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CN-122000371-A - Application of copper cluster-based metal covalent organic framework material as catalyst in methanol-assisted zinc-air battery

CN122000371ACN 122000371 ACN122000371 ACN 122000371ACN-122000371-A

Abstract

The invention belongs to the field of electrocatalysis, and particularly discloses application of a copper cluster-based metal covalent organic framework material as a catalyst in a methanol-assisted zinc-air battery. The invention solves the problems of slow transfer of two half-reaction protons of discharging and charging in the prior methanol-assisted zinc-air battery by utilizing the copper cluster-based metal covalent organic framework material.

Inventors

  • QIAO SHANLIN
  • HAN JIAMING
  • Zhai pengda
  • WANG YUE
  • LI QING
  • ZHANG BOYING
  • LIU HAINING

Assignees

  • 河北科技大学

Dates

Publication Date
20260508
Application Date
20260306

Claims (10)

  1. 1. Use of copper cluster-based metal-covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries.
  2. 2. The use of claim 1, wherein the copper-cluster-based metal-covalent organic framework material is supported on an air cathode of the methanol-assisted zinc-air cell.
  3. 3. The use according to claim 2, wherein the copper cluster-based metal-covalent organic framework material is supported on the air cathode in a loading amount of 1-1.5mg/cm 2 .
  4. 4. The use of claim 1, wherein the copper cluster-based metal-covalent organic framework material is synthesized by any one of the following methods: in inert atmosphere, synthesizing a copper cluster-based metal covalent organic framework material by a solvent-thermal method under the conditions of a solvent and a catalyst by using a cyclic trinuclear copper cluster precursor and a second monomer; synthesizing the copper cluster-based metal covalent organic framework material by a solvothermal method through a third monomer, copper salt and a fourth monomer under the conditions of a solvent and a catalyst; And 3, synthesizing the copper cluster-based metal covalent organic framework material by using a fifth monomer, cuprous oxide and a sixth monomer through a room-temperature synthesis method under the condition of a catalyst.
  5. 5. The use according to claim 4, wherein, The cyclic trinuclear copper cluster precursor is synthesized by cuprous oxide and a first monomer through a solvothermal method under the condition of a solvent, or the cyclic trinuclear copper cluster precursor is a cyclic trinuclear copper metal cluster containing amino or aldehyde groups; The first monomer is 3, 5-dimethyl-1H-pyrazol-4-amine and/or 1H-pyrazole-4-formaldehyde; the second monomer is at least one of trialdehyde phloroglucinol, 1, 4-phthalic dialdehyde, 2, 5-dihydroxyterephthalic acid, terephthalic acid, 1,2,4, 6-tetramethylpyridine iodide, 1,2,4, 6-tetramethylpyridine-1-tetrafluoroboric acid and 2, 2'' (benzene 1,3, 5-triyl) triacetonitrile.
  6. 6. The use according to claim 4, wherein, The copper salt is copper nitrate trihydrate; The third monomer is 3, 5-dimethyl-1H-pyrazol-4-amine; the fourth monomer is pyromellitic dianhydride.
  7. 7. The use according to claim 4, wherein, The fifth monomer is at least one of 4-amino-2-methoxybenzoyl hydrazine, 1H-pyrazole-4-formyl hydrazine and 1,3, 5-tri- (4-aminophenyl) triazine; the sixth monomer is at least one of 1H-pyrazole-4-formaldehyde, 1,3, 5-tri (4-formylphenyl) benzene and pyruvic acid.
  8. 8. The use according to claim 5, wherein the solvent of method 1, the solvent for synthesizing the copper cluster precursor and the solvent of method 2 are each independently at least one of 1,3, 5-trimethylbenzene, absolute ethanol, 1, 4-dioxane, N dimethylformamide, water, pyridine, o-dichlorobenzene and N-butanol.
  9. 9. The use according to claim 5, wherein the catalyst of process 1, the catalyst of process 2 and the catalyst of process 3 are each independently at least one of pyridine, piperidine, 1, 8-diaza [5,4,0] undecene-7 and an aqueous acetic acid solution at a concentration of 4-6 mol/L.
  10. 10. The process according to claim 4, wherein in the process 1 and the process 2 the volume ratio of catalyst to solvent is independently 1 (5-20).

Description

Application of copper cluster-based metal covalent organic framework material as catalyst in methanol-assisted zinc-air battery Technical Field The invention belongs to the field of electrocatalysis, and in particular relates to an application of a copper cluster-based metal-covalent organic framework material as a catalyst in a methanol-assisted zinc-air battery. Background Rechargeable zinc-air batteries (ZABs) are considered to be promising energy storage systems in the next generation renewable energy technology because of their higher theoretical energy density, intrinsic safety, and zinc-rich use. However, their practical performance is fundamentally limited by oxygen reduction (ORR) and Oxygen Evolution (OER) pairs, where OER, which is slow in nature and kinetically irreversible, dominates the energy loss during charging, leading to large overpotential, low round trip efficiency, and fast catalyst degradation. To solve this fundamental bottleneck, replacing OER with a thermodynamically and kinetically more favorable anodic reaction has recently become an effective strategy. Among them, the Methanol Oxidation Reaction (MOR) in alkaline medium shows lower activation barrier and faster charge transfer kinetics, and can greatly reduce the charge voltage without generating oxygen intermediate with high oxidability. Unlike OER, MOR proceeds preferentially to formate by successive C-H bond activation and dehydrogenation, involving adsorptionCH3OH、CH 3 OHCO intermediates, the rate-determining step of which is usually associated with C-H bond cleavage orHCO oxidation is involved. Therefore, the MOR can be used for replacing OER to obviously reduce the charge overpotential and the charge voltage and inhibit the catalyst degradation, so that the methanol-assisted zinc-air battery (ZMAB) structure has higher voltage efficiency and lower energy consumption. However, the implementation of this hybrid ZMAB places new stringent requirements on the cathode catalyst. In addition to providing high ORR activity during discharge, the catalyst must remain stable and kinetic efficient in systems where the anodic reaction is radically altered. Importantly, both ORR and MOR are controlled by a multi-step proton-coupled electron transfer (PCET) process. Inspired by the biological enzyme system, the hydrogen bond network acts as a directional proton "lead" to realize quick and efficient PCET, and the construction of an artificial hydrogen bond assisted proton transmission path becomes a reasonable strategy for overcoming the limitation of double reactions. Therefore, there is a need to propose the use of copper cluster-based metal-covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries. Disclosure of Invention The invention aims at overcoming the defects of the prior art and provides application of a copper cluster-based metal-covalent organic framework material as a catalyst in a methanol-assisted zinc-air battery. The invention solves the problems of slow transfer of two half-reaction protons of discharging and charging in the prior methanol-assisted zinc-air battery by utilizing the copper cluster-based metal covalent organic framework material. In order to achieve the above object, the present invention provides the use of copper cluster-based metal-covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries. According to the present invention, preferably, the copper cluster-based metal-based covalent organic framework material is supported on an air cathode of the methanol-assisted zinc-air battery. According to the present invention, preferably, the copper cluster-based metal-covalent organic framework material is supported on the air cathode at a loading of 1-1.5mg/cm 2. According to the invention, preferably, the copper cluster-based metal-covalent organic framework material is synthesized by adopting any one of the following methods: in inert atmosphere, synthesizing a copper cluster-based metal covalent organic framework material by a solvent-thermal method under the conditions of a solvent and a catalyst by using a cyclic trinuclear copper cluster precursor and a second monomer; synthesizing the copper cluster-based metal covalent organic framework material by a solvothermal method through a third monomer, copper salt and a fourth monomer under the conditions of a solvent and a catalyst; And 3, synthesizing the copper cluster-based metal covalent organic framework material by using a fifth monomer, cuprous oxide and a sixth monomer through a room-temperature synthesis method under the condition of a catalyst. According to the invention, preferably, the cyclic trinuclear copper cluster precursor is synthesized by cuprous oxide and a first monomer through a solvothermal method under the condition of a solvent, or the cyclic trinuclear copper cluster precursor is a cyclic trinuclear copper metal cluster containing amino or aldehyde groups. According to the