Cu-based metal organic framework material as well as preparation method and application thereof

Abstract

The invention discloses a Cu-based metal organic framework material as well as a preparation method and application thereof. The Cu-based metal organic framework material disclosed by the invention is Cu-1 or Cu-2, wherein the chemical formula of the Cu-based metal organic framework material is [Cu (DIN) (BTC) (H2O) 2]. (H2O) 2; the chemical formula of Cu-2 is [Cu2 (BTC) 2 (DIN) 2]. (DMA) 2 (H2O), DIN represents 1, 4-bis (imidazole-1-yl) naphthalene, and the molecular formula of the 1, 4-bis (imidazole-1-yl) naphthalene is C16H12N4; bTC represents 1, 3, 5-benzene tricarboxylic acid, and the molecular formula of BTC is C9H6O6; dMA represents N, N-dimethylacetamide, and the molecular formula of DMA is C4H9NO. The Cu-1 material and the Cu-2 material have remarkable antibacterial effects on Escherichia coli under a dark condition and an illumination condition, and the antibacterial effect under the illumination condition is 50% or above higher than that under the dark condition. According to the present invention, the Cu-2 with the more significant effect on the Escherichia coli further has the strong inhibition activity on the pectobacterium carotovorum and the Xanthomonas oryzae, and the Cu-2 provides the significant adsorption and degradation effects on the Congo red pollutant, such that the Cu-2 can provide the significant adsorption and degradation effects on the Congo red,

Description

Technical Field

[0001] The present invention belongs to the technical field of functional materials, and in particular relates to a Cu-based metal organic framework material and a preparation method and application thereof. Background Art

[0002] Infections caused by pathogenic microorganisms (such as bacteria, fungi, and viruses) are the main causes of morbidity and mortality. Bacterial contamination exists in water, air, food processing, health care, agriculture, and other aspects, seriously endangering the health of humans and plants. Antimicrobial materials are widely used to inhibit the growth of bacteria due to their broad-spectrum antimicrobial effects. However, with the emergence of drug-resistant bacteria, there is an urgent need to develop new antimicrobial materials to address the problem of increasing drug resistance.

[0003] At present, the research on new antibacterial materials is growing exponentially, including metal ion materials (such as Ag, Zn and Cu-based nanomaterials), organic materials (such as aldehydes, phenols) and semiconductor photocatalytic materials (such as TiO2, ZnO). Although these antibacterial materials have played a certain role in the past few years, they also have disadvantages. For example, the efficacy of metal ions and organic antibacterial materials discovered so far is short, and their active substances are released too quickly in a short period of time, which will cause excessive environmental burden. The semiconductor photocatalytic antibacterial materials discovered so far have limited light absorption capacity, insufficient catalytic activity and low efficiency. Therefore, antibacterial materials with the advantages of small dosage, high efficiency, long duration and low environmental pollution are in demand.

[0004] Congo red is an insoluble azo dye used as an adsorption indicator, acid-base indicator and biological stain, and is widely used in experiments and industrial processes. It is easy to enter the water body during use, which is very destructive to the environment. Congo red dye wastewater has the characteristics of high chroma, strong toxicity and difficulty in degradation, so it is very important to degrade Congo red in the environment. At present, photocatalytic oxidation technology (PCO) is considered to be one of the methods for degrading Congo red. SnO2, ZnO, TiO2, etc. are traditionally used as photocatalytic materials in PCO technology. Its advantages are stable corrosion resistance, high photosensitivity, low cost, and stable performance. The disadvantage is that its band gap (Eg) is greater than 3eV, and the utilization rate of solar energy is not high in technology, accounting for less than 5% of the UV part of solar energy, so the degradation effect of Congo red is not ideal. Therefore, new materials need to be discovered to improve the utilization rate.

[0005] Metal-organic frameworks (MOFs) are a type of coordination polymer that has developed rapidly in the past 20 years. Due to their superior properties, they have become a popular application material in the fields of gas storage and separation, heterogeneous catalysis, environmental remediation, cancer treatment, and drug delivery.

[0006] In recent years, MOFs and MOFs composite photocatalysts have been widely studied due to their unique morphology, high photocatalytic performance, good chemical stability, easy synthesis and low cost.

[0007] HKUST-1, first reported by Chui et al. in 1999, is a well-known Cu-based MOF material with Cu as metal and 1,3,5-benzenetricarboxylic acid as ligand [Chui SY.A chemically functionalizable nanoporous material[Cu3(TMA)2(H2O)3] n, Science, 1999, 283, 1148-1150.], with extraordinary specific surface area and significant porosity. HKUST-1 has been widely studied by scholars in terms of antibacterial properties, including Escherichia coli, Staphylococcus aureus [Abbasi AR, Akhbari K, Morsali A. Dense coating of surface mounted CuBTC metal-organic framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with antibacterial activity, Ultrasonics Sonochemistry, 2012, 19(4): 846-852.], Saccharomyces cerevisiae and Geotrichum candidum [Chiericatti C, Basilico JC, Basilico MLZ, Zamaro JM. Novel application of HKUST-1 metal-organic framework as antifungal: biological tests and physicochemical characterizations, Microporous and Mesoporous Materials, 2012, 162(1): 60-63.] have good antibacterial activity. At the same time, it has a certain photocatalytic antibacterial effect. Under the excitation of 808nm light source, 500mg / L HKUST-1, irradiated for 20min, the antibacterial rate of Escherichia coli was 16% [Yu P, Han Y, Han D, Liu X, Liang Y, Li Z, Zhu S, Wu S. In-situ sulfuration of Cu-based metal-organic framework for rapid near-infrared light sterilization, Journal of Hazardous Materials, 2020, 15(390): 122126.].

[0008] The iron-based MOF material [MIL-100(Fe)] reported by Gérard et al. in 2007 was prepared by a solvothermal method, in which iron (III) ions were used as coordination centers and tris(III) carboxylate (H3BTC) was used as an organic ligand [Horcajada P, Surbl S, Serre C. Synthesis and catalytic properties of MIL-100(Fe), an iron(iii)carboxylate with large pores, Chemical Communications, 2007, 27: 2820-2822.], and is a potential multifunctional therapeutic platform for cancer treatment [Yu S, Wan J, Chen KA facile synthesis of superparamagnetic Fe3O4supraparticles@MIL-100(Fe)core-shell nanostructures: Preparation, characterization and biocompatibility, Journal of Colloid and Interface Science, 2016, 461: 173-178.]. Li et al. measured its photocatalytic antibacterial effect. The results showed that after 120 minutes of irradiation with simulated sunlight, the inhibition rate of MIL-100 at a concentration of 500 mg / L against Escherichia coli was 91% [Li P, Li JZ, Feng X, LiJ, Hao YC, Zhang JW, Wang H, Yin AX, Zhou JW, Ma XJ, WangB. Metal-organic frameworks with photocatalytic bactericidal activity for integrated air cleaning, Nature Communication, 2019, 10: 2177.].

[0009] MIL-125 was reported by Dan-Hardi et al. in 2009. It was synthesized by solvothermal method, with TiO5(OH) as the metal center and connected by terephthalic acid to form a three-dimensional network structure [Dan-Hardi M, Serre C, Frot T, A new photoactive crystalline highly porous titanium(IV)dicarboxylate, Journal of the American Chemical Society, 2009, 131(31): 10857-10859.], which has good photon sensitivity and photocatalytic performance. There are two types of cavities in the structure of MIL-125, tetrahedral and octahedral. It has the characteristics of large specific surface area, strong stability, strong operability, and easy introduction of functional groups on the framework structure. At present, it has certain application value in photocatalysis, gas adsorption, drug delivery, etc. Functionalized NH2-MIL-125 materials can be obtained by introducing functional amino groups, which have higher stability and photocatalytic activity because both NH2-ligands and Ti-clusters are excited under visible light [Solís RR, Gomez-Aviles A, Belver C, Rodriguez JJ, Bedia J, Microwave-assisted synthesis of NH2-MIL-125(Ti)for the solar photocatalytic degradation ofaqueous emerging pollutants in batch and continuous tests, Journal ofEnvironmental Chemical Engineering,2021,9(5):106230.]. Li et al. measured its photocatalytic antibacterial effect and found that the inhibition rate of Escherichia coli was 96% after 120 minutes of treatment under simulated sunlight [LiP, Li JZ, Feng X, Li J, Hao YC, Zhang JW, Wang H, Yin AX, Zhou JW, Ma XJ, Wang B. Metal-organic frameworks with photocatalytic bactericidal activity for integrated air cleaning, Nature Communications, 2019, 10: 2177.].

[0010] In 2008, Cavka et al. synthesized a metal organic framework material (UIO-66) with Zr as the metal center and terephthalic acid (H2BDC) as the organic ligand [Cavka JH, Jakobsen S, Olsbye UA new zirconium inorganic building brick forming metal organic frameworks with exceptional stability, Journal of the American Chemical Society, 2008, 130: 13850-13851.]. It has the advantages of good stability, large specific surface area, and low toxicity, and is considered to have a wide range of application scenarios. By adding amine groups to the ligand, the formed NH2-UiO-66 captures more light from the visible light region than the unmodified MOF, and exhibits better photocatalytic activity [Manuel PG, Maria JS, Wang YL, Jorge B, Rodriguez JJ, Belver C, Silva CG, Faria JL. Solar photocatalytic degradation of parabens using UiO-66-NH2, Separation And Purification Technology, 2022, 286: 120467.], and the antibacterial rate against Escherichiacoli was 89% after 120 minutes of sunlight irradiation [Li P, Li JZ, Feng X, Li J, Hao YC, Zhang JW, Wang H, Yin AX, Zhou JW, Ma XJ, Wang B. Metal-organic frameworks with photocatalytic bactericidal activity for integrated air cleaning, Nature Communications, 2019, 10: 2177.].

[0011] In 2006, Park et al. synthesized a zinc-based MOF material (ZIF-8) composed of 2-methylimidazole (2-mim) and Zn 2+It is synthesized by heating and stirring [Park KS, Ni Z, Adrien PC. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks, Proceedings of the National Academy of Sciences, 2006, 103 (27): 10186-10191.], has a high surface area and relatively low cytotoxicity, and is one of the most widely used MOFs materials. Compared with MOFs containing heavy metals (Zr and Cr), Zn 2+ It is relatively safe for the environment [Walde M, Ricco CF, Mushtaq R, Terzopoulou F, 'Chen A, Mello XZ, Doonan AJ, Falcaro CJ, Nelson PB. Biocompatibility characteristics of the metal organic framework ZIF-8 for therapeutical applications. Applied Materials Today, 2018, 11: 13-21.]. Compared with MOFs materials, it also has a stronger photocatalytic effect. Under sunlight, 300 mg / L ZIF-8 has an antibacterial rate of 99% against Escherichia coli after 120 minutes of treatment [Li P, Li JZ, Feng X, Li J, Hao YC, Zhang JW, Wang H, Yin AX, Zhou JW, Ma XJ, Wang B. Metal-organic frameworks with photocatalytic bactericidal activity for integrated air cleaning, Nature Communications, 2019, 10: 2177.].

[0012] In 2006, Park et al. reported another zinc-based MOF material (ZIF-11), which uses zinc salt as metal and benzimidazole as ligand, and can be synthesized by stirring method and microwave method [Park KS, Ni Z, Adrien PC, Exceptional chemical and thermal stability of zeolitic imidazolate frameworks, Proceedings of the National Academy of Sciences, 2006, 103 (27): 10186-10191.]. ZIF-11 has a large porosity and a large cavity. and small aperture It is one of the most suitable zeolite imidazolate frameworks for gas separation and adsorption [Assfour B, Leoni S, Seifert G. Hydrogen adsorption sites in zeolite imidazolate frameworks ZIF-8 and ZIF-11, Journal of Physical Chemistry C, 2010, 114: 13381.]. It also has a certain photocatalytic antibacterial ability. Under light conditions, 500 mg / L ZIF-11 has an antibacterial rate of 86% against Escherichia coli within 120 minutes [Li P, Li JZ, Feng X, Li J, Hao YC, Zhang JW, WangH, Yin AX, Zhou JW, Ma XJ, Wang B. Metal-organic frameworks with photocatalyticbactericidal activity for integrated air cleaning, Nature Communications, 2019, 10: 2177.].

[0013] Through the rational design and adjustment of traditional MOFs materials, the light response range and charge separation efficiency of MOFs materials can be significantly improved, thereby improving their photocatalytic effect.

[0014] Yu et al. prepared a Cu-based metal-organic framework (CuS@HKUST-1) embedded with sulfurized CuNPs by a simple in-situ sulfurization process. Under near-infrared (NIR) light irradiation for 20 min, the disinfection effects against Staphylococcus and Escherichia coli were 99.70% and 99.80%, respectively, due to the synergistic effect of the photodynamic effect and photothermal effect of the composite material [Yu P, Han Y, Han D, Liu X, Liang Y, Li Z, Zhu S, Wu S. In-situ sulfuration of Cu-based metal-organic framework for rapid near-infrared lightsterilization. Journal of Hazardous Materials, 2020, 15(390): 122126.].

[0015] Han et al. introduced Cu into the porphyrin ring of PCN224 via a simple hydrothermal method. 2+ Formation of Cu 10 MOF, improves the photocatalytic performance of MOF. Under 660nm light irradiation, Cu doped 2+ It can capture electrons, inhibit electron-hole recombination, accelerate carrier transfer, and thus increase the yield of reactive oxygen species (ROS). 10 The antibacterial effect of MOF against Staphylococcus is 99.71%, and the antibacterial effect against Escherichia coli is 97.14% [Han D, Han Y, Li J, Liu X, Kwok Yeung KW, Zheng Y, Cui Z, Yang X, Liang Y, Li Z, Zhu S, Yuan X, Feng X, Yang C, Wu S. Enhanced photocatalytic activity and photothermal effects of Cu-doped metal-organic frameworks for rapid treatment of bacteria-infected wounds, Applied Catalysis B: Environmental, 2019, 261: 118248.].

[0016] Zhang et al. prepared Cu-doped K2Ti6O by combining sol-gel and hydrothermal methods. 13(Cu-KTO) nanowires, increasing the K2Ti6O 13 Enhanced photocatalytic and antibacterial activities of K2Ti6O 13 nanowires induced by copper doping,Crystals,2020,10:400.].

[0017] As can be seen from the above, metal organic framework materials have good photocatalytic antibacterial effects, but most of the current research is aimed at Escherichia coli and Staphylococcus aureus, and there are few reports on the effects on plant pathogens, and the antibacterial rate still needs to be improved. Therefore, new metal organic framework materials with spectral antibacterial effects and high antibacterial activity and multifunctional materials that can achieve Congo red degradation need to be further developed. Summary of the invention

[0018] The purpose of the present invention is to provide a Cu-based metal organic framework material and a preparation method and application thereof. The Cu-based metal organic framework materials Cu-1 and Cu-2 have significant antibacterial effects on Escherichia coli both under dark conditions and under light conditions. Further experimental results show that Cu-2, which has a more significant effect on Escherichia coli, also has strong inhibitory activity on plant pathogenic bacteria: Pectobacterium carotovorum, the pathogen of cabbage soft rot, and Xanthomonas oryzae, the pathogen of rice white leaf blight. Moreover, Cu-2 has significant adsorption and degradation effects on the pollutant Congo red.

[0019] In a first aspect, the present invention provides a Cu-based metal organic framework material, which is the following Cu-1 or Cu-2:

[0020] Cu-1, chemical formula is [Cu(DIN)(BTC)(H2O)2]·(H2O)2; DIN stands for 1,4-di(imidazol-1-yl)naphthalene, molecular formula is C 16 H 12 N4; BTC stands for 1,3,5-Benzenetricarboxylic acid, with the molecular formula of C9H6O6;

[0021] Cu-2, chemical formula is [Cu2(BTC)2(DIN)2]·(DMA)2(H2O): DIN stands for 1,4-di(imidazol-1-yl)naphthalene, molecular formula is C 16 H 12 N4; BTC stands for 1,3,5-Benzenetricarboxylic acid, with the molecular formula C9H6O6; DMA stands for N,N-dimethylacetamide, with the molecular formula C4H9NO.

[0022] In the above-mentioned Cu-based metal organic framework material, the asymmetric unit of Cu-1 includes 1 Cu 2+ , 1 DIN and 1 deprotonated BTC (HBTC 2- ) ligand and 4 H2O molecules; Cu 2+ The coordination environment of DIN is composed of two N atoms of the imidazole moiety and HBTC. 2- The DIN ligand is connected to the three O atoms of the H2O ligand; the DIN ligand is connected to the two Cu atoms using the μ2 bridge mode. 2+ , HBTC 2- The ligands coordinate with the central ion as terminal ligands; DIN and Cu 2+ Connect to each other along the c-axis to form a straight line;

[0023] The asymmetric unit of Cu-2 includes a Cu ion, a deprotonated BTC (HBTC 2- ) ligand, 1 DIN and 1 free H2O and 1 free DMA molecule; Cu ion is coordinated by 2 N atoms in imidazole groups and 2 O atoms in carboxylic acid; Cu ion is coordinated by DIN ligand along Axis bridge, and by HBTC 2- The ligands are attached along the b-axis; the final architecture of Cu-2 is a two-dimensional layer.

[0024] In a second aspect, the present invention provides a method for preparing the Cu-based metal organic framework material described in any one of the above items, which is as follows 1) or 2):

[0025] 1) The Cu-based metal organic framework material is Cu-1, comprising the following steps:

[0026] Dispersing Cu salt, DIN and BTC in a solvent, and heating in a closed system for reaction to obtain Cu-1;

[0027] 2) The Cu-based metal organic framework material is Cu-2, comprising the following steps:

[0028] The Cu salt, DIN and BTC are dispersed in a solvent containing DMA, and heated in a closed system for reaction to obtain the Cu-2.

[0029] In the above-mentioned method for preparing the Cu-based metal organic framework material, in method 1) and method 2), the molar ratio of the Cu salt, the DIN and the BTC is (1-2):1:(1-2), such as 1:1:1, 2:1:1 or 2:1:2.

[0030] As an example, in method 1), the molar ratio of the Cu salt, the DIN and the BTC is 1:1:1;

[0031] As an example, in method 2), the molar ratio of the Cu salt, the DIN and the BTC is 1:1:1.

[0032] In the above-mentioned method for preparing the Cu-based metal organic framework material, in method 1), the Cu salt is one or more of CuSO4·5H2O, Cu(NO3)2·3H2O, CuCl2·2H2O and Cu(ClO4)2·6H2O;

[0033] The solvent is composed of ethanol and water, wherein the volume ratio of ethanol to water is (1-4):1, such as 1:1, 2:1 or 4:1;

[0034] The ratio of the Cu salt to the solvent is 0.5 mmol: 8 to 80 mL, such as 0.5 mmol: 80 mL;

[0035] In method 2), the Cu salt is one or more of Cu(ClO4)2·6H2O, Cu(NO3)2·3H2O, CuCl2·2H2O and Cu(ClO4)2·6H2O;

[0036] The solvent containing DMA is composed of DMA and water, wherein the volume ratio of DMA to water is (1-4):1, such as 1:1, 2:1 or 4:1;

[0037] The ratio of the Cu salt to the solvent containing DMA is 0.5 mmol:8-80 mL, such as 0.5 mmol:80 mL.

[0038] In the above-mentioned method for preparing the Cu-based metal organic framework material, in method 1) and method 2), the heating temperature is 80-120° C. and the heating time is 24-48 h, such as heating at 120° C. for 48 h.

[0039] In a third aspect, the present invention protects the use of the Cu-based metal organic framework material described in any one of the above items or the Cu-based metal organic framework material obtained by the preparation method described in any one of the above items in inhibiting Escherichia coli under darkness or sunlight.

[0040] The Escherichia coli may specifically be Escherichia coli ATCC 25922.

[0041] In a fourth aspect, the present invention protects the use of the Cu-based metal organic framework material Cu-2 described in any one of the above items or the Cu-based metal organic framework material Cu-2 obtained by the preparation method described in any one of the above items in any of the following items:

[0042] A1) Inhibition of plant pathogenic bacteria;

[0043] A2) Kill plant pathogenic bacteria;

[0044] A3) Prevention and control of plant diseases;

[0045] The steps A1) to A3) are carried out in the dark or under sunlight.

[0046] In the above application, the plant pathogenic bacteria include Pectobacterium carotovorum or Xanthomonas oryzae;

[0047] The carrot pectin bacterium (Pectobacterium carotovorum) can specifically be ATCC 39048;

[0048] The Xanthomonas oryzae pv.oryzae may specifically be XO35933;

[0049] The plant disease is cabbage soft rot or rice bacterial blight.

[0050] In a fifth aspect, the present invention protects the use of the Cu-based metal-organic framework material described in any of the above items or the Cu-based metal-organic framework material obtained by the preparation method described in any of the above items in the adsorption and / or degradation of the pollutant Congo red under darkness or sunlight.

[0051] The present invention has the following beneficial effects:

[0052] (1) The present invention synthesized two new Cu-based MOF materials (Cu-1, Cu-2). Both materials have significant antibacterial effects on Escherichia coli in the dark and in the light.

[0053] (2) Cu-2 also has strong antibacterial activity against plant pathogenic bacteria Pectobacterium carotovorum, the pathogen of cabbage soft rot, and Xanthomonas oryzae, the pathogen of rice bacterial leaf blight.

[0054] (3) The antibacterial modes of Cu-1 and Cu-2 in darkness and light are not likely to induce drug resistance.

[0055] (4)Cu-2 has a significant adsorption and degradation effect on the pollutant Congo red.

[0056] The present invention synthesized two new Cu-based MOF materials (Cu-1 and Cu-2) and characterized them in detail. Cu-1 and Cu-2 have good antibacterial effects on Escherichia coli. Cu-2 with better effect was selected to carry out antibacterial experiments on plant pathogenic bacteria. The results showed that Cu-2 had good antibacterial effects on Pectobacterium carotovorum, the pathogen of cabbage soft rot, and Xanthomonas oryzae, the pathogen of rice bacterial leaf blight. Subsequently, the antibacterial mechanism and the reasons for the difference in the effects of the two materials were explored. Under dark conditions, chelation inhibition is mainly carried out through surface active sites; under light conditions, antibacterial inhibition is mainly carried out through photocatalytic generation of active oxygen (hydrogen peroxide, superoxide radicals, hydroxyl radicals, singlet oxygen), H2O2 is the key active substance, and both antibacterial methods are not easy to produce drug resistance. It is hoped that it will provide a reference for the construction of photocatalytic MOF materials and provide new ideas for the field of inhibiting pathogenic microorganisms. It was subsequently discovered that Cu-1 and Cu-2 had adsorption and degradation effects on the pollutant Congo red under dark and light conditions, and Cu-2 was more significant. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 Schematic diagram of the synthesis of Cu-based metal organic framework materials Cu-1 and Cu-2 in Example 1 of the present invention.

[0058] Figure 2 This is the minimum asymmetric unit of Cu-1 in Example 1 of the present invention, and the structure diagram in the c-axis direction.

[0059] Figure 3 This is the minimum asymmetric unit of Cu-2 in Example 1 of the present invention, and the structure diagram in the c-axis direction.

[0060] Figure 4 The powder X-ray diffraction (PXRD) patterns of Cu-1 and Cu-2 in Example 1 of the present invention are shown in FIG.

[0061] Figure 5This is the Fourier transform infrared spectrum (FT-IR) of Cu-1 and Cu-2 in Example 1 of the present invention.

[0062] Figure 6 This is a thermogravimetric analysis (TGA) curve of Cu-1 and Cu-2 in Example 1 of the present invention.

[0063] Figure 7 N2 adsorption (blue) and desorption isotherms (red) of Cu-1 (A) and Cu-2 (B) at 77K in Example 1 of the present invention.

[0064] Figure 8 The inhibitory effects of the Cu-based metal organic framework materials Cu-1 and Cu-2 on Escherichia coli under light and dark conditions in Example 2 of the present invention are shown.

[0065] Fig. 9 This is a bar graph showing the inhibitory effect of 300 mg / L Cu-1 and Cu-2 on Escherichia coli under light and dark conditions in Example 2 of the present invention.

[0066] Fig.10 The figures show the inhibitory effects of different concentrations of Cu-1 on Escherichia coli under dark and light conditions in Example 2 of the present invention.

[0067] Fig.11 The figures show the inhibitory effects of different concentrations of Cu-2 on Escherichia coli in Example 2 of the present invention under dark and light conditions.

[0068] Fig.12 This is a 3D graph of the inhibitory effects of different concentrations of Cu-1 and Cu-2 on Escherichia coli under dark and light conditions in Example 2 of the present invention (A: Cu-1 in the dark; B: Cu-1 in the light; C: Cu-2 in the dark; D: Cu-2 in the light).

[0069] Fig.13 The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows:

[0070] Fig.14 The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows: The results are as follows:

[0071] Fig.15 This is a release curve diagram of Cu-1 and Cu-2 in Example 2 of the present invention.

[0072] Fig.16 This is the ultraviolet diffuse reflectance (DRS) spectrum of Cu-1 and Cu-2 in Example 2 of the present invention.

[0073] Fig.17 It is the electron paramagnetic resonance (EPR) spectrum of Cu-1 and Cu-2 superoxide radicals, hydroxyl radicals, singlet oxygen, photogenerated electrons, and oxygen vacancies in Example 2 of the present invention.

[0074] Fig.18 The effect of Cu-2 on inhibiting Escherichia coli in Example 2 of the present invention is affected by different quenchers.

[0075] Fig.19 This is the degradation effect of Cu-based metal organic framework materials Cu-1 and Cu-2 on Congo red in Example 3 of the present invention. DETAILED DESCRIPTION

[0076] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0077] The methods used in the following examples, unless otherwise specified, are all conventional methods, carried out according to the techniques or conditions described in the literature in the art or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial sources.

[0078] Test strains

[0079] Escherichia coli ATCC 25922 is recorded in "Parsaei M, Akhbari K, White J. Synthesis, characterization and comprehensive study of a 3D Co(II) coordination polymer antibacterial activity, Journal of Molecular Structure, 2023, 1283, 135224." The public can obtain it through commercial channels or from the applicant. The biological material is only used to repeat the relevant experiments of the present invention and cannot be used for other purposes.

[0080] Pectobacterium carotovorum ATCC 39048 is recorded in the document "Monson RE, Jones K, Salmond GPC. Draft genome sequence of Pectobacterium carotovorum subsp. carotovorum ATCC 39048, a carbapenem-producing phytopathogen, Microbiology Resource Announcements, 2018, 7: e00825-18.", which is available to the public from the applicant. The biological material is only used for repeating the relevant experiments of the present invention and cannot be used for other purposes.

[0081] Xanthomonas oryzae pv. oryzae XO35933 is recorded in the document "Midha1 S, Bansal K, Kumar1 S, Girija AM, Mishra D, Brahma K, Laha GS, Sundaram RM, Sonti RV, Patil PB. Population genomic insights into variation and evolution of Xanthomonas oryzae pv. Oryzae, Scientific Reports, 2017, 7, 40694." and can be obtained by the public from the applicant. The biological material is only used for repeating the relevant experiments of the present invention and cannot be used for other purposes.

[0082] Reagents

[0083] All chemicals were obtained commercially without further purification. Cu(ClO4)2·6H2O, CuSO4·5H2O, 1,3,5-benzenetricarboxylic acid (BTC), N,N-dimethylacetamide (DMA) and ethanol (EtOH) were provided by Aladdin Holding Group Co., Ltd. 1,4-di(imidazol-1-yl)naphthalene (DIN) was synthesized according to the method described in the literature “Yang L, Li X, Sun C, Wu H, Wang C, Su ZA stable pillared-layer Cu(II) metal-organic framework for dye adsorption and separation and magnetic properties, New Journal of Chemistry, 2017, 41: 3661-3666.”

[0084] Preparation of culture medium

[0085] Liquid Luria-Bertani (LB) medium: 10 g tryptone, 5 g yeast extract, 10 g sodium chloride, adjust pH to 7.0, and make up to 1000 mL.

[0086] Solid Luria-Bertani (LB) medium: 10 g tryptone, 5 g yeast extract, 10 g sodium chloride, 15-20 g agar powder, adjust pH to 7.0, and make up to 1000 mL.

[0087] Example 1: Synthesis of Cu-based metal organic framework materials

[0088] 1. Synthesis

[0089] according to Figure 1 The schematic diagram shown uses the solvothermal method to synthesize two Cu-based MOF materials (Cu-1 and Cu-2). The specific steps are as follows:

[0090] Cu-1[Cu(DIN)(BTC)(H2O)4] n Synthesis: CuSO4·5H2O (12.5 mg, 0.05 mmol), DIN (13 mg, 0.05 mmol) and BTC (10.5 mg, 0.05 mmol) were ultrasonically mixed in 8 mL of solvent (EtOH:H2O=1:1) for 5 minutes, then placed in a stainless steel autoclave and heated at 120°C for 48 hours. The obtained blue crystals were repeatedly washed with deionized water and filtered out, and dried at room temperature overnight to obtain 30 mg of the final product (yield: 60.7%). Elemental analysis C 25 H 24 CuN4O10 (604.2) Theoretical calculation: C, 55.93%; H, 3.67%; N, 11.34%, Actual detection: C, 55.79%; H, 3.12%; N, 11.82%, Infrared spectrum peak position (neat, ν / cm -1 ):3466(w),3112(w),1675(w),1617(m),1505(m),1436(m),1353(s),1235(s),1181(s) ,1103(m),1036(m),950(m),823(m),741(s),654(s),514(s),439(s),421(s),406(s).

[0091] Cu-2[Cu2(DIN)2(BTC)2(DMA)2(H2O)] n Synthesis: Cu(ClO4)2·6H2O (18.5 mg, 0.05 mmol), DIN (13 mg, 0.05 mmol) and BTC (10.5 mg, 0.05 mmol) were ultrasonically mixed in 8 mL of solvent (DMA:H2O=1:1) for 5 minutes, the mixture was placed in a stainless steel autoclave, and heated at 120°C for 48 hours. The obtained blue-purple crystals were filtered out and repeatedly washed with deionized water, and dried at room temperature overnight to obtain 30 mg of the final product (yield: 47.8%). Elemental analysis C 58 H 52 Cu2N 10 O 15 (1256.17) Theoretical calculation: C, 55.46%; H, 4.17%; N, 11.15%;, Actual detection: C 55.21%, H 3.98%, N 11.36%, Infrared spectrum peak position (neat, ν / cm -1 ):3127(w),2925(w),1710(m),1582(m),1505(m),1397(m),1336(s),1230(s),1175(m),11 80(m),1036(m),952(m),836(m),754(s),726(s),654(s),596(m),523(m),439(m),406(m).

[0092] 2. Characterization

[0093] Single crystal X-ray diffraction (SCXRD) data were recorded using a Bruker D8 Quest diffractometer equipped with a Mo-Kα radiation Photon III detector. The structure was solved by direct method and the refinement was performed by full matrix least squares for all reflections on F2 using SHELXL software. Non-hydrogen atoms were refined anisotropically and the experimentally measured structural information is shown in Table S1, while the bond length and angle information are shown in Tables S2 and S3. Powder X-ray diffraction (PXRD) analysis of the samples was performed using a Rigaku SmartLab (Cu-Kα radiation) diffractometer. Thermogravimetric analysis (TGA) was performed using a STA 449F3 Jupiter analyzer in nitrogen and air with a heating rate of 10 °C / min to 800 °C. Fourier transform infrared (FT-IR) spectra of Cu-CPs were measured using a JASCO FT-IR-6300 spectrometer (JASCO International Ltd., Tokyo, Japan) in the spectral region of 4000–400 cm -1 , resolution 4cm -1 The adsorption-desorption of nitrogen and the pore size distribution were detected by a specific surface area micropore analyzer (BSD-PM1). DIN and Cu were determined by high performance liquid chromatography (HPLC, Agilent 1200) and atomic absorption spectrometry (AAS, AA-6300), respectively. 2+ The release concentration of 2.5 wt. % was 2.3 wt. % by mass. The UV-visible diffuse reflectance spectra (UV-vis DRS) were measured on a TU-1901 UV-visible spectrophotometer. X-ray photoelectron spectroscopy (XPS, VG Multilab 2000) was performed using Al Kα radiation at 2×10 -6 The spectroscopy was carried out under vacuum at 1000 Pa, and the binding energy was calibrated using the C1s peak (284.8 eV) as the standard. In addition, the ultraviolet photoelectron spectrum (UPS) of the sample was measured to determine the energy band structure of the sample. From the UPS spectrum, according to the formula Φ = hν-(E Fermi -E cutoff )Calculate the work function Φ of the sample, where hν=21.22eV.

[0094] Table S1 Crystal data of Cu-1 and Cu-2

[0095]

[0096] a R1=Σ1|F0|-|F C | / Σ1|F0|, b wR2=[Σ[w(F0 2 -F C 2 ) 2 ] / Σ[(F0 2 ) 2 ]] 1 / 2 .

[0097] surface Bond length of S2 Cu-1 and bond angle [°] information

[0098]

[0099] Symmetric code: #1 x,y,-1+z; #2 x,y,1+z.

[0100] surface S3 Cu-2 bond length and bond angle [°] information

[0101]

[0102]

[0103] Symmetric code: #1 1-x,1 / 2+y,1 / 2-z; #2 -1+x,y,-1+z; #3 1-x,-1 / 2+y,1 / 2-z; #4 1+x,y,1+z.

[0104] Figure 2 Cu-1 is clustered in the P21 (no.4) space group of the monoclinic system. The asymmetric unit of Cu-1 consists of 1 Cu 2 + , 1 DIN and 1 deprotonated BTC (HBTC 2- ) ligand and 4 H2O molecules; Cu 2+ The coordination environment of DIN is composed of two N atoms of the imidazole moiety and HBTC. 2- The DIN ligand is connected to the three O atoms of the H2O ligand; the DIN ligand is connected to the two Cu atoms using the μ2 bridge mode. 2+ , HBTC 2- The ligands coordinate with the central ion as terminal ligands; DIN and Cu 2+ Connect to each other along the c-axis to form a straight line.

[0105] Figure 3 Cu-2 crystallizes in the monoclinic system P21 / c (no.14) space group. The asymmetric unit of Cu-2 consists of a Cu ion, a deprotonated BTC (HBTC 2- ) ligand, 1 DIN and 1 free H2O and 1 free DMA molecule; Cu ion is coordinated by 2 N atoms in imidazole groups and 2 O atoms in carboxylic acid; Cu ion is coordinated by DIN ligand along Axis bridge, and by HBTC 2- The ligands are attached along the b-axis; the final architecture of Cu-2 is a two-dimensional layer.

[0106] Figure 4 The crystal phase purity of Cu-1 and Cu-2 was analyzed by powder XRD method. The results showed that the PXRD spectra of the two materials were highly similar to the simulated spectra, indicating that the prepared compounds were of high purity.

[0107] like Figure 5 As shown in the infrared spectrum of Cu-1, 3112cm -1 The absorption peak at 1351 cm is due to the water molecules (free water and coordinated water) in the structure. The stretching vibration absorption peak of the CN bond in the DIN structure appears at 1351 cm -1 Position, and appears at 1675cm -1 The peak at the position belongs to the C=N bond, and the absorption peak of the Cu-O bond appears at 645cm -1 In the infrared spectrum of Cu-2, 3127cm -1 The absorption peak at 2925 cm is mainly attributed to the OH of free water molecules. The stretching vibration region of CH is located at 2925 cm -1 The C=O and CO stretching absorption peaks of the carboxyl group on BTC appear at 1710 and 1036 cm -1 Position. At 1582cm -1 The stretching vibration peak of C=N of DIN ligand was observed at 1505cm -1 The stretching vibration of C=C is 654cm -1 The absorption peak at belongs to Cu-O.

[0108] The thermal stability of the materials was examined by thermogravimetric analysis. Figure 6 The thermogravimetric curves of Cu-1 and Cu-2 are shown respectively. Cu-1 first experiences a small amount of weight loss (about 11.2%) at around 50°C, and the theoretical calculated value is 11.9%, which is due to the degradation of solvent molecules. The second weight loss (about 50%) occurs at around 300°C, which is due to the overall disintegration of the structure. Cu-2 experiences the first weight loss of about 14.6% at around 50°C, and the theoretical calculated value is 15.3%, which is due to the evaporation of free water molecules and solvent molecules in the material. As the sample temperature gradually increases, a large weight loss occurs at around 300°C due to the overall disintegration of the structure. Both Cu-1 and Cu-2 will undergo large-scale decomposition above 300°C, indicating that the materials have good thermal stability.

[0109] The N2 adsorption-desorption isotherms of Cu-1 and Cu-2 are shown in Figure 7 As shown in Figure 1, the isotherms of the two materials are identified as type I, which is a characteristic of microporous materials. The specific surface area, pore size and pore volume data of Cu-1 and Cu-2 are shown in Table 1. The specific surface areas of the two materials tested by the BET multi-point method are 3.0491 and 4.6753 m2 / g, the pore sizes are 6.0346 and 3.9356nm respectively, and the pore volumes are the same. Cu-2 has a larger specific surface area and smaller pore size than Cu-1, so Cu-2 has a higher porosity.

[0110] Table 1 Specific surface area and average pore size data of Cu-1 and Cu-2

[0111]

[0112] Example 2, antibacterial experiment

[0113] 1. Antibacterial experiments under light and dark conditions

[0114] The Gram-negative bacterium Escherichia coli was used as a model bacterium to evaluate the photocatalytic antibacterial performance of Cu-BTC. All instruments and materials were sterilized in an autoclave before the sterilization experiment. Escherichia coli was cultured in LB liquid medium at 37°C and 200rpm in a constant temperature incubator for 12 hours, and the bacterial concentration (OD 600 ), then add sterile saline (0.9% (w / v) to dilute to obtain about 10 6 1, 2, and 4 mg of Cu-1 and Cu-2 were added to 4 mL of bacterial solution, and then simulated sunlight (300 W xenon lamp with AM 1.5 filter) was used at 100 mW·cm -2 The bacterial suspension was irradiated with an optical density of . At different time points (10min, 20min, 30min, 40min), the bacterial suspension was pipetted for dilution, and 20μL was spread on a solid LB medium plate. The culture dish was incubated at 37°C for 20h, and the bacterial concentration was calculated by colony counting method. Each group of experiments was repeated three times. Under the same conditions, the corresponding dark antibacterial experiment was carried out. The same method was used to test the antibacterial effect of Cu-2 on Pectobacterium carotovorum and Xanthomonas oryzae.

[0115] Figure 8 This is the inhibitory effect diagram of Cu-1 and Cu-2 on Escherichia coli under light and dark conditions. The concentration of both materials is 300 mg / L. Then the inhibition data is sorted and the inhibition effect bar chart is drawn ( Fig. 9 ), the results of the control group (CK) showed that 30 minutes of simulated sunlight exposure had almost no effect on Escherichia coli.

[0116] When Cu-1 was treated in the dark for 30 minutes, the antibacterial rate against Escherichia coli was 54%, and when it was treated in the light for 30 minutes, the antibacterial rate against Escherichia coli was 70%. The photocatalytic antibacterial effect of the material can be reflected by observing the difference between the antibacterial rates in the dark and in the light. After 10 minutes of treatment, there was almost no difference in the antibacterial effect of Cu-1 in the dark and in the light (about 1.9%). After 20 minutes of treatment, Cu-1 showed a large difference of about (30%), indicating that the material has a certain photocatalytic antibacterial effect.

[0117] After 30 minutes of dark treatment, Cu-2 can achieve about 60% antibacterial effect on Escherichia coli. After 30 minutes of light treatment, the antibacterial effect on Escherichia coli can reach 100%. When treated for 10 minutes, there is no difference in the antibacterial effect of Cu-2 in the dark and light (about 1.2%), and no photocatalytic effect is reflected. When the time lasts for 20 minutes, the material shows a significant photocatalytic effect, and the difference reaches 53%. After 30 minutes, because the light bactericidal effect has reached 100%, the difference between the two is reduced (about 41%).

[0118] The above results show that 300 mg / L Cu-1 and Cu-2 have antibacterial effects in both darkness and light, and Cu-2 has more significant photocatalytic activity than Cu-1.

[0119] Fig.10 and Fig.11 The following are the inhibitory effects of Cu-1 and Cu-2 at different concentrations (100 mg / L, 300 mg / L, 500 mg / L) on Escherichia coli in darkness and light. It can be seen from the CK group that the effect of sunlight on Escherichia coli is negligible. With the increase of time and concentration, the antibacterial effect of the material gradually increases. Based on the antibacterial data, a 3D data graph of the antibacterial effect was drawn ( Fig.12 ).

[0120] Under dark conditions, when the Cu-1 concentration was 500 mg / L, the maximum antibacterial effect of 80% could be achieved in 40 min ( Fig.12 A), with the addition of light, the antibacterial effect of Cu-1 was improved, and Cu-1 could achieve 100% antibacterial rate at 40 min ( Fig.12 B) From Fig.12It can be seen from C that under dark conditions, when the Cu-2 concentration is 300 mg / L, mixing with Escherichia coli for 40 minutes can achieve 100% antibacterial effect. When the concentration is changed to 500 mg / L, mixing with Escherichia coli for 20 minutes can achieve 100% antibacterial effect. Fig.12 It can be seen from D that under light conditions, when the concentration is 100 mg / L, mixing with Escherichia coli for 40 minutes can achieve 100% antibacterial effect, and when the concentration is 300 mg / L, mixing with Escherichia coli for 20 minutes can achieve 100% antibacterial effect. When the concentration is 500 mg / L, mixing with Escherichia coli for 10 minutes can achieve 90% antibacterial rate, which has a more prominent antibacterial effect compared with dark conditions.

[0121] Overall, the antibacterial effect of Cu-2 is better than that of Cu-1 under both dark and light conditions. 10 MOF) (Table 2), Cu-2 has better antibacterial effect, and Cu-1 also has certain advantages over some traditional MOF materials (HKUST-1, MIL-100, NH2-MIL-125, UIO-66, ZIF-8 and ZIF-11).

[0122] Table 2 Comparison of photocatalytic antibacterial activity (Escherichia coli) of Cu-1, Cu-2 and other reported catalysts

[0123]

[0124] The references in Table 2 are as follows:

[0125] [1]Zhang WW,Wang X,Ma YH,Wang HR,Qi YM,Cui CX.Enhanced photocatalytic and antibacterial activities of K2Ti6O 13 nanowires induced by copper doping,Crystals,2020,10:400.

[0126] [2] Yu P, Han Y, Han D, Liu

[0127] [3]Han D, Han Y, Li J, Liu X, Yeung KW, Zheng Y, Cui Z, Yang X, Liang Y, Li Z, Zhu S, Yuan X, Feng B:Environmental,2019,261:118248.

[0128] [4]Li P, Li JZ, Feng

[0129] The above experiments prove that Cu-2 has better antibacterial effect than Cu-1, so Cu-2 was selected to determine the antibacterial effect on plant pathogens. Fig.13This is the inhibitory effect of Cu-2 on Pectobacterium carotovorum under light and dark conditions. Under dark conditions, 1000 mg / L of Cu-2 can completely kill bacteria after mixing with bacteria for 40 minutes. Under light conditions, 250 mg / L of Cu-2 can achieve 100% antibacterial effect after 40 minutes of light exposure. When the concentration reaches 500 mg / L, 20 minutes of light exposure can achieve an inhibition rate of 99%. The results show that Cu-2 has a good antibacterial effect on Pectobacterium carotovorum and there is a significant difference in the inhibition rate between light and darkness, indicating that the material has a strong photocatalytic antibacterial effect.

[0130] Fig.14 The inhibition effect of Cu-2 on Xanthomonas oryzae under light and dark conditions. Under dark conditions, 1000 mg / L Cu-2 can kill more than 50% of pathogens after mixing with bacteria for 60 minutes. The contrast between light and dark conditions is strong. Under light, 250 mg / L Cu-2 can achieve more than 90% inhibition after 60 minutes of light. When the concentration reaches 500 mg / L, 40 minutes of light can achieve 99% inhibition.

[0131] 2. Antibacterial Mechanism

[0132] Component release experiment: 16 mg of Cu-1 and Cu-2 were placed in 80 mL of ultrapure water and stirred at room temperature. 5 mL of the solution was taken out periodically, centrifuged, and DIN and Cu were detected by high performance liquid chromatography (Agilent 1200) and atomic absorption spectrometry (AA-6300) respectively. 2+ release concentration.

[0133] (1) Dark antibacterial

[0134] Fig.15 The release curves of Cu-1 and Cu-2 are shown in Figure 2. 2+ And the concentration of DIN. The release trends of the two materials are basically the same. They are released in a short period of time first, reaching equilibrium in about 16 hours, and then maintaining the equilibrium concentration for a long time. After calculation, the molar ratio of the concentrations released by the two is consistent with the molar ratio of the material itself, indicating that the material is released by overall disintegration. Until 109h, it still maintained a low concentration, the Cu ion concentration was about 1.5mg / L, and the DIN ligand concentration was maintained at 4.3mg / L. According to laboratory antibacterial (Table 3), the half inhibitory concentration (EC50) of Cu(ClO4)2 for Escherichia coli 50 ) is 768.5 mg / L, and the EC of CuSO4 50The value is 751.95 mg / L, and the EC value of DIN for Escherichia coli 50 The value is 1702.6 mg / L. The concentration required for the antibacterial effect under dark conditions is much higher than the released concentration. Therefore, we reasonably speculate that the antibacterial effect of Cu-1 and Cu-2 under dark conditions is not mainly dependent on the released Cu 2+ Instead, it uses overall chelation to fight bacteria.

[0135] Table 3 Antibacterial effect of each component on Escherichia coli

[0136]

[0137] (2) Light inhibition

[0138] Photocatalytic performance testing

[0139] Photoelectrochemical measurements: All photoelectrochemical tests were performed by a CHI 660E three-electrode electrochemical workstation, with platinum as the counter electrode and calomel electrode as the reference electrode. The working electrode was prepared as follows: Cu-BTC (20 mg) was ultrasonically dispersed in 0.5% Nafion solution (0.5 mL) to generate a slurry, which was then dip-coated on a FTO glass electrode (1 × 1 cm 2 ). Using 0.5M Na2SO4 solution as the electrolyte, the electrolyte was exposed to simulated sunlight (300W Xe lamp with AM 1.5 filter, 100mW·cm -2 ) The photocurrent density was measured under alternating changes of light irradiation and no light irradiation. The electrochemical impedance spectroscopy (EIS) detection and processing method was the same as above, with a range of 100kHz~0.01Hz and an amplitude of 10Mv.

[0140] It is speculated that the antibacterial effect of light may rely on photocatalysis, which forms various free radicals with bactericidal activity through the stimulation of sunlight. For photocatalytic materials, it is necessary to detect the absorption spectrum (ultraviolet diffuse reflectance) of the materials, such as Fig.16 As shown, both Cu-1 and Cu-2 have two main peaks. The yellow part is the ultraviolet spectrum of AM1.5 simulated sunlight. The range of the sunlight spectrum under ultraviolet wavelength is mainly 400-800nm. The results of ultraviolet diffuse reflection ensure that Cu-1 and Cu-2 can show excellent photocatalytic ability under simulated sunlight. The absorption range of Cu-2 is larger than that of Cu-1, and it can absorb more sunlight energy. This may be one of the reasons why the photocatalytic effect of Cu-2 is better than that of Cu-1. It is worth noting that if a light source with a corresponding range is used, the material may produce a better photocatalytic effect (in the ultraviolet diffuse reflection experiment, the wavelength with the highest peak has the best effect, Cu-1: 319 and 675nm, Cu-2: 320 and 590nm).

[0141] Study on the photocatalytic mechanism

[0142] Free radical quenching experiment: Sodium chromate was used to quench photogenerated electrons (Cr(VI), 2.5 mM, Sigma, 99.5%); TEMPO was used to quench ·O2 (2.5 mM, Sigma, 99%); L-histidine was used to quench 1 O2 (2.5 mM, Sigma, 99%); catalase quenched H2O2 (300 U mL -1 , Sigma); isopropanol quenching ·OH (2.5mM, Sigma, 99.5%) and sodium oxalate quenching photogenerated holes (2.5mM, Sigma, 99.5%). The scavenger was added to the bacterial suspension before illumination. The bacterial suspension was diluted at different time points (10min, 20min, 40min), and 20μL was drawn and spread on the culture medium plate. The culture dish was incubated at 37℃ for 20h, and the antibacterial effect was calculated by colony counting method. Each group of experiments was repeated three times.

[0143] Electron paramagnetic resonance (EPR): The material was prepared into a 1 mg / mL solution and illuminated under a xenon lamp (radiation intensity = 100 mW cm -2 ) under irradiation. Photogenerated electrons: first measure the signal of TEMPO capture agent under no illumination, then add the prepared liquid sample and illuminate for 10 minutes to measure the signal again. Hydroxyl free radicals: measure the signal of the prepared liquid sample once without illumination, then add DMPO capture agent to the prepared sample and illuminate for 10 minutes to measure the signal (water system). Superoxide free radicals: first measure the signal of the prepared sample without illumination, then add DMPO capture agent and mix with methanol (methanol system) and illuminate for 10 minutes to measure the signal. Singlet oxygen: first measure the signal of the prepared sample without illumination, then add TEMP without capture agent and mix with ethanol and illuminate for 10 minutes to measure the signal (ethanol system).

[0144] The presence of superoxide radicals, hydroxyl radicals, singlet oxygen, photogenerated electrons and oxygen vacancies was verified by electron paramagnetic resonance spectroscopy ( Fig.17), as shown in the figure, both Cu-1 and Cu-2 contain photogenerated electrons, proving that sunlight can excite electrons to generate carriers. Cu-1 did not detect the presence of superoxide radicals because it did not reach the redox potential of superoxide radicals, but detected the presence of hydroxyl radicals, singlet oxygen and oxygen vacancies, and oxygen vacancies mediated the production of singlet oxygen. Cu-2 detected the presence of photogenerated electrons, superoxide radicals, hydroxyl radicals, singlet oxygen and oxygen vacancies, proving that Cu-1 can excite photogenerated electrons through sunlight, and electrons jump to the surface of the material to react with oxygen to generate superoxide radicals, which can be converted into hydroxyl radicals and singlet oxygen. The superoxide radicals, hydroxyl radicals, singlet oxygen, photogenerated electrons and oxygen vacancies intensities of Cu-2 are all higher than those of Cu-1 (the higher the intensity, the higher the content).

[0145] The contribution of active components was investigated by free radical quenching experiments. Sodium chromate was used to quench photogenerated electrons, TEMPO was used to quench O2, and L-histidine was used to quench 1 O2, catalase quenches H2O2, isopropanol quenches OH· and sodium oxalate quenches photogenerated holes. Fig.18 As shown in Figure 2, the introduction of catalase significantly affected the inhibition rate, indicating that H2O2 is a key species. - and h + It also plays a bactericidal role in antibacterial reactions, and other free radicals have almost no effect on Escherichia coli.

[0146] Example 3: Pollutant degradation experiment

[0147] Pollutant degradation experiment: 0.6 mg of the material was added to 40 mL of a 20 mg / L Congo red solution and adsorbed for 2 h in the dark. Samples were taken every 1 h and then transferred to a xenon lamp (300 W, AM 1.5 filter, 100 mW cm -2 ) for 2 h, remove 2 mL of the solution every 0.5 h, centrifuge to obtain the supernatant, and then use an ultraviolet spectrophotometer to detect the degradation of Congo red.

[0148] like Fig.19As shown in the figure, the degradation effect of Cu-1 and Cu-2 on Congo red was tested. The black curve shows that Congo red itself did not undergo significant degradation under the conditions of darkness and sunlight. Both materials have degradation effects. The degradation effect of Cu-1 on Congo red under dark conditions for 2h is about 16%, and the degradation effect of Cu-2 on Congo red under dark conditions for 2h is about 42%. The degradation effect under dark conditions is mainly due to physical adsorption. According to the specific surface area pore size data in the above characterization part, the specific surface area of ​​Cu-2 is larger than that of Cu-1. The larger the specific surface area, the higher the porosity of the material, and the better the adsorption effect. The degradation rate of Cu-1 on Congo red under 2h of light is about 23%, and Cu-2 can degrade about 90% of Congo red under 2h of light. Cu-2 has a more significant degradation effect than Cu-1, and it once again confirms that Cu-2 has a good photocatalytic effect.

[0149] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, can implement the present invention in a wider range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principle of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departing from the disclosed scope in the application and the changes made with conventional techniques known in the art.

Claims

1. A Cu-based metal organic framework material, characterized in that: It is Cu-1 or Cu-2 as follows: Cu-1, chemical formula is [Cu(DIN)(BTC)(H2O)2]·(H2O)2; DIN represents 1,4-di(imidazol-1-yl)naphthalene, molecular formula is C 16 H 12 N4; BTC stands for 1,3,5-benzenetricarboxylic acid, with the molecular formula of C9H6O6; Cu-2, chemical formula is [Cu2(BTC)2(DIN)2]·(DMA)2(H2O): DIN represents 1,4-di(imidazol-1-yl)naphthalene, molecular formula is C 16 H 12 N4; BTC stands for 1,3,5-benzenetricarboxylic acid, with the molecular formula C9H6O6; DMA stands for N,N-dimethylacetamide, with the molecular formula C4H9NO.

2. The Cu-based metal organic framework material according to claim 1, characterized in that: The asymmetric unit of Cu-1 includes 1 Cu 2+ , 1 DIN and 1 deprotonated BTC (HBTC 2- ) ligand and 4 H2O molecules; Cu 2+ The coordination environment is composed of two N atoms of the imidazole part of DIN and HBTC 2- The DIN ligand is connected to the three O atoms of the H2O ligand; the DIN ligand is connected to the two Cu atoms using the μ2 bridge mode. 2+ , HBTC 2- The ligands coordinate with the central ion as terminal ligands; DIN and Cu 2+ Connect to each other along the c-axis to form a straight line; The asymmetric unit of Cu-2 includes a Cu ion, a deprotonated BTC (HBTC 2- ) ligand, 1 DIN, 1 free H2O and 1 free DMA molecule; the Cu ion is coordinated by the N atoms of the 2 imidazole groups and the O atoms of the 2 carboxyl groups; the Cu ion is bridged by the DIN ligand along the a∩c axis and by the HBTC 2- The ligands are attached along the b-axis; the final architecture of Cu-2 is a two-dimensional layer.

3. The method for preparing the Cu-based metal organic framework material according to any one of claims 1 to 2, characterized in that: It is as follows 1) or 2): 1) The Cu-based metal organic framework material is Cu-1, comprising the following steps: Dispersing Cu salt, DIN and BTC in a solvent, and heating in a closed system for reaction to obtain Cu-1; 2) The Cu-based metal organic framework material is Cu-2, comprising the following steps: The Cu salt, DIN and BTC are dispersed in a solvent containing DMA, and heated in a closed system for reaction to obtain the Cu-2.

4. The method for preparing a Cu-based metal organic framework material according to claim 3, characterized in that: In method 1) and method 2), the molar ratio of the Cu salt, the DIN and the BTC is (1-2):1:(1-2).

5. The method for preparing a Cu-based metal organic framework material according to any one of claims 3 to 4, characterized in that: In method 1), the Cu salt is one or more of CuSO4·5H2O, Cu(NO3)2·3H2O, CuCl2·2H2O and Cu(ClO4)2·6H2O; The solvent is composed of ethanol and water, wherein the volume ratio of ethanol to water is (1-4):1; The ratio of the Cu salt to the solvent is 0.5 mmol: 8-80 mL; In method 2), the Cu salt is one or more of Cu(ClO4)2·6H2O, Cu(NO3)2·3H2O, CuCl2·2H2O and Cu(ClO4)2·6H2O; The solvent containing DMA is composed of DMA and water, wherein the volume ratio of DMA to water is (1-4):1; The ratio of the Cu salt to the solvent containing DMA is 0.5 mmol:8-80 mL.

6. The method for preparing a Cu-based metal organic framework material according to any one of claims 3 to 5, characterized in that: In method 1) and method 2), the heating temperature is 80-120° C. and the heating time is 24-48 hours.

7. Use of the Cu-based metal organic framework material according to any one of claims 1 to 2 or the Cu-based metal organic framework material obtained by the preparation method according to any one of claims 3 to 6 in inhibiting Escherichia coli in darkness or under sunlight.

8. Use of the Cu-based metal organic framework material Cu-2 according to any one of claims 1 to 2 or the Cu-based metal organic framework material Cu-2 obtained by the preparation method according to any one of claims 3 to 6 in any of the following: A1) Inhibition of plant pathogenic bacteria; A2) Kill plant pathogenic bacteria; A3) Prevention and control of plant diseases; The steps A1) to A3) are carried out in the dark or under sunlight.

9. The use according to claim 8, characterized in that: The plant pathogenic bacteria include Pectobacterium carotovorum or Xanthomonas oryzae; The plant disease is cabbage soft rot or rice bacterial blight.

10. Use of the Cu-based metal organic framework material according to any one of claims 1 to 2 or the Cu-based metal organic framework material obtained by the preparation method according to any one of claims 3 to 6 in adsorbing and / or degrading the pollutant Congo red in darkness or under sunlight.

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