepared in examples 1 and 2 and comparative examples 1 to 3.
Fig. 8 is an SEM image of the electrocatalyst prepared in comparative example 2.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
When Organic small molecules are used as ligands and central atoms, the compound with a periodic network structure is formed by self-assembly and is called a Metal-Organic framework (MOF) compound, the MOF compound is a coordination polymer which develops rapidly in recent decades, has a three-dimensional pore structure, generally takes Metal ions as connecting points, is supported by Organic ligands to form a space 3D extension, is another important novel porous material besides zeolite and carbon nanotubes, and is widely applied to catalysis, energy storage and separation.
The ultrathin nickel-cobalt oxide nanosheet tubular catalyst disclosed by the invention has a hollow nanofiber structure and a metal-organic framework (MOF) structure at the same time, so that the catalyst has good OER and ORR dual-functional electrocatalytic performance.
Specifically, the ultrathin nickel cobalt oxide nanosheet tubular catalyst according to the present invention has a hollow nanofibrous structure with a length of 1 to 10 μm and a hollow diameter of 10nm to 1 μm, the surface of the hollow nanofibrous structure is a rough lamellar structure with a length of 1 μm to 10 μm and a lamellar thickness of 1nm to 50nm, while the bimetallic nickel cobalt oxide of the catalyst also has a metal-organic framework (MOF) structure with a molar ratio of metallic nickel to cobalt of 1:20 to 1: 0.05.
Wherein MoO3The nanofibers act as templating agents, their length has no particular effect on the final product properties, but the MoO3The diameter (coarseness) of the nanofibers has some effect on the final product properties. If MoO3Too small a diameter of the nanofibers (too fine) results in too little NiCo-MOF growing thereon, which may not form a tubular catalyst; if MoO3If the diameter of the nanofibers is too large (too thick), the bonding between the nanosheets after ammonia corrosion is not strong enough, and collapse may occur.
Fig. 1 is a schematic flow chart of a preparation method of the ultrathin nickel cobalt oxide nanosheet tubular catalyst according to the invention. The preparation method of the ultrathin nickel cobalt oxide nanosheet tubular catalyst comprises the following steps: dissolving ammonium molybdate in nitric acid solution, uniformly dispersing, and preparing to obtain MoO by a hydrothermal method3A nanofiber; adding MoO3Ultrasonically dispersing the nanofibers in a precursor solution of NiCo-MOF, and carrying out hydrothermal treatment to obtain MoO3A @ NiCo-MOF core-shell structure; use of ammonia water for MoO3Etching the @ NiCo-MOF core-shell structure to obtain the ultrathin nickel-cobalt hydroxide nanosheet tubular catalyst; annealing and oxidizing in the air to obtain an ultrathin nickel-cobalt oxide nanosheet tubular catalyst; and finally, using the prepared ultrathin nickel-cobalt oxide nanosheet tubular catalyst as an OER and ORR dual-function electrocatalyst for testing.
Wherein MoO is added3The nano-fibers are uniformly dispersed in a NiCo-MOF precursor solution to carry out hydrothermal reaction to prepare MoO with a core-shell structure3@NiCo-MIn the OF composite catalyst precursor step, the MoO is based on a 100mLNiCo-MOF precursor solution3The concentration of the nano-fiber is 0.01-10 mg/mL, if MoO3Too small a concentration of nanofibers, e.g., less than 0.01mg/mL, the excess NiCo-MOF cannot be completely coated on the MoO3On the surface of the nanofibers if MoO3Too high a nanofiber concentration, e.g., greater than 10mg/mL, then MoO3The NiCo-MOF coated on the surface of the nanofiber is too small in amount, and the number of layers is too small after ammonia etching, so that the mechanical stability is poor.
The molar ratio between the Ni salt and the Co salt is not particularly limited, and is any ratio as long as it does not affect the properties of the final product, but the molar ratio of the metallic nickel and cobalt may be 1:20 to 1:0.05, more preferably 1:2, for reasons of convenience of handling and the like.
The preparation method designed by the invention is simple to operate, does not need special experimental conditions and is low in cost. The product has stable and controllable appearance, the ultrathin sheet structure provides more reaction active sites, the tubular catalyst provides more stable structure foundation, and the stacking and agglomeration among the sheets are not easy to occur, thereby being beneficial to the reaction stability for a longer time. Therefore, the catalyst has excellent OER and ORR electrocatalytic activity and is a transition metal-based bifunctional electrocatalyst with great potential.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
The structure, properties and theoretical basis of the samples prepared in the examples are characterized and illustrated by means of characterization means such as SEM, TEM and EDX-mapping in the following examples. The reagents and solvents disclosed below were purchased from Sigma-Aldrich, SEM, mapping, EDX by Zeiss, Sigma 500; electrochemical performance was tested by Shanghai Chenghua CHI 760E electrochemical workstation and Gamry RDE710 rotating disk electrode.
Example 1
1) Dissolving 3g of ammonium molybdate in 100mL of 2.5M nitric acid, ultrasonically dispersing for 20min until the solution is uniform, transferring the solution to a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 20 hours, cooling to room temperature, washing with water and alcohol, and drying at 60 ℃ to obtain white MoO3A nanofiber;
2) 0.225g PTA, 2.25g PVP-30, 0.03g NiCl2·6H2O and 0.03g CoCl2·6H2Dissolving O in 100mL of mixed solution of water, ethanol and DMF (the volume ratio of the water to the ethanol to the DMF is 1:1:1) to prepare NiCo-MOF precursor solution;
3) 0.1g of MoO was taken3Dispersing the nano-fibers in the precursor solution of NiCo-MOF obtained in the step 2), carrying out hydrothermal reaction for 10 hours at 150 ℃, cooling to room temperature, centrifugally collecting, and then carrying out vacuum drying at 70 ℃ to obtain MoO with a core-shell structure3A @ NiCo-MOF composite catalyst precursor;
4) 1M ammonia water is used for reacting MoO obtained in the step 3)3Etching the @ NiCo-MOF core-shell structure for 30min, wherein the MoO is3The concentration of @ NiCo-MOF is 15g/L, the ultrathin nickel-cobalt hydroxide nanosheet tubular catalyst is obtained, and MoO is removed3A nanofiber;
5) and annealing for 2 hours at 300 ℃ in the air to obtain the ultrathin nickel-cobalt oxide nanosheet tubular catalyst.
FIG. 2 shows the MoO prepared in step 1) of this example3SEM image of the nanofiber, from which the MoO prepared can be seen3The nanofibers are uniform in structure, about 1 to 10 μm in length and about 10nm to 1 μm in diameter.
FIG. 3 shows the MoO prepared in step 3) of this example3SEM image of @ NiCo-MOF, from which it can be seen that in MoO3A multilayer result of NiCo-MOF was formed on the surface of the nanofibers.
Fig. 4 and 5 are SEM images of the ultra-thin nickel cobalt hydroxide nanosheet tubular catalyst etched in step 4) and the ultra-thin nickel cobalt oxide nanosheet tubular catalyst annealed in step 5) of this example, respectively. It can be seen from the figure that the etched and annealed products maintain the fibrous morphology while the surface is a rough sheet structure and MoO3The nanofibers have been etched away.
FIG. 6 shows the MoO prepared in this example3An element distribution mapping diagram of the @ NiCo-MOF ultrathin nickel cobalt hydroxide nanosheet tubular catalyst indicates that the final product contains the elements Ni, Co and O and does not contain Mo element.
Example 2
1) Dissolving 5g of ammonium molybdate in 150mL of 2.5M nitric acid, ultrasonically dispersing for 20min until the solution is uniform, transferring the solution to a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 18 hours, cooling to room temperature, washing with water and alcohol, and drying at 60 ℃ to obtain white MoO3A nanofiber;
2) 0.225g PTA, 2.25g PVP-30, 0.05g NiCl2·6H2O and 0.07g CoCl2·6H2Dissolving O in 100mL of mixed solution of water, ethanol and DMF (the volume ratio of the water to the ethanol to the DMF is 1:1:1) to prepare NiCo-MOF precursor solution;
3) 0.3g of MoO was taken3Dispersing the nano-fibers in the precursor solution of NiCo-MOF obtained in the step 2), carrying out hydrothermal reaction at 170 ℃ for 9 hours, cooling to room temperature, centrifugally collecting, and then carrying out vacuum drying at 70 ℃ to obtain MoO with a core-shell structure3A @ NiCo-MOF composite catalyst precursor;
4) the MoO obtained in step 3) was treated with 3M ammonia3Etching the @ NiCo-MOF core-shell structure for 1h, wherein the MoO is3The concentration of @ NiCo-MOF is 10g/L, and the ultrathin nickel-cobalt hydroxide nanosheet tubular catalyst is obtained, and MoO is removed3A nanofiber;
5) and annealing for 2 hours at 280 ℃ in the air to obtain the ultrathin nickel-cobalt oxide nanosheet tubular catalyst.
Comparative example 1
1) Dissolving 3g of ammonium molybdate in 100mL of 2.5M nitric acid, ultrasonically dispersing for 20min until the solution is uniform, transferring the solution to a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 20 hours, cooling to room temperature, washing with water and alcohol, and drying at 60 ℃ to obtain white MoO3A nanofiber;
2) dissolving 0.225g of PTA, 2.25g of PVP-30, 0.03g of NiCl2 & 6H2O and 0.03g of CoCl2 & 6H2O in 100mL of a mixed solution of water, ethanol and DMF (the volume ratio of the three is 1:1:1) to prepare a NiCo-MOF precursor solution;
3) 0.1g of MoO was taken3Dispersing the nano-fibers in the precursor solution of NiCo-MOF obtained in the step 2), carrying out hydrothermal reaction for 10 hours at 150 ℃, cooling to room temperature, centrifugally collecting, and then carrying out vacuum drying at 70 ℃ to obtain MoO with a core-shell structure3A @ NiCo-MOF composite catalyst precursor;
4) annealing at 300 deg.C for 2 hr in air.
The nanosheet array cannot be formed without the ammonia etching step, and the product has the advantages of small specific surface, few active sites and poor electrocatalytic performance as shown in figure 2.
Comparative example 2
1) Dissolving 3g of ammonium molybdate in 100mL of 2.5M nitric acid, ultrasonically dispersing for 20min until the solution is uniform, transferring the solution to a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 20 hours, cooling to room temperature, washing with water and alcohol, and drying at 60 ℃ to obtain white MoO3A nanofiber;
2) 0.225g PTA, 2.25g PVP-30, 0.06g CoCl2·6H2Dissolving O in 100mL of mixed solution of water, ethanol and DMF (the volume ratio of the water to the ethanol to the DMF is 1:1:1) to prepare a Co-MOF precursor solution;
3) 0.1g of MoO was taken3Dispersing the nano-fibers in the precursor solution of the Co-MOF obtained in the step 2), carrying out hydrothermal reaction for 10 hours at 150 ℃, cooling to room temperature, centrifugally collecting, and then carrying out vacuum drying at 70 ℃ to obtain the MoO with the core-shell structure3@ Co-MOF composite catalyst precursor;
4) 1M ammonia water is used for reacting MoO obtained in the step 3)3Etching the @ Co-MOF core-shell structure, wherein the concentration of ammonia water is 1M, the concentration of MoO3@ Co-MOF is 15g/L, and the etching time is 30min.
5) Annealing at 300 deg.C for 2 hr in air.
No Ni exists, the size of the etched nanosheet is extremely small, the interior of the nanosheet also exists in a blocky shape, the diameter is too large, the specific surface area is small, and the catalytic activity is greatly influenced (figure 8)
Comparative example 3
1) 0.225g PTA, 2.25g PVP-30, 0.03g NiCl2·6H2O and 0.03g CoCl2·6H2O dissolved in 100mL of water, ethanol and DMF (Tris)Preparing a NiCo-MOF precursor solution in a mixed solution with the volume ratio of 1:1: 1);
2) dispersing 0.1g of carbon nanofibers in the precursor solution of NiCo-MOF obtained in the step 1), carrying out hydrothermal reaction for 10 hours at 150 ℃, cooling to room temperature, centrifugally collecting, and then drying in vacuum at 70 ℃ to obtain a C @ NiCo-MOF composite catalyst precursor with a core-shell structure;
3) and (3) etching the C @ NiCo-MOF core-shell structure obtained in the step 2) by using 1M ammonia water, wherein the concentration of the ammonia water is 1M, the concentration of MoO3@ NiCo-MOF is 15g/L, and the etching time is 30min.
4) Annealing at 300 deg.C for 2 hr in air.
The template is replaced by carbon fiber, a nanosheet array can be formed after ammonia etching, but the template is not removed, and a hollow structure cannot be formed.
Test example 1
The ultra-thin nickel cobalt oxide nanosheet tubular catalysts prepared in examples 1 and 2 and comparative examples 1 to 3 were subjected to OER and ORR dual-function electrocatalytic performance testing.
ORR and OER polarization curves were tested at 30 ℃ on CHI 760D electrochemical workstation and Gamry RDE710 rotating disk electrode, and all electrochemical experiments used a three-electrode electrochemical system including a saturated calomel electrode (reference electrode), a Pt electrode (auxiliary counter electrode) and a catalyst modified glassy carbon electrode (working electrode). 10mg of the electrocatalyst was uniformly dispersed in 1mL of isopropanol and 4mL of ultrapure water, and 10. mu.L of the electrocatalyst dispersion was dropwise added onto a glassy carbon electrode having a diameter of 5mm, and dried at room temperature. All potentials are scaled relative to the reversible hydrogen electrode potential (RHE). The ORR test was performed in 0.1M KOH saturated with oxygen and the OER test was performed in 1M KOH saturated with nitrogen.
Fig. 7(a) is an ORR test chart of ultra-thin nickel cobalt oxide nanosheet tubular catalysts prepared in examples 1 and 2 and comparative examples 1 to 3; fig. 7(b) is an OER test chart of the ultra-thin nickel cobalt oxide nanosheet tubular catalysts prepared in examples 1 and 2 and comparative examples 1 to 3. The figure shows that the ultrathin nickel-cobalt oxide nanosheet tubular catalyst prepared by the method has good OER and ORR dual-functional electrocatalytic performance.
Claims (6)
1. An ultra-thin nickel cobalt oxide nanosheet tubular catalyst has a hollow nanofibrous structure with a length of 1 to 10 μm and a hollow diameter of 10nm to 1 μm, the surface of the hollow nanofibrous structure is a rough lamellar structure with a length of 1 μm to 10 μm and a thickness of 1nm to 50nm, while the bimetallic nickel cobalt oxide of the catalyst also has a metal-organic framework (MOF) structure with a molar ratio of metallic nickel to cobalt of 1:20 to 1: 0.05.
2. An ultra-thin nickel cobalt oxide nanosheet tubular catalyst as recited in claim 1, wherein the molar ratio of metallic nickel to cobalt is 1: 2.
3. The method of preparing an ultra-thin nickel cobalt oxide nanosheet tubular catalyst of claim 1 or 2, comprising the steps of:
1) dissolving ammonium molybdate in strong acid, uniformly dispersing by ultrasonic wave, transferring to a reaction kettle, carrying out hydrothermal reaction at 160-240 ℃ for 8-24 hours, cooling to room temperature, washing with water and alcohol, and drying at 60 ℃ to obtain white MoO3A nanofiber;
2) mixing terephthalic acid (PTA), polyvinylpyrrolidone (PVP-30) and NiCl2·6H2O and CoCl2·6H2Dissolving O in a mixed solution of water, ethanol and Dimethylformamide (DMF) in a volume ratio of 1:1:1 to prepare a NiCo-MOF precursor solution;
3) the MoO prepared in the step 1) is added3Uniformly dispersing the nano fibers in the NiCo-MOF precursor solution in the step 2), carrying out hydrothermal reaction at 120-180 ℃ for 4-12 hours, cooling to room temperature after the reaction is finished, centrifugally collecting, and carrying out vacuum drying at 70 ℃ to obtain the MoO with the core-shell structure3@ NiCo-MOF composite catalyst precursor wherein MoO3The concentration of the nano-fibers is 0.01-10 mg/mL;
4) the MoO obtained in the step 3) is treated3Adding the @ NiCo-MOF composite catalyst precursor into ammonia waterEtching to remove MoO3The nano-fiber contains 0.01-10M ammonia water and MoO3The concentration of the @ NiCo-MOF is 0.1-100 g/L, and the etching time is 10 min-5 h;
5) and (3) annealing the ultrathin nickel-cobalt oxide nanosheet tubular catalyst obtained in the step 4) in air at 200-400 ℃ for 1-4 hours.
4. The method according to claim 3, wherein the strong acid in step 1) is selected from nitric acid or hydrochloric acid.
5. Use of an ultra-thin nickel cobalt oxide nanosheet tubular catalyst of claim 1 or 2 as an electrode material or catalyst in batteries, capacitors and electrolytic cells.
6. Use according to claim 5, the battery being a zinc-air battery.
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