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

Abstract

The invention belongs to the field of electro-catalysis, 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 copper-cluster-based metal covalent organic framework material is utilized to solve the problem of slow proton transfer of two half reactions of discharging and charging in the current methanol-assisted zinc-air battery.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalysis, and more specifically, relates to the application of copper cluster-based metal covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries. Background Technology

[0002] Rechargeable zinc-air batteries (ZABs) are considered promising energy storage systems among next-generation renewable energy technologies due to their high theoretical energy density, inherent safety, and zinc-rich utilization. However, their practical performance is fundamentally limited by the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) pair, with the inherently slow and kinetically irreversible OER dominating energy loss during charging, resulting in high overpotential, low round-trip efficiency, and rapid catalyst degradation.

[0003] To address this fundamental bottleneck, replacing OER with thermodynamically and kinetically more favorable anodic reactions has recently become an effective strategy. Among these, methanol oxidation (MOR) in alkaline media exhibits a lower activation barrier and faster charge transfer kinetics, enabling a significant reduction in charging voltage without generating highly oxidizing oxygen intermediates. Unlike OER, MOR preferentially proceeds via sequential CH bond activation and dehydrogenation to formate, involving adsorption... CH3OH, CH3O and HCO intermediates, the rate-determining steps of which are usually associated with CH bond cleavage or The oxidation of HCO is involved. Therefore, replacing OER with MOR can significantly reduce the charging overpotential and charging voltage, and inhibit catalyst degradation, thereby giving the methanol-assisted zinc-air battery (ZMAB) structure higher voltage efficiency and lower energy consumption.

[0004] However, the realization of this hybrid ZMAB places new and stringent requirements on the cathode catalyst. Besides providing high ORR activity during discharge, the catalyst must maintain stability and kinetic efficiency in a system where the anodic reaction is fundamentally altered. Importantly, both ORR and MOR are controlled by a multi-step proton-coupled electron transfer (PCET) process. Inspired by biological enzyme systems, hydrogen bond networks act as directional proton "wires" to achieve rapid and efficient PCET; therefore, constructing artificial hydrogen bond-assisted proton transport pathways becomes a rational strategy to overcome this dual reaction limitation.

[0005] Therefore, there is an urgent need to propose the application of copper cluster-based metal covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by proposing the application of copper cluster-based metal covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries. This invention utilizes copper cluster-based metal covalent organic framework materials to solve problems such as slow proton transfer in the two half-reactions of discharge and charging in current methanol-assisted zinc-air batteries.

[0007] To achieve the above objectives, this invention provides the application of copper cluster-based metal covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries.

[0008] According to the present invention, preferably, the copper cluster-based metal covalent organic framework material is loaded on the air cathode of the methanol-assisted zinc-air battery.

[0009] According to the present invention, preferably, the loading amount of the copper cluster-based metal covalent organic framework material on the air cathode is 1-1.5 mg / cm³. 2 .

[0010] According to the present invention, preferably, the copper cluster-based metal covalent organic framework material is synthesized by any of the following methods: Method 1: Under an inert atmosphere, the copper cluster-based metal covalent organic framework material is synthesized by a solvothermal method using a cyclic trinuclear copper cluster precursor and a second monomer in the presence of a solvent and a catalyst. Method 2: The copper cluster-based metal covalent organic framework material is synthesized by a solvothermal method using a third monomer, a copper salt, and a fourth monomer under solvent and catalyst conditions; Method 3: The copper cluster-based metal covalent organic framework material is synthesized by room temperature synthesis of the fifth monomer, cuprous oxide and the sixth monomer under the condition of a catalyst.

[0011] According to the present invention, preferably, the cyclic trinuclear copper cluster precursor is synthesized by a solvothermal method from cuprous oxide and a first monomer under solvent conditions, or the cyclic trinuclear copper cluster precursor is a cyclic trinuclear copper metal cluster containing amino or aldehyde groups.

[0012] According to the present invention, preferably, the first monomer is 3,5-dimethyl-1H-pyrazole-4-amine and / or 1H-pyrazole-4-carboxaldehyde.

[0013] According to the present invention, preferably, the second monomer is at least one selected from trialdehyde phloroglucinol, 1,4-o-phthalaldehyde, 2,5-dihydroxyterephthalic acid, terephthalic acid, 1,2,4,6-tetramethylpyridine iodide (TMPI-I), 1,2,4,6-tetramethylpyridine-1-tetrafluoroboronic acid (TMPI-BF4), and 2,2′,2′′(benzene-1,3,5-trimethyl)triacetonitrile.

[0014] According to the present invention, preferably, the copper salt is copper nitrate trihydrate.

[0015] According to the present invention, preferably, the third monomer is 3,5-dimethyl-1H-pyrazole-4-amine.

[0016] According to the present invention, preferably, the fourth monomer is pyromellitic dianhydride.

[0017] According to the present invention, preferably, the fifth monomer is at least one selected from 4-amino-2-methoxybenzoylhydrazine, 1H-pyrazole-4-carbamoylhydrazine, and 1,3,5-tris-(4-aminophenyl)triazine.

[0018] According to the present invention, preferably, the sixth monomer is at least one selected from 1H-pyrazole-4-carboxaldehyde, 1,3,5-tris(4-formylphenyl)benzene and pyruvic acid.

[0019] In this invention, the copper cluster-based metal covalent organic framework material is connected by at least one of imine, hydrazone, quinoline, polyimide, vinyl cyanide, ethylene, and β-ketoenamine.

[0020] According to the present invention, preferably, the solvent of method 1, the solvent for synthesizing the cyclic trinuclear copper cluster precursor, and the solvent of method 2 are each independently at least one selected from 1,3,5-trimethylbenzene, anhydrous ethanol, 1,4-dioxane, N,N-dimethylformamide, water, pyridine, o-dichlorobenzene, and n-butanol.

[0021] According to the present invention, preferably, the catalyst of method 1, the catalyst of method 2 and the catalyst of method 3 are each independently at least one selected from pyridine, piperidine, 1,8-diazacyclo[5,4,0]undecene-7 and an aqueous solution of acetic acid with a concentration of 4-6 mol / L.

[0022] According to the present invention, preferably, in methods 1 and 2, the volume ratio of catalyst to solvent is independently 1:(5-20).

[0023] The technical principle of this invention, which uses copper cluster-based metal covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries, is as follows: Covalent organic frameworks (COFs) possess ordered porous structures, modular molecular designs, and precisely tunable chemical functions. In particular, metal-coordinated COFs (MCOFs) enable deterministic control over the coordination geometry and electronic structure of the metal center, while allowing the integration of hydrogen-bonding functional groups into the framework. This unique combination provides a powerful means of constructing continuous hydrogen bond networks within well-defined channels, thereby facilitating the directed transport of protons between catalytically active sites.

[0024] The beneficial effects of the technical solution of the present invention are as follows: This invention utilizes copper cluster-based metal covalent organic framework materials to solve the problems of slow proton transfer and high charging voltage in the two half-reactions of current methanol-assisted zinc-air batteries or traditional zinc-air batteries. This results in the battery exhibiting excellent catalytic activity in oxygen reduction, oxygen evolution, and methanol oxidation, as well as extremely high charge-discharge stability. The methanol-assisted zinc-air battery of this invention exhibits excellent power density and stability.

[0025] The copper cluster-based metal covalent organic framework material of the present invention has a well-defined active site (copper cluster), an ordered hydrogen bond network, and a large specific surface area. The well-defined active site (copper cluster) combined with the introduction of hydrogen bonds can effectively promote proton-electron coupling and transfer. At the same time, the copper cluster, as the active center, endows the copper cluster-based metal covalent organic framework material with excellent bifunctional electrocatalytic activity (bifunctional means that the copper cluster-based metal covalent organic framework material of the present invention can simultaneously and efficiently catalyze the two half-reactions of methanol-assisted zinc-air battery discharge (ORR) and charge (MOR).

[0026] The method for preparing the copper cluster-based metal covalent organic framework material of the present invention is low in cost and simple.

[0027] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0028] The above and other objects, features and advantages of the present invention will become more apparent from the more detailed description of exemplary embodiments of the invention in conjunction with the accompanying drawings.

[0029] Figure 1 The batteries of Examples 1 and 2 are shown at a current density of 5 mA cm⁻¹. -2 Constant current cyclic charge-discharge curves ("voltage" means voltage; "time" means time; "VE" means voltage efficiency; "replace electrolyte" means electrolyte replacement).

[0030] Figures 2-9 The bonding configuration of the copper cluster-based metal covalent organic framework material of the present invention is shown. Figure 2 The imine is used, corresponding to Preparation Example 2 and Preparation Example 3; Figure 3 For imine and hydrazone bonds, see preparation example 4; Figure 4 It is a hydrazone bond, corresponding to preparation example 5; Figure 5 The product is quinoline, corresponding to preparation example 6; Figure 6 It is a β-ketoenamine, corresponding to Preparation Example 7; Figure 7 For polyimide, see Preparation Example 8; Figure 8 For ethylene, corresponding to Preparation Example 9 and Preparation Example 10; Figure 9 (This refers to vinyl cyanide, corresponding to preparation example 11). Detailed Implementation

[0031] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0032] Preparation Example 1: Synthesis of Cu-CTC, a precursor to a cyclic trinuclear copper cluster

[0033] Cuprous oxide (Cu₂O, 21.5 mg, 0.15 mmol) and 3,5-dimethyl-1H-pyrazole-4-amine (HL, 50.0 mg, 0.45 mmol) were reacted under an inert atmosphere in a 10 mL Pyrex tube at 120 °C for 72 h, using a mixed solution of pyridine and anhydrous ethanol as the solvent. The cyclic trinuclear copper cluster precursor Cu-CTC (colorless needle-like crystals) was collected by centrifugation and drying.

[0034] Preparation Example 2: Synthesis of Copper Cluster-Based Metal Covalent Organic Framework Material COF-Cu3-TA (Method 1)

[0035] Cu-CTC (26.1 mg, 0.05 mmol obtained in Preparation Example 1) and 1,4-o-phenylenedialdehyde (6.7 mg, 0.05 mmol) were added to a 10 mL Schlenk tube to obtain a mixture. Solvents 1,4-dioxane (0.5 mL), 1,3,5-trimethylbenzene (0.5 mL), and 6M acetic acid aqueous solution (0.1 mL) were added to the mixture. The Schlenk tube was then frozen in liquid nitrogen at 77 K and degassed using argon in three freeze-thaw cycles. The Schlenk tube was then flame-sealed under vacuum. The material in the Schlenk tube was then heated to room temperature and then heated at 120 °C for 72 h to obtain a solid powder. After filtration, washing with ethoxyacetic acid, DMF (N,N-dimethylformamide), and acetone, the powder was dried under vacuum at 100 °C for 12 h to obtain the product COF-Cu3-TA.

[0036] Preparation Example 3: Synthesis of Copper Cluster-Based Metal Covalent Organic Framework Material COF-Cu3-DHBA (Method 1)

[0037] Cu-CTC (26.1 mg, 0.05 mmol obtained in Preparation Example 1) and 2,5-dihydroxyterephthalic acid (DHBA, 12.46 mg, 0.075 mmol) were added to a 10 mL Schlenk tube to obtain a mixture. To the mixture, o-dichlorobenzene (0.25 mL), n-butanol (1.25 mL), and a 6M aqueous acetic acid solution (0.15 mL) were added. The Schlenk tube was then frozen in liquid nitrogen at 77 K and degassed using three freeze-thaw cycles with argon. The Schlenk tube was then flame-sealed under vacuum. The material in the Schlenk tube was then heated to room temperature and then heated at 120 °C for 72 h to obtain a solid powder. After filtration, washing with ethoxyacetic acid, DMF (N,N-dimethylformamide), and acetone, the powder was dried under vacuum at 100 °C for 12 h to obtain the product COF-Cu3-DHBA.

[0038] Preparation Example 4: Synthesis of JNU-302, a copper cluster-based metal covalent organic framework material (Method 3)

[0039] 4-Amino-2-methoxybenzoylhydrazide (AMBH, 40.8 mg, 0.225 mmol), 1H-pyrazole-4-carboxaldehyde (Pz-CHO, 43.5 mg, 0.45 mmol), and Cu2O (0.225 mmol, 32.3 mg) were weighed into a test tube, and 6 mL of acetic acid aqueous solution (4 M) was added. The mixture was sonicated continuously at 25 °C for 1 h to obtain a solid. The solid was first centrifuged three times with ethanol, and then Soxhlet extracted with ethanol for 24 h. Finally, the sample was vacuum dried at 80 °C for 12 h to obtain JNU-302.

[0040] Preparation Example 5: Synthesis of JNU-310, a copper cluster-based metal covalent organic framework material (Method 3)

[0041] Weigh 1H-pyrazole-4-carboxyhydrazide (Pz-CON2H3, 56.8 mg, 0.45 mmol), 1,3,5-tris(4-formylphenyl)benzene (TFPB, 58.6 mg, 0.15 mmol), and Cu2O (0.225 mmol, 32.3 mg) into a test tube, add 6 mL of acetic acid aqueous solution (4 M), and sonicate continuously at 25 °C for 1 h to obtain a solid. First, centrifuge three times with ethanol, then perform Soxhlet extraction with ethanol for 24 h. Finally, vacuum dry the sample at 80 °C for 12 h to obtain JNU-310.

[0042] Preparation Example 6: Synthesis of NSU-211, a copper cluster-based metal covalent organic framework material (Method 3)

[0043] Weigh 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol), 1H-pyrazole-4-carboxaldehyde (Pz-CHO, 43.5 mg, 0.45 mmol), Cu₂O (0.225 mmol, 32.3 mg), and pyruvic acid (30 μL) into a test tube, add 6 mL of acetic acid aqueous solution (4 M), and sonicate continuously at 25 °C for 1 h to obtain a solid. First, centrifuge three times with ethanol, then extract with ethanol using a Soxhlet extractor for 24 h. Finally, vacuum dry the sample at 80 °C for 12 h to obtain NSU-211.

[0044] Preparation Example 7: Synthesis of Cu-TP, a copper cluster-based metal covalent organic framework material (Method 1)

[0045] (1) Synthesis of Cu3L3, a precursor of cyclic trinuclear copper clusters

[0046] Weigh 200 mg of copper nitrate trihydrate (0.83 mmol) and 96 mg of 1H-pyrazole-4-carboxaldehyde (1.0 mmol) into a 25 mL sample vial, add 6.7 mL of N,N-dimethylformamide (DMF), 5 mL of H2O, and 6.7 mL of ethanol. Seal the sample vial and place it in a 100 °C oven for 12 h. After the reaction is complete, pale yellow needle-like crystals are obtained. Filter the obtained solid and soak it in water for 3 days, changing the water every 8 h. Finally, wash the obtained Cu3L3 three times with acetone (30 mL × 3), and dry it under vacuum at 120 °C for 24 h, with a yield of 65%. (2) Synthesis of Cu-TP Cu3L3 (0.05 mmol) and terephthalic acid (TP, 0.05 mmol) were added to a 10 mL Schlenk tube to obtain a mixture. Solvents 1,4-dioxane (0.5 mL), 1,3,5-trimethylbenzene (0.5 mL), and 6M acetic acid aqueous solution (0.1 mL) were added to the mixture. The Schlenk tube was then frozen in liquid nitrogen at 77 K and degassed using three freeze-thaw cycles with argon. The Schlenk tube was then flame-sealed under vacuum. The material in the Schlenk tube was then heated to room temperature and then heated at 120 °C for 72 h to obtain a solid powder. After filtration, washing with ethoxyacetic acid, DMF (N,N-dimethylformamide), and acetone, the powder was dried under vacuum at 100 °C for 12 h to obtain the product Cu-TP.

[0047] Preparation Example 8: Synthesis of copper cluster-based metal covalent organic framework material 3D-JNM-4 (Method 2)

[0048] 3,5-Dimethyl-1H-pyrazole-4-amine (HL, 22 mg, 0.2 mmol), PMDA (pyromellitic dianhydride, 21.8 mg, 0.1 mmol), Cu(NO3)2·3H2O (48.2 mg, 0.2 mmol), 2 mL anhydrous ethanol, 2 mL LDM, and 0.2 mL pyridine were placed in a 25 mL reaction flask and heated in an oven at 120 °C for 72 h. After cooling to room temperature, the orange solid was separated by filtration and washed with NMP (N-methylpyrrolidone) and EtOH (ethanol). The obtained product was dried under vacuum at 120 °C for 8 h to obtain orange crystalline powder 3D-JNM-4.

[0049] Preparation Example 9: Synthesis of copper cluster-based metal covalent organic framework material TMPI-Cu-MCOF-I (Method 1)

[0050] (1) Preparation of TMPI-I

[0051] 2,4,6-Trimethylpyridine (2 mL, 15 mmol) and iodomethane (2.85 mL, 45 mmol) were dissolved in 10 mL of CH₂Cl₂ and stirred overnight at room temperature. The mixture was filtered to obtain a white solid. The solid was then recrystallized from methanol, filtered again, and dried under vacuum at 60 °C for 6 h. (2) Synthesis of TMPI-Cu-MCOF-I Cu3L3 (23.9 mg, 0.05 mmol, obtained from Preparation Example 7) and TMPI-I (1,2,4,6-tetramethylpyridine iodide, 13.2 mg, 0.05 mmol) were added to a 10 mL Schlenk tube to obtain a mixture; N,N-dimethylformamide (DMF, 1.5 mL), o-dichlorobenzene (o-DCB, 0.5 mL), and 100 μL piperidine (catalyst) were added to the mixture, and the mixture was sonicated for 5 min; then it was heated in liquid nitrogen at 77 K. The Schlenk tube was frozen and degassed using nitrogen through three freeze-thaw cycles. The Schlenk tube was then sealed with a flame under vacuum. The material in the Schlenk tube was then heated to room temperature and then heated at 180°C for 96 hours to obtain the reactant. The reactant was washed 2-3 times with DMF, methanol, and CH2Cl2 (to remove oligomers or monomers from the system) and then dried under vacuum at 100°C for 12 hours. The solid was collected by filtration to obtain the reddish-brown metal cluster-based crystalline porous material TMPI-Cu-MCOF-I.

[0052] Preparation Example 10: Synthesis of copper cluster-based metal covalent organic framework material TMPI-Cu-MCOF-BF4 (Method 1)

[0053] (1) Preparation of TMPI-BF4

[0054] 2,4,6-Trimethylpyridine (2.5 mmol) and tetrafluoroboric acid (2.5 mmol) were mixed in an ice-water bath, and the temperature was then raised to room temperature and maintained for 1 h. After the reaction was complete, the solvent in the resulting mixture was evaporated under reduced pressure and then dried under vacuum. Trimethyl orthoformate (7.5 mmol) was added to the solid obtained above, and the mixture was kept in a microwave reactor (150 °C, 100 W) for 10 min. After cooling to room temperature, the resulting solid was filtered, washed with ethanol, and dried under vacuum to obtain the product (TMPI-BF4). (2) Synthesis of TMPI-Cu-MCOF-BF4 Cu3L3 (23.9 mg, 0.05 mmol, obtained from Preparation Example 7) and TMPI-BF4 (1,2,4,6-tetramethylpyridine-1-tetrafluoroboric acid, 9.2 mg, 0.05 mmol) were added to a 10 mL Schlenk tube to obtain a mixture; N,N-dimethylformamide (DMF, 1.5 mL), 1,3,5-trimethylbenzene (0.5 mL), and 100 μL piperidine (catalyst) were added to the mixture, and the mixture was sonicated for 5 min; then, the Sc was heated in liquid nitrogen at 77 K. Schlenk tubes were frozen and degassed using nitrogen through three freeze-thaw cycles. The Schlenk tubes were then flame-sealed under vacuum. The material in the Schlenk tubes was then heated to room temperature and then heated at 180°C for 96 hours to obtain the reactants. The reactants were washed 2-3 times with DMF, methanol, CH2Cl2, and ethanol (to remove oligomers or monomers from the system), and then vacuum-dried at 100°C for 12 hours. The solid was collected by filtration to obtain the wine-red ionic vinyl metal covalent organic framework material TMPI-Cu-MCOF-BF4.

[0055] Preparation Example 11: Synthesis of copper cluster-based metal covalent organic framework material TN-Cu3L3COF (Method 1)

[0056] Cu3L3 (47.6 mg, 0.1 mmol, obtained from Preparation Example 7) and 2,2′,2′′(benzene 1,3,5-trimethyl)triacetonitrile (TN, 19.5 mg, 0.1 mmol) were added to a 10 mL Schlenk tube to obtain a mixture; o-dichlorobenzene (1 mL) and 1,8-diazacyclo[5,4,0]undecene-7 (catalyst, DBU, 0.2 mL) were added to the mixture and sonicated for 5 min; then the mixture was heated in liquid nitrogen at 77 K. The Schlenk tube was frozen and degassed using nitrogen through three freeze-thaw cycles. The Schlenk tube was then sealed with a flame under vacuum. The material in the Schlenk tube was then heated to room temperature and then heated at 160°C for 120 h to obtain the reactant. After washing with DMF (to remove oligomers or monomers from the system), the reactant was dried under vacuum at 100°C for 24 h. The solid was collected by filtration to obtain a wine-red ionic vinyl metal covalent organic framework material TN-Cu3L3COF.

[0057] Example 1

[0058] In this embodiment, the copper cluster-based metal covalent organic framework material COF-Cu3-TA prepared in Example 2 is used as a catalyst in a methanol-assisted zinc-air battery. In the methanol-assisted zinc-air battery of this embodiment: Alkaline electrolyte: 6 mol / L KOH, 0.2 mol / L zinc acetate, and 15% methanol (v / v). The carbon paper (1 cm² area) supported by the catalyst (the copper cluster-based metal covalent organic framework material of Preparation Example 2) was used as the air cathode. 2 Catalyst loading 1.25 mg / cm³ 2 The loading method is as follows: the catalyst (the copper cluster-based metal covalent organic framework material of Preparation Example 2) is dispersed in ethanol, coated on carbon paper, and air-dried.

[0059] The zinc sheet is polished smooth to serve as the metal anode.

[0060] Example 2

[0061] The only difference between this embodiment and Example 1 is that this embodiment uses the copper cluster-based metal covalent organic framework material COF-Cu3-DHBA prepared in Example 3 as a catalyst in a methanol-assisted zinc-air battery.

[0062] Test Example 1

[0063] To verify whether the catalytic performance of the copper cluster-based metal covalent organic framework materials prepared in Examples 2 and 3 can be used in practical applications, charge-discharge efficiency and cycle stability tests were conducted on the batteries from Examples 1 and 2 (constant current charge-discharge mode, current density of 5 mA cm⁻¹). -2The Pt / C+IrO2 mixed catalyst (Pt / C 20%, IrO2 20%, mass ratio 1:1) was used as the control sample.

[0064] See results Figure 1 .

[0065] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. Application of copper cluster-based metal covalent organic framework materials as catalysts in methanol-assisted zinc-air batteries.

2. The application according to claim 1, wherein, The copper cluster-based metal covalent organic framework material is loaded onto the air cathode of the methanol-assisted zinc-air battery.

3. The application according to claim 2, wherein, The copper cluster-based metal covalent organic framework material loaded on the air cathode has a loading rate of 1-1.5 mg / cm³. 2 .

4. The application according to claim 1, wherein, The copper cluster-based metal covalent organic framework material is synthesized using any of the following methods: Method 1: Under an inert atmosphere, the copper cluster-based metal covalent organic framework material is synthesized by a solvothermal method using a cyclic trinuclear copper cluster precursor and a second monomer in the presence of a solvent and a catalyst. Method 2: The copper cluster-based metal covalent organic framework material is synthesized by a solvothermal method using a third monomer, a copper salt, and a fourth monomer under solvent and catalyst conditions; Method 3: The copper cluster-based metal covalent organic framework material is synthesized by room temperature synthesis of the fifth monomer, cuprous oxide and the sixth monomer under the condition of a catalyst.

5. The application according to claim 4, wherein, The cyclic trinuclear copper cluster precursor is synthesized by a solvothermal method from cuprous oxide and a first monomer under solvent conditions, 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-pyrazole-4-amine and / or 1H-pyrazole-4-carboxaldehyde; The second monomer is at least one of the following: trialdehyde phloroglucinol, 1,4-o-phthalaldehyde, 2,5-dihydroxyterephthalic acid, terephthalic acid, 1,2,4,6-tetramethylpyridine iodide, 1,2,4,6-tetramethylpyridine-1-tetrafluoroboronic acid, and 2,2′,2′′(benzene-1,3,5-trimethyl)triacetonitrile.

6. The application according to claim 4, wherein, The copper salt is copper nitrate trihydrate; The third monomer is 3,5-dimethyl-1H-pyrazole-4-amine; The fourth monomer is pyromellitic dianhydride.

7. The application according to claim 4, wherein, The fifth monomer is at least one of 4-amino-2-methoxybenzoylhydrazide, 1H-pyrazole-4-carbamoylhydrazide and 1,3,5-tris-(4-aminophenyl)triazine; The sixth monomer is at least one of 1H-pyrazole-4-carboxaldehyde, 1,3,5-tris(4-formylphenyl)benzene, and pyruvic acid.

8. The application according to claim 5, wherein, The solvents of Method 1, the solvents for synthesizing the cyclic trinuclear copper cluster precursor, and the solvents of Method 2 are each independently at least one selected from 1,3,5-trimethylbenzene, anhydrous ethanol, 1,4-dioxane, N,N-dimethylformamide, water, pyridine, o-dichlorobenzene, and n-butanol.

9. The application according to claim 5, wherein, The catalysts of Method 1, Method 2, and Method 3 are each independently selected from at least one of pyridine, piperidine, 1,8-diazacyclic[5,4,0]undecene-7, and an aqueous solution of acetic acid with a concentration of 4-6 mol / L.

10. The application according to claim 4, wherein, In methods 1 and 2, the volume ratio of catalyst to solvent is independently 1:(5-20).

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