CN111995760A - Cobalt-metal organic framework nanosheet and preparation method and application thereof - Google Patents

Cobalt-metal organic framework nanosheet and preparation method and application thereof Download PDF

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CN111995760A
CN111995760A CN202010691422.3A CN202010691422A CN111995760A CN 111995760 A CN111995760 A CN 111995760A CN 202010691422 A CN202010691422 A CN 202010691422A CN 111995760 A CN111995760 A CN 111995760A
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cobalt
nanosheet
reaction
bipyridine
metal organic
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庞欢
柏杨
郑莎莎
刘春丽
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Yangzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J35/33—
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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 cobalt-metal organic framework nanosheet and a preparation method and application thereof2+The organic ligand is pyridine and 4, 4' -bipyridine, the nano-sheet is in a two-dimensional sheet structure, the length is 500-4000 nm, the width is 200-1000 nm,the thickness is 10-70 nm, the material can be used as an electrocatalytic oxygen evolution reaction electrode material and a super capacitor electrode material, has uniform appearance and large length-width/thickness ratio, and shows excellent oxygen evolution reaction electrocatalytic capacity and super capacitor electricity storage capacity.

Description

Cobalt-metal organic framework nanosheet and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrocatalytic water decomposition and supercapacitor electrode material preparation, and particularly relates to a cobalt-metal organic framework material and a preparation method thereof, and application of the cobalt-metal organic framework material in electrocatalytic water decomposition and supercapacitors.
Background
Currently, most of the energy sources used for industrial production and transportation depend on fossil energy sources such as coal, natural gas and oil. The consumption of these limited resources and their impact on the environment has forced researchers to seek alternative energy sources. The hydrogen energy has the advantages of cleanness, reproducibility, high thermal efficiency and the like, plays a great role in promoting pollution control and greenhouse effect, and attracts more and more attention in recent years. Electrocatalytic water splitting is an effective means of producing hydrogen, but relies on catalysis by electrocatalytic materials. At present, the commercialized electrocatalytic material mainly reduces the electrolytic overpotential through noble metals such as platinum, ruthenium, iridium and the like and oxides thereof, but has the defects of low storage capacity, high price, easy poisoning and limited large-scale commercial application. Therefore, the research on the scientific problems related to the replacement of the noble metal catalyst by the non-noble metal catalyst provides theoretical and experimental basis for realizing cost reduction and promoting the commercialization of novel energy sources. Meanwhile, with the increasing demand of the modern society for mobile and portable energy sources, the research and development of a green and safe chemical power source with high power density and high energy density is the key research point of the modern times. A supercapacitor, also known as an electrochemical capacitor, is an energy storage device between a conventional capacitor and a secondary battery. Supercapacitors have faster charge and discharge rates and higher power densities than batteries; compared with a fuel cell, the source of the electrode material is wider, and the manufacturing cost of the device is lower. At present, the super capacitor has been widely applied in the fields of electronic equipment, mobile communication, electric vehicles and the like.
In the electrocatalytic water decomposition reaction, the initial potential of the oxygen evolution reaction generated on the anode is larger, the required potential is larger than the equilibrium potential, namely, the overpotential is high, the reaction kinetics is slow, the stability is poor, and the further application and development of electrochemical hydrogen production are restricted. The wide application of the super capacitor is limited by the capacitance, the stability of the electrode material of the super capacitor is improved, andconductivity is a critical issue to be addressed. Therefore, in order to improve the electrochemical performance of the electrode, increase the catalytic activity and enhance the energy storage efficiency of the super capacitor, research and development of novel functional materials have attracted attention from a plurality of researchers (J. Mater. Chem. A, 2019, 7, 15851; Small, 2019, 1903410; Adv. Funct. Mater., 2017, 27, 1605784.)
Metal organic framework Materials (MOFs), also known as coordination polymers, are one of the most rapidly developing and most pyrophoric materials in recent years. The porous material has a three-dimensional pore structure, generally takes metal ions as connecting points, is supported by organic ligands to form space 3D extension, is another important novel porous material except zeolite and carbon nano tubes, and is widely applied to catalysis, energy storage and separation. Compared with other materials, because of large specific surface area, high porosity and easy structure control, MOFs are considered to be one of the most promising materials in the future nano-field. At present, MOFs have been developed to some extent as oxygen evolution reaction catalysts and supercapacitor electrode materialsAngew. Chem. Int. Ed., 2019, 58, 7051; Adv. Mater., 2019, 31, 1901139; Adv. Mater. Interfaces2018, 5, 1701548.), but the catalytic activity and the stability of the catalyst still need to be further improved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a cobalt-metal organic framework material which can improve the electrocatalytic activity and stability of oxygen evolution reaction and improve the energy storage efficiency of a super capacitor.
A cobalt-metal organic framework nanosheet is formed by self-assembling cobalt ions and organic ligands, wherein the cobalt ions are divalent ions Co2+The organic ligand is pyridine and 4, 4' -bipyridine.
Preferably, the nano-sheet is in a two-dimensional sheet structure, the length is 500-4000 nm, the width is 200-1000 nm, and the thickness is 10-70 nm.
The preparation steps of the metal organic framework nanosheet are as follows: mixing cobalt sulfate, 4' -bipyridine and water, stirring and mixing uniformly, adding pyridine and a solvent, continuing stirring, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating reaction, and after the reaction is finished, centrifuging, washing and drying in vacuum to obtain the metal organic framework nanosheet.
Preferably, the cobalt sulfate is a hydrated or non-hydrated sulfate having the formula CoSO4Or CoSO4·nH2O; n is 1, 6, 7.
Preferably, the ratio of the amount of cobalt sulfate to the amount of 4, 4' -bipyridine is (0.2-5.0): 1, preferably 1: 1.
Preferably, the mass ratio of 4, 4' -bipyridine to pyridine is 0.1 to 0.5, preferably 0.2 to 0.35.
Preferably, the solvent is any one of methanol, ethanol and N, N' -dimethylformamide, and preferably methanol or ethanol.
Preferably, the temperature-raising reaction temperature is 80-200 deg.CoC, preferably 100 to 120 oC; the reaction time is 12-48 h, preferably 12-24 h.
Compared with the prior art, the metal organic framework nanosheet based on non-noble metal cobalt provided by the invention is uniform in appearance, large in length-width/thickness ratio, excellent in oxygen evolution reaction electrocatalysis capability and supercapacitor electricity storage capability, and wide in application prospect in the aspects of hydrogen energy preparation, intelligent wearing, new energy automobiles and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the cobalt-metal organic framework material Co-MOF-1 in example one, and the scale bar is 2 μm.
FIG. 2 is an image of a Transmission Electron Microscope (TEM) image of the cobalt-metal organic framework material Co-MOF-1 of example one, with a scale bar of 1 μm.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the cobalt-metal organic framework material Co-MOF-2 of example two, with a scale bar of 2 μm.
FIG. 4 is a cyclic voltammogram of the working electrode prepared in example three, with a sweep rate of 0.05V/s.
FIG. 5 is a polarization curve obtained by scanning the working electrode prepared in example three by Linear Sweep Voltammetry (LSV) at a sweep rate of 0.005V/s.
FIG. 6 is a cyclic voltammogram of the working electrode prepared in example four, with a sweep rate of 0.02V/s.
FIG. 7 is a charge/discharge curve of the working electrode prepared in the fourth example under a constant current with a current density of 0.5A/g and a test voltage range of 0-0.5V.
Detailed Description
The invention is further illustrated, but not limited, by the following examples in connection with the accompanying drawings and the detailed description.
The cobalt-metal organic framework material prepared by the method is subjected to Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) imaging tests, and the results show that the cobalt-metal organic framework material has a nanosheet shape, is basically uniform in shape and size, is 500-4000 nm long, is 200-1000 nm wide, is smooth in nanosheet surface and uniform in thickness, and is 10-70 nm thick.
The cobalt-metal organic framework nanosheet prepared by the method is used as an active material, is modified on the surface of a glassy carbon electrode and is used as an electrocatalytic oxygen evolution reaction electrode, so that the electrocatalytic capacity of the oxygen evolution reaction can be improved, and the method comprises the following steps:
and (3) sufficiently oscillating and ultrasonically mixing the nanosheets and the binder solution (for 30-60 minutes), then decorating 2-5 mu L of the nanosheets on the surface of a glassy carbon electrode, and airing at room temperature or placing the electrode in an oven for drying to obtain the electrocatalytic oxygen evolution reaction electrode.
The binder is a solution of a perfluorosulfonic acid polymer, the solvent is water, ethanol or a mixture of water and ethanol in any proportion, the volume ratio of water to ethanol is preferably 1: 2-2: 1, and the mass fraction content of the perfluorosulfonic acid polymer is 0.1% -2.0%, preferably 0.2% -0.5%.
The prepared electro-catalytic oxygen evolution reaction electrode is used as a working electrode, a carbon rod is used as a counter electrode, Hg/HgO is used as a reference electrode to form a three-electrode device, an electrochemical workstation is used for carrying out catalytic oxygen evolution reaction in 1.0 mol/L potassium hydroxide solution, the scanning rate is controlled to be 0.005-0.2V/s under the potential of 0.1-0.6V, cyclic voltammetry scanning is carried out, Linear Scanning Voltammetry (LSV) scanning is carried out at the scanning rate of 0.005V/s to obtain a polarization curve, and the magnitude of overpotential is inspected.
The cobalt-metal organic framework nanosheet prepared by the method is used as an active material, loaded on a current collector and used as a supercapacitor electrode, and the electricity storage capacity can be improved, and the method comprises the following steps:
sequentially ultrasonically cleaning foamed nickel with the length of 5 cm, the width of 1 cm and the thickness of 0.8-1.6 mm for 10 minutes by using 1.0 mol/L HCl solution, acetone and deionized water respectively, and drying for later use;
mixing the nanosheets, the binder and the conductive agent, grinding for 15-45 minutes, adding 2 mL of solvent, continuously grinding for 2-5 minutes to enable the nanosheets, the binder and the conductive agent to be mixed uniformly, dipping the mixed solution by using the foamed nickel to enable the area covered by the active substance to be 1 cm multiplied by 1 cm, drying, pressing under the pressure of 5-12 MPa to form a thin foil serving as a working electrode of the supercapacitor, weighing and recording the mass of the loaded substance, and calculating the mass of the loaded active substance on each foamed nickel according to the proportion.
Wherein, in the mixture of the nano-sheets, the binder and the conductive agent, the mass ratio of the nano-sheets is 80-90%. The conductive agent is any one of acetylene black, graphene, carbon nanotubes, conductive carbon black and the like, and the mass ratio of the conductive agent to the nano sheet to the mixture of the binder and the conductive agent is 2-8%. The binder is one of polytetrafluoroethylene, polyvinylidene fluoride and cellulose, and the mass ratio of the binder to the mixture of the nanosheets, the binder and the conductive agent is 5-15%. Solvents include, but are not limited to, ethanol, ethylene glycol, propanol, isopropanol. Current collectors include, but are not limited to, nickel foam, copper foam.
And (3) taking the prepared supercapacitor electrode as a working electrode, forming a three-electrode system with a platinum wire and an Hg/HgO electrode, placing the three-electrode system in a 3.0 mol/L potassium hydroxide solution for measurement, controlling the scanning rate to be 0.02-0.2V/s within a voltage range of 0-0.6V, performing cyclic voltammetry scanning, and observing a current response result. The charge and discharge test is carried out under the constant current with the current density of 0.5-20A/g, and the charge and discharge curve within the voltage range of 0-0.5V is tested.
Example one
The embodiment provides a preparation method of a cobalt-metal organic framework material, which comprises the following steps:
adding CoSO4·7H2O (1.0 mmol, 0.28 g), 4' -bipyridine (1 mmol, 0.16 g)g) After mixing with 25 mL of deionized water, the mixture was stirred at room temperature for 1 hour to dissolve.
1.0 g pyridine and 5 mL ethanol were added to the solution, stirring was continued for 15 minutes, then transferred to a 50 mL Teflon lined reactor and placed in a preheated 100 mL autoclaveoC, reacting in an oven for 20 hours.
And after the reaction is finished, slowly cooling to room temperature, centrifugally collecting a sample, washing with water and ethanol for three times, and placing the sample in a vacuum drying oven to dry at an inner chamber temperature to obtain the cobalt-metal organic framework material Co-MOF-1.
SEM test of Co-MOF-1: FIG. 1 is a scanning electron microscope photograph of Co-MOF-1 magnified 10000 times, and test results show that the Co-MOF-1 is in a flaky shape, the shape and the size are basically uniform, the length is in the range of 500-4000 nm, and the width is in the range of 200-1000 nm.
TEM test of Co-MOF-1: FIG. 2 is a transmission electron micrograph of Co-MOF-1, further confirming that Co-MOF-1 is a sheet-like morphology with uniform thickness.
Example two
The embodiment provides a preparation method of a cobalt-metal organic framework material, which comprises the following steps:
adding CoSO4·7H2O (2.0 mmol, 0.28 g), 4' -bipyridine (2 mmol, 0.16 g) and 50 mL of deionized water were mixed, and then stirred at room temperature for 30 minutes to dissolve them.
3.0 g pyridine and 10 mL methanol were added to the solution, stirred for 10 minutes, transferred to a 100 mL Teflon lined reactor and placed in a preheated 90 mL reactoroC, reacting in an oven for 12 hours.
And after the reaction is finished, slowly cooling to room temperature, centrifugally collecting a sample, washing with water and ethanol for three times, and placing the sample in a vacuum drying oven to dry at an inner chamber temperature to obtain the cobalt-metal organic framework material Co-MOF-2.
SEM test of Co-MOF-2: FIG. 3 is a scanning electron micrograph of Co-MOF-2 magnified 10000 times, and the test results also show that Co-MOF-2 has a flaky morphology and is substantially uniform in shape and size.
EXAMPLE III
The embodiment provides an application of an electrocatalytic oxygen evolution reaction of a cobalt-metal organic framework nanosheet:
a glassy carbon electrode having a diameter of 3 mm was polished with a sandpaper having a 1 μm alumina suspension adsorbed thereon and a sandpaper having a 0.05 μm alumina suspension adsorbed thereon, respectively. And (3) sequentially placing the polished glassy carbon electrode in absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic cleaning for 3 minutes, and then drying for later use.
5 mg of the cobalt-metal organic framework material Co-MOF-1 prepared in the first embodiment is dispersed in 1 mL of a 1% perfluorosulfonic acid polymer water/ethanol (1:1, volume ratio) solution, ultrasonically mixed to prepare a mixed solution, then 5 mu L of the mixed solution is modified on the surface of a clean glassy carbon electrode with the diameter of 3 mm by a coating method, and the Co-MOF-1 electrocatalytic working electrode is obtained after natural airing.
1.0 mol/L potassium hydroxide solution is prepared as electrolyte. The Co-MOF-1 electrocatalytic electrode, a carbon rod and an Hg/HgO electrode form a three-electrode system, and the three-electrode system is placed in a 1.0 mol/L potassium hydroxide solution for determination. And under the potential of 0.1-0.6V, controlling the scanning rate to be 0.05V/s, and carrying out cyclic voltammetry scanning. FIG. 4 is a cyclic voltammogram of a Co-MOF-1 electrocatalytic working electrode at a sweep rate of 0.05V/s, and the reduction potential at 0.32V can be assigned to Co3+/Co2+. Linear Sweep Voltammetry (LSV) scanning was performed at a sweep rate of 0.005V/s to obtain a polarization curve, and the magnitude of the overpotential was examined. FIG. 5 is a polarization curve at 0.005V/s sweep rate for a Co-MOF-1 electrocatalytic working electrode at 10 mA/cm2The overpotential at current density was 288 mV, showing excellent oxygen evolution catalytic efficiency.
Example four
This example provides a supercapacitor application of cobalt-metal organic frameworks:
and (3) sequentially ultrasonically cleaning foamed nickel with the length of 5 cm, the width of 1 cm and the thickness of 0.8-1.6 mm for 10 minutes by using 1.0 mol/L HCl solution, acetone and deionized water respectively, and drying for later use.
Co-MOF-18.0 mg, acetylene black 1.5 mg, and polytetrafluoroethylene 0.5 mg were mixed and ground for 30 minutes, and 2 mL of isopropyl alcohol was added and grinding was continued for 2 minutes. Dipping the mixed solution by using foamed nickel to ensure that the area covered by the active substance is 1 cm multiplied by 1 cm, drying and pressing into a thin foil (10 MPa) to be used as a working electrode of the Co-MOF-1 super capacitor.
3.0 mol/L potassium hydroxide solution is prepared as electrolyte. The Co-MOF-1 super capacitor working electrode, a platinum wire and an Hg/HgO electrode form a three-electrode system, and the three-electrode system is placed in a 3.0 mol/L potassium hydroxide solution for determination. And under the potential of 0-0.6V, controlling the scanning rate to be 0.01V/s, carrying out cyclic voltammetry scanning, and observing a current response result. FIG. 6 is a cyclic voltammogram of a working electrode of a Co-MOF-1 supercapacitor at a sweep rate of 0.01V/s, and oxidation and reduction potentials at 0.47 and 0.31V can be assigned to Co3+/Co2+. And (3) carrying out charge-discharge test under the constant current with the current density of 0.5A/g, and testing the charge-discharge curve within the voltage range of 0-0.5V. FIG. 7 is a charge-discharge curve of a working electrode of a Co-MOF-1 supercapacitor under constant current with the current density of 0.5A/g, the capacity can reach 208.4F/g, and good electrochemical energy storage potential is shown.

Claims (10)

1. The cobalt-metal organic framework nanosheet is characterized in that the nanosheet is formed by self-assembly of cobalt ions and organic ligands, wherein the cobalt ions are divalent ions Co2+The organic ligand is pyridine and 4, 4' -bipyridine.
2. Nanosheet of claim 1, wherein the nanosheet is a two-dimensional platelet structure having a length of 500 to 4000 nm, a width of 200 to 1000 nm, and a thickness of 10-70 nm.
3. A process for the preparation of nanoplatelets according to claim 1 or 2 comprising the steps of: mixing cobalt sulfate, 4' -bipyridine and water, stirring and mixing uniformly, adding pyridine and a solvent, continuing stirring, heating the mixed solution in a reaction kettle for reaction, and centrifuging, washing and vacuum drying after the reaction is finished to obtain the nanosheet.
4. The method of claim 3, wherein the cobalt sulfate is cobalt sulfateIs hydrated or non-hydrated cobalt sulfate and has a structural formula of CoSO4Or CoSO4·nH2O; n is 1, 6, 7.
5. The method according to claim 3, wherein the ratio of the amount of cobalt sulphate to the amount of 4, 4' -bipyridine species is (0.2-5.0): 1, preferably 1: 1.
6. The process according to claim 3, wherein the mass ratio of 4, 4' -bipyridine to pyridine is 0.1 to 0.5, preferably 0.2 to 0.35.
7. The method according to claim 3, wherein the solvent is any one of methanol, ethanol, and N, N' -dimethylformamide, preferably methanol or ethanol.
8. The method according to claim 3, wherein the reaction temperature is increased to 80 to 200%oC, preferably 100 to 120oC; the reaction time is 12-48 h, preferably 12-24 h.
9. Use of nanoplatelets according to claim 1 or 2 as electrocatalytic oxygen evolution reaction electrode material.
10. Use of nanoplatelets according to claim 1 or 2 as supercapacitor electrode material.
CN202010691422.3A 2020-07-17 2020-07-17 Cobalt-metal organic framework nanosheet and preparation method and application thereof Pending CN111995760A (en)

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CN113249754A (en) * 2021-05-19 2021-08-13 扬州大学 Preparation method and application of Co/Fe-MOF LDHs composite material
CN113699551A (en) * 2021-08-23 2021-11-26 陕西科技大学 IrO2Nanoparticle self-assembly modified metal oxide electrode, preparation method and application
CN114512351A (en) * 2022-02-11 2022-05-17 辽宁大学 Co2+-Zr2+/(2-MeIm)x@ PPy/GO nanosheet and modified electrode and application thereof

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