Cu-zn metal organic framework material-based electrocatalyst and preparation method and application thereof

Abstract

The application relates to the technical field of electrocatalysts, in particular to an electrocatalyst based on Cu-Zn metal organic framework material and a preparation method and application thereof. x -Zn y MOFs, which is in-situ converted into hollow Cu-Zn metal organic framework material through ligand exchange. Compared with a conventional synthesis method of organic metal framework material, the metal organic framework material obtained through the in-situ conversion method has a hollow structure, so that the specific surface area is larger, and more catalytically active sites can be exposed. Meanwhile, due to the unique structure and electronic properties of the Cu-Zn metal organic framework material, the problems of low selectivity, low Faraday efficiency (FE) and low yield in the existing electrocatalytic synthesis of amino acids are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalysts, in particular to an electrocatalyst based on Cu-Zn metal organic framework material and a preparation method and application thereof. BACKGROUND

[0002] The information disclosed in this Background section is for the purpose of increasing the understanding of the background of the present application and does not necessarily constitute an admission that the information forms part of the prior art already known in this country.

[0003] Amino acids are a class of amphoteric organic compounds containing basic amino groups and acidic carboxyl groups, and are the basic building blocks of biological functional macromolecules of proteins. Amino acids play an important role in life, including the synthesis of neurotransmitters, hormones and nucleotides. In addition, amino acids also have many potential uses, such as: as an additive for animal feed, flavoring agent, biochemical reagent, pharmaceutical agent and cosmetic, etc.

[0004] Currently, amino acids are mainly produced by microbial fermentation process and protein hydrolysis method, which can produce 20 kinds of amino acids that constitute proteins, but the production efficiency is low. In addition, the fermentation process has potential problems such as strict requirement for sterile operation conditions, long time consumption, high energy consumption for microbial culture, and complex product separation and purification process. Other chemical synthesis methods, including Strecker synthesis, Erlenmeyer-Plochl reaction and Bucherer-Bergs reaction, provide more efficient synthesis methods. However, these methods usually rely on the use of toxic compounds such as hydrogen cyanide (HCN) and ammonium cyanide (NH4CN), and non-renewable ammonia, which poses a great challenge to large-scale and sustainable production. Therefore, there is an urgent need to develop cost-effective and efficient amino acid synthesis technology to overcome these limitations.

[0005] The method of electrocatalytic synthesis of amino acids can overcome the above-mentioned shortcomings, unlike traditional methods of synthesizing amino acids, the field of electrocatalytic synthesis of amino acids has not been studied, and there are few reports on the application of electrocatalysts. SUMMARY

[0006] In order to overcome the above problems, the present application provides an electrocatalyst based on Cu-Zn metal organic framework material and a preparation method and application thereof.

[0007] To achieve the above technical purposes, the present application adopts the following technical solutions:

[0008] In a first aspect of the present application, a Cu-Zn metal organic framework material is provided, which has a structural formula as shown in Formula I, Formula II or Formula III:

[0009]

[0010]

[0011] In a second aspect of the present application, a preparation method of the Cu-Zn metal organic framework material is provided.

[0012] (1) Dissolving benzenetricarboxylic acid (H3BTC) in a lye solution to obtain a BTC lye solution; mixing a copper salt solution, a zinc salt solution and the BTC lye solution to obtain a mixed salt solution, adding the mixed salt solution into a sodium salt solution, and reacting to obtain a precursor HKUST-1-Cu x -Zn y MOF;

[0013] (2) dispersing the HKUST-1-Cu x -Zn y MOF in a solvent, adding an organic ligand thereto, stirring to exchange the ligand, and obtaining the Cu-Zn metal organic framework material;

[0014] When the organic ligand is benzenehexathiol (BHT), the Cu-Zn metal organic framework material shown in Formula I is obtained.

[0015] When the organic ligand is 1,3,5-triamino-2,4,6-benzene triol (TABTO), the Cu-Zn metal organic framework material shown in Formula II is obtained.

[0016] When the organic ligand is hexamino benzene hydrochloride (HAB), the Cu-Zn metal organic framework material shown in Formula III is obtained.

[0017] In a third aspect of the present application, the Cu-Zn metal organic framework material is used as an electrocatalyst to catalyze the synthesis of amino acids.

[0018] In a fourth aspect of the present application, a synthesis method of amino acids is provided, which uses the Cu-Zn metal organic framework material as an electrocatalyst to catalyze the synthesis of amino acids from carbon sources and nitrogen sources.

[0019] The present application has the following advantages:

[0020] (1) In the present application, the precursor HKUST-1-Cu x -Zn yMOFs, by ligand exchange in situ conversion into hollow Cu-Zn metal organic framework material. Compared with the traditional synthesis method of organic metal framework material, the metal organic framework material obtained by the method of in situ conversion by ligand exchange has a hollow structure, so it has a larger specific surface area and can expose more catalytically active sites. At the same time, due to the unique structure and electronic properties of Cu-Zn metal organic framework material, the problems of low selectivity, low Faraday efficiency (FE) and low yield in the existing electrocatalytic synthesis of amino acids are solved. The experimental results show that the BHT-Cu9-Zn1 synthesized in the examples in the present application can maintain a FE of more than 80% for up to 240 hours, showing excellent stability.

[0021] (2) The Cu-Zn metal organic framework material provided by the present application has successfully synthesized leucine, alanine, valine, phenylalanine, methylalanine, norvaline, glycine, tryptophan, homophenylalanine and cyclobutylglycine 10 kinds of essential amino acids.

[0022] (3) The Cu-Zn metal organic framework material provided by the present application has the advantages of simple preparation process, economy and practicality, no need for special equipment and harsh conditions, practical value and easy scale production. BRIEF DESCRIPTION OF DRAWINGS

[0023] The drawings accompanying the specification of the present application serve to provide a further understanding of the present application, and the illustrative embodiments of the present application and their descriptions serve to explain the present application, and do not constitute an improper limitation on the present application.

[0024] Figure 1 XRD test results of BHT-Cu9-Zn1, TABTO-Cu9-Zn1 and HAB-Cu9-Zn1 prepared in Examples 1, 2 and 3;

[0025] Figure 2 TEM, SEM, HRTEM and HADDF images of BHT-Cu9-Zn1 prepared in Example 1 (a), (b), (c) and (d);

[0026] Figure 3 Linear sweep voltammetry (LSV) curves of BHT-Cu9-Zn1, TABTO-Cu9-Zn1 and HAB-Cu9-Zn1 prepared in Examples 1, 2 and 3;

[0027] Figure 4 Nuclear magnetic resonance (NMR) spectrum of leucine after BHT-Cu9-Zn1 reaction for 2 hours, as well as the structure of the original material, intermediate product and final leucine;

[0028] Figure 5Potentiostatic Faradaic efficiency (FE) of BHT-Cu9-Zn1, TABTO-Cu9-Zn1 and HAB-Cu9-Zn1 for the reduction of nitrate to leucine in a flow cell;

[0029] Figure 6 Potentiostatic Faradaic efficiency (FE) of BHT-Cu9-Zn1 for leucine in a flow cell (a) and the best Faradaic efficiency observed at -1.0 V (b);

[0030] Figure 7 Optimized Faradaic efficiency of BHT-Cu9-Zn1 for different amino acids in a flow cell (a), photo of synthesized leucine (b) and the structure of each amino acid (c). DETAILED DESCRIPTION

[0031] It should be noted that the following detailed description is exemplary in nature and is intended to provide further description of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0032] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting, as the scope of the exemplary embodiments of this application will be limited only by the appended claims. As used herein, unless the context clearly dictates otherwise, the use of the singular herein is intended to include the plural. Furthermore, to the extent that any term is used in the singular herein, we also intend that to include plural forms.

[0033] A first exemplary embodiment of the present application provides a Cu-Zn metal organic framework material, which has a structure as shown in Formula I, Formula II or Formula III:

[0034]

[0035] A second exemplary embodiment of the present application provides a preparation method of the Cu-Zn metal organic framework material as described above, which comprises:

[0036] (1) dissolving benzenetricarboxylic acid (H3BTC) in a lye solution to obtain a BTC lye solution; mixing a copper salt solution, a zinc salt solution and the BTC lye solution to obtain a mixed salt solution, and adding the mixed salt solution into a sodium salt solution to obtain a precursor HKUST-1-Cu x -Zn y MOFs;

[0037] (2) dissolving the HKUST-1-Cu x -Zny The MOFs are dispersed in a solvent, and an organic ligand is added thereto, and ligand exchange occurs upon stirring to obtain a Cu-Zn metal organic framework material;

[0038] When the organic ligand is benzene-1,2,3,5-hexathiol (BHT), a Cu-Zn metal organic framework material represented by Formula I is obtained;

[0039] When the organic ligand is 1,3,5-triamino-2,4,6-benzene triol (TABTO), a Cu-Zn metal organic framework material represented by Formula II is obtained;

[0040] When the organic ligand is hexaaminobenzene hydrochloride (HAB), a Cu-Zn metal organic framework material represented by Formula III is obtained.

[0041] In one or more embodiments, in step (1), the alkali solution comprises one or more of sodium hydroxide solution, ammonia, methylamine, ethylamine, and triethylamine, and preferably is triethylamine.

[0042] In one or more embodiments, in step (1), the molar ratio of the trimesic acid to the basic substance in the alkali solution is 1:5-10, and preferably is 1:7.2.

[0043] In one or more embodiments, in step (1), the concentration of the BTC alkali in the BTC alkali solution is 0.008-0.012 mol / L, and preferably is 0.01 mol / L.

[0044] In one or more embodiments, in step (1), the sodium salt comprises one or more of sodium chloride, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium sulfate, and sodium acetate, and preferably is sodium nitrate.

[0045] In one or more embodiments, in step (1), the solvent of the sodium salt solution comprises one or more of water, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, methanol, or N-methylpyrrolidone, and preferably is a water / ethanol mixed solvent.

[0046] Further preferably, the volume ratio of water to ethanol is 4-6:6-4, and preferably is 1:1.

[0047] In one or more embodiments, in step (1), the concentration of the sodium salt solution is 0.04-0.06 mol / L, and preferably is 0.05 mol / L.

[0048] In one or more embodiments, in step (1), the copper salt comprises one or more of cuprous iodide, cuprous chloride, cuprous nitrate, cuprous bromide, copper iodide, copper chloride, copper nitrate, and copper bromide, and preferably is copper nitrate.

[0049] In one or more embodiments, in step (1), the concentration of the copper salt solution is 0.08-0.1 mol / L, preferably 0.09 mol / L.

[0050] In one or more embodiments, in step (1), the zinc salt includes one or more of zinc gluconate, zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, preferably zinc nitrate.

[0051] In one or more embodiments, in step (1), the concentration of the zinc salt is 0.008-0.012 mol / L, preferably 0.01 mol / L.

[0052] In one or more embodiments, in step (1), the molar ratio of the sodium salt, the copper salt, the zinc salt, and the BTC base in the BTC base solution is 60-90:1.2-1.5:0.12-0.18:0.8-1.2, preferably 75:1.35:0.15:1.

[0053] In one or more embodiments, in step (1), the stirring reaction time is 2-10 min, preferably 5 min.

[0054] In one or more embodiments, in step (2), the solvent includes one or more of water, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, methanol, or N-methylpyrrolidone, preferably a water / methanol mixed solvent.

[0055] Further preferably, the volume ratio of water to methanol is 4-6:6-4, preferably 1:1.

[0056] In one or more embodiments, in step (2), the HKUST-1-Cu x -Zn y The mass ratio of the HKUST-1-Cu

[0057] In one or more embodiments, in step (2), the stirring reaction time is 0.5-2 h, preferably 1 h.

[0058] A third typical embodiment of the present application provides the use of the above-mentioned Cu-Zn metal organic framework material as an electrocatalyst for catalyzing the synthesis of amino acids.

[0059] A fourth aspect of the present application provides a method for synthesizing amino acids, which uses the above-mentioned Cu-Zn metal organic framework material as an electrocatalyst to catalyze the synthesis of amino acids from carbon sources and nitrogen sources.

[0060] In one or more embodiments, the carbon source comprises: an alpha-keto acid; the alpha-keto acid comprises: alpha-ketoisocaproic acid, pyruvic acid, alpha-ketoisovaleric acid, phenylpyruvic acid, alpha-ketoisobutyric acid, alpha-ketopentanoic acid, aminoacetic acid, indole-3-pyruvic acid, alpha-ketocaproic acid, cyclobutylpyruvic acid.

[0061] In one or more embodiments, the nitrogen source comprises a nitrate salt.

[0062] In one or more embodiments, the synthetic amino acid comprises leucine, alanine, valine, phenylalanine, methylalanine, norvaline, glycine, tryptophan, homophenylalanine, and cyclobutylglycine.

[0063] In order to enable a person skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in conjunction with specific examples.

[0064] Example 1

[0065] (1) 2.1 g (0.01 mol) of H3BTC was dissolved in 10 mL of triethylamine solution, and a dry BTC triethylammonium salt was obtained. The dry BTC triethylammonium salt was dissolved in distilled water to form a 0.1 M BTC triethylammonium solution. 6.375 g of NaNO3 was dissolved in 1500 mL of a 1:1 (v / v) ethanol and water mixture to prepare a 0.05 M NaNO3 solution. 15 mL of a mixed aqueous solution of 0.09 M Cu(NO3)2·3H2O and 0.01 M Zn(NO3)2·3H2O was mixed with 10 mL of 0.1 M BTC triethylammonium solution. The mixture was added dropwise to the NaNO3 solution under vigorous stirring. After 5 minutes of reaction at room temperature, the blue HKUST-1 solid was collected by filtration, washed with ethanol and water, and dried at 90°C to obtain HKUST-1-Cu9-Zn1 nanoparticles represented by Formula IV.

[0066]

[0067] (2) 10 mg of the synthesized HKUST-1-Cu9-Zn1 was dispersed in 5 mL of a methanol / water = 1:1 (v / v) mixed solution to form a light blue solution. 5 mg of benzenehexathiol (BHT) dissolved in 3 mL of methanol was added to the above solution. The reaction was stirred at room temperature for 1 hour. The deep purple precipitate obtained was filtered, washed with water and acetone, and vacuum dried at 90°C overnight to obtain hollow BHT-Cu9-Zn1 nanocubes, i.e., Cu-Zn metal organic framework materials represented by Formula I.

[0068] Example 2

[0069] (1) 2.1 g (0.01 mol) of H3BTC was dissolved in 10 mL of triethylamine solution, and dried to obtain a BTC triethylammonium salt. The dried BTC triethylammonium salt was dissolved in distilled water to form a 0.1 M BTC triethylammonium solution. 6.375 g of NaNO3 was dissolved in 1500 mL of a 1:1 (v / v) ethanol and water mixture to prepare a 0.05 M NaNO3 solution. 15 mL of a mixed aqueous solution of 0.09 M Cu(NO3)2·3H2O and 0.01 M Zn(NO3)2·3H2O was mixed with 10 mL of the 0.1 M BTC triethylammonium solution. The mixture was added dropwise to the NaNO3 solution under vigorous stirring. After 5 minutes of reaction at room temperature, the blue HKUST-1 solid was collected by filtration, washed with ethanol and water, and dried at 90°C to obtain HKUST-1-Cu9-Zn1 nanoparticles.

[0070] (2) 10 mg of the synthesized HKUST-1-Cu9-Zn1 was dispersed in 5 mL of a methanol / water = 1:1 (v / v) mixed solution to form a light blue solution. 5 mg of 1,3,5-triamino-2,4,6-benzene triol (TABTO) dissolved in 3 mL of methanol was added to the above solution. The reaction was stirred at room temperature for 1 hour. The deep purple precipitate obtained was filtered, washed with water and acetone, and vacuum dried at 90°C overnight to obtain hollow TABTO-Cu9-Zn1 nanocubes, which are Cu-Zn metal organic framework materials represented by Formula II.

[0071] Example 3

[0072] (1) 2.1 g (0.01 mol) of H3BTC was dissolved in 10 mL of triethylamine solution, and dried to obtain a BTC triethylammonium salt. The dried BTC triethylammonium salt was dissolved in distilled water to form a 0.1 M BTC triethylammonium solution. 6.375 g of NaNO3 was dissolved in 1500 mL of a 1:1 (v / v) ethanol and water mixture to prepare a 0.05 M NaNO3 solution. 15 mL of a mixed aqueous solution of 0.09 M Cu(NO3)2·3H2O and 0.01 M Zn(NO3)2·3H2O was mixed with 10 mL of the 0.1 M BTC triethylammonium solution. The mixture was added dropwise to the NaNO3 solution under vigorous stirring. After 5 minutes of reaction at room temperature, the blue HKUST-1 solid was collected by filtration, washed with ethanol and water, and dried at 90°C to obtain HKUST-1-Cu9-Zn1 nanoparticles.

[0073] (2) 10 mg of the synthesized HKUST-1-Cu9-Zn1 was dispersed in 5 mL of a methanol / water = 1:1 (v / v) mixed solution to form a light blue solution. 5 mg of hexaaminobenzene hydrochloride (HAB) dissolved in 3 mL of methanol was added to the above solution. The reaction was stirred at room temperature for 1 hour. The resulting dark purple precipitate was filtered, washed with water and acetone, and vacuum dried at 90°C overnight to obtain hollow HAB-Cu9-Zn1 nanocubes, i.e., Cu-Zn metal organic framework material shown in Formula III.

[0074] Figure 1 The XRD test results of BHT-Cu9-Zn1, TABTO-Cu9-Zn1 and HAB-Cu9-Zn1 prepared in Examples 1, 2 and 3 show that the obvious diffraction peaks in the figure indicate that the synthesized MOF has phase purity and high crystallinity. The presence of unique peaks of each MOF highlights their different crystal planes, which are directly related to their catalytic performance and stability.

[0075] Figure 2 The transmission electron microscopy (TEM) image of BHT-Cu9-Zn1 prepared in Example 1 shows that the hollow nanocubes have uniform morphology and size, with a lateral length of 400-500 nm. This layered hollow structure is crucial for improving catalytic performance, as it provides a larger surface area and facilitates efficient mass transfer. Figure 2 a) shows that the hollow nanocubes have uniform morphology and size, with a lateral length of 400-500 nm. This layered hollow structure is crucial for improving catalytic performance, as it provides a larger surface area and facilitates efficient mass transfer. The scanning electron microscopy (SEM) image Figure 2 b) illustrates the surface morphology, showing a clear textured structure. The high-resolution TEM (HRTEM) image Figure 2 c) shows lattice fringes with a spacing of 0.33 nm, corresponding to the 001 crystal plane, indicating high crystallinity at the atomic scale. Finally, the high-angle annular dark-field (HAADF) image Figure 2 d) confirms the uniform distribution of Cu and Zn within the nanocubes, which is crucial for improving catalytic performance.

[0076] Example 4

[0077] Using the electrocatalyst obtained in Example 3, the reduction of nitrate to amino acid by electrolysis was tested in an electrolysis cell using a standard three-electrode system, with a carbon rod as the counter electrode and a mercury / mercurous sulfate electrode as the reference electrode. The test was conducted in a nitrate (0.1 M) and alpha-keto acid (0.2 M) solution.

[0078] Figure 3Linear sweep voltammetry (LSV) curves were performed for BHT-Cu9-Zn1, TABTO-Cu9-Zn1, and HAB-Cu9-Zn1 prepared in Examples 1, 2, and 3, respectively, to further test the electrochemical activity of the MOFs. BHT-Cu9-Zn1 exhibited the highest current density among the tested materials, indicating that it has the most electrocatalytic active sites. This superior activity suggests that BHT-Cu9-Zn1 is well-suited for amino acid synthesis, outperforming TABTO-Cu9-Zn1 and HAB-Cu9-Zn1. This is due to the higher current density being associated with better electron transfer ability and more efficient catalytic performance.

[0079] Figure 4 The nuclear magnetic resonance (NMR) spectrum of leucine after 2 hours of reaction with BHT-Cu9-Zn1, along with the structures of the starting materials, intermediates, and final leucine. This spectrum shows not only leucine but also intermediates and some unreacted starting monomers. This indicates that there is a reaction pathway involving intermediates before leucine is fully formed. The identification of intermediates helps to understand the reaction mechanism and optimize conditions for higher yields of the desired amino acid.

[0080] Figure 5 The potential-dependent Faradaic efficiency (FE) of BHT-Cu9-Zn1, TABTO-Cu9-Zn1, and HAB-Cu9-Zn1 for the reduction of nitrate to leucine in a flow cell. BHT-Cu9-Zn1, with Cu-S / Zn-S active sites, exhibits the best performance, with FE exceeding 80%. In contrast, TABTO-Cu9-Zn1 and HAB-Cu9-Zn1 have lower FE, approximately 40% and 50%, respectively. The specific BHT-Cu9-Zn1 structure is more efficient for amino acid production compared to the other two MOFs, and this difference demonstrates that active site composition plays a crucial role in the catalytic efficiency of the material.

[0081] Figure 6 a is the potential-dependent Faradaic efficiency of BHT-Cu9-Zn1 for leucine in a flow cell. The best Faradaic efficiency is observed at -1.0 V, indicating that this potential is most suitable for leucine production in a continuous flow system. This finding is crucial for scaling up the process and applying it to practical industrial applications. Figure 6 b shows the potential-dependent Faradaic efficiency (FE) and stability of BHT-Cu9-Zn1 for electrocatalytic leucine production at -1.0 V vs. RHE. The data show that BHT-Cu9-Zn1 can maintain an FE of over 80% for up to 240 hours, demonstrating excellent stability.

[0082] Figure 7The optimized Faraday efficiencies (FE) of BHT-Cu9-Zn1 in a flow cell for different amino acids are shown, including leucine, alanine, valine, phenylalanine, methylalanine, norvaline, glycine, tryptophan, homophenylalanine, and cyclobutylglycine, ranked in descending order. The FE of leucine is the highest, while the FE of cyclobutylglycine is the lowest, close to 40%. This comparison shows that BHT-Cu9-Zn1 can be widely used to synthesize various essential amino acids with significant efficiency, especially highlighting its effectiveness for those amino acids that are more difficult to produce.

[0083] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. The present application can have various modifications and changes for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a Cu-Zn metal organic framework material, characterized by, The application relates to a method for preparing a metal-organic framework (MOF) material. The method comprises the following steps: The copper salt solution, the zinc salt solution and the BTC base solution are mixed to obtain a mixed salt solution, the mixed salt solution is added into the sodium salt solution, and a precursor HKUST-1-Cu of a Cu-Zn metal organic framework material is obtained by reaction x -Zn y MOFs; (2) HKUST-1-Cu is dispersed in solvent, organic ligand is added, stirring ligand exchange occurs, and Cu-Zn metal organic framework material is obtained; x -Zn y MOFs are dispersed in solvent, organic ligand is added, stirring ligand exchange occurs, and Cu-Zn metal organic framework material is obtained; (1) dissolving trimellitic acid (H3BTC) in a base solution to obtain a BTC base solution; The organic ligand is benzene-1, 3, 5-hexathiol, 1, 3, 5-triamino-2, 4, 6-benzene triol or hexamino benzene hydrochloride; In step (1), the molar ratio of the sodium salt, the copper salt, the zinc salt and the BTC in the BTC base solution is (60-90):(1.2-1.5):(0.12-0.18):(0.8-1.2). In step (2), HKUST-1-Cu x -Zn y The mass ratio of MOFs to organic ligand is 1-4:

1. In step (1), the reaction time is 2-10 min.

2. The production method according to claim 1, wherein In step (2), the stirring reaction time is 0.5-2 h.

3. The production method according to claim 2, wherein In step (1), the base solution comprises one or more of the following: sodium hydroxide solution, ammonia water, methylamine, ethylamine and triethylamine.

4. The production method according to claim 1, wherein The base solution is triethylamine.

5. The production method according to claim 4, wherein In step (1), the molar ratio of the trimellitic acid and the alkaline substance in the base solution is 1:5-10.

6. The production method according to claim 1, wherein The molar ratio of the trimellitic acid and the alkaline substance in the base solution is 1:7.

2.

7. The production method according to claim 6, wherein In step (1), the sodium salt comprises one or more of the following: sodium chloride, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium sulfate and sodium acetate.

8. The production method according to claim 1, wherein In step (1), the sodium salt is sodium nitrate.

9. The production method according to claim 8, wherein In step (1), the solvent of the sodium salt solution comprises one or more of the following: water, acetone, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, ethanol, methanol and N-methyl pyrrolidone.

10. The production method according to claim 9, wherein The solvent of the sodium salt solution is a water / ethanol mixed solvent.

11. The production method according to claim 10, wherein In the water / ethanol mixed solvent, the volume ratio of water to ethanol is (4-6):(6-4).

12. The production method according to claim 1, wherein The volume ratio of water to ethanol is 1:

1.

13. The production method according to claim 12, wherein In step (1), the concentration of the sodium salt solution is 0.04-0.06 mol / L.

14. The production method according to claim 1, wherein The concentration of the sodium salt solution is 0.05 mol / L.

15. The production method according to claim 14, wherein In step (1), the copper salt comprises one or more of the following: cuprous iodide, cuprous chloride, cuprous nitrate, cuprous bromide, copper iodide, copper chloride, copper nitrate and copper bromide.

16. The production method according to claim 1, wherein The copper salt is copper nitrate.

17. The production method according to claim 16, wherein In step (1), the concentration of the copper salt solution is 0.08-0.1 mol / L.

18. The production method according to claim 1, wherein The concentration of the copper salt solution is 0.09 mol / L.

19. The production method according to claim 18, wherein In step (1), the zinc salt comprises one or more of the following: zinc gluconate, zinc sulfate, zinc chloride, zinc nitrate and zinc acetate.

20. The production method according to claim 1, wherein The zinc salt is zinc nitrate.

21. The production method according to claim 20, wherein In step (1), the concentration of the zinc salt solution is 0.008-0.012 mol / L.

22. The preparation method according to claim 1, wherein The concentration of the zinc salt solution is 0.01 mol / L.

23. The production method according to claim 1, wherein In step (1), the molar ratio of the sodium salt, the copper salt, the zinc salt and the BTC in the BTC base solution is 75:1.35:0.15:

1.

24. The production method according to claim 1, wherein In step (1), the reaction time is 5 min.

25. The production method according to claim 24, wherein In step (2), the solvent comprises one or more of the following: water, acetone, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, ethanol, methanol and N-methyl pyrrolidone.

26. The production method according to claim 25, wherein The solvent is a water / methanol mixed solvent.

27. The production method according to claim 26, wherein In the water / methanol mixed solvent, the volume ratio of water to methanol is (4-6):(6-4).

28. The production method according to claim 1, wherein In step (2), HKUST-1-Cu x -Zn y The mass ratio of MOFs to organic ligands is 2:

1.

29. The production method according to claim 1, wherein In the water / methanol mixed solvent, the volume ratio of water to methanol is 1:

1. In step (2), the stirring reaction time is 1 h.

30. Use of the Cu-Zn metal organic framework material prepared by the preparation method of any one of claims 1-29 as an electrocatalyst for catalyzing synthesis of amino acids.

31. A method of synthesizing an amino acid, comprising: The Cu-Zn metal organic framework material prepared by the preparation method of any one of claims 1-29 is used as an electrocatalyst for catalyzing synthesis of amino acids from a carbon source and a nitrogen source.

32. The method of synthesis of claim 31, wherein, The carbon source includes a-ketoisocaproic acid, pyruvic acid, a-ketoisovaleric acid, phenylpyruvic acid, a-ketoisobutyric acid, a-ketopentanoic acid, aminoacetic acid, indole-3-pyruvic acid, a-ketocaproic acid, and cyclobutylpyruvic acid.

33. The method of synthesis of claim 31, wherein, The nitrogen source includes nitrate.

34. The method of synthesis of claim 31, wherein, The synthesized amino acids include leucine, alanine, valine, phenylalanine, methylalanine, norvaline, glycine, tryptophan, homophenylalanine, and cyclobutylglycine.

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