Antibacterial material of copper / iron ion doped metal-organic framework and preparation method of antibacterial material

Abstract

The invention provides a copper / iron ion doped metal-organic framework antibacterial material and a preparation method thereof, and the preparation method comprises the following steps: mixing a metal source, an organic ligand, soluble copper / iron salt and a solvent, carrying out a reaction at a temperature of 20-50 DEG C, and carrying out post-treatment to obtain the copper / iron ion doped metal-organic framework antibacterial material, the metal source comprises a zinc source and / or a cobalt source; the organic ligand includes an at least bidentate organic compound. According to the preparation method, high-temperature and high-pressure equipment is not needed, the environmental condition is mild, the preparation process is simple in technology, safe and controllable, and the production difficulty, cost and equipment requirements are greatly reduced; the prepared antibacterial material can generate reactive oxygen free radicals in a bright or dark environment, is high in sterilization efficiency, can decompose bacterial metabolites and bacterial toxins, and has a good killing effect on molds and viruses.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial materials, and in particular to an antibacterial material of a copper / iron ion doped metal-organic framework and a preparation method thereof. Background Art

[0002] Pathogenic microorganisms have always threatened human health and have become the second leading cause of death after cardiovascular disease. Using antibiotics to treat diseases caused by bacterial infections is an effective strategy. However, with the overuse of antibiotics, the emergence of super bacteria has gradually revealed the limitations of this method. Bacteria develop drug resistance quickly, and the research and development cycle of new antibiotics is long. Therefore, the development and utilization of efficient and safe non-antibiotic antibacterial materials and technologies have become an urgent need and research hotspot in the field of antibacterial. Traditional antibacterial materials, such as metal nano-antibacterial materials, including nano-silver, nano-gold, nano-copper, etc., have good antibacterial effects, but are prone to biotoxicity during use; organic antibacterial agents have good bactericidal effects, but poor thermal stability, short effective period, and are prone to biosafety issues; nano-oxide antibacterial materials, such as titanium oxide, zinc oxide, copper oxide, etc., kill bacteria by releasing ions or generating active oxygen free radicals under light, but the effect is slow and the bactericidal efficiency is low.

[0003] In recent years, as an emerging material, metal-organic framework materials have shown a rapid increase in the innovative design and application research of antibacterial materials due to their multi-selectivity of metal ions and organic ligands, large specific surface area, high porosity and structural functional diversity, as well as the synergistic effect between metal ions and ligands.

[0004] CN113425850A discloses a photosensitizing antibacterial modified porphyrin metal organic framework material and a preparation method thereof. The carbodiimide method is used to first activate the carboxyl group of the porphyrin metal organic framework material having photosensitizing activity; then, an amino-containing targeting ligand is subjected to amide condensation with the activated porphyrin metal organic framework material to obtain a functionalized nano antibacterial material whose morphology and crystal structure are not affected, and the material has enhanced bactericidal properties against bacteria.

[0005] CN117447714A discloses a method for preparing a nano-scale copper-based metal organic framework material, including the first step of preparing raw materials, the raw materials including copper nitrate trihydrate, anhydrous methanol, anhydrous ethanol, polyvinyl pyrrolidone and trimesic acid; the second step of preparing the dissolution before the reaction, the third step of carrying out the coordination reaction of the mixed solution, the fourth step of crystallizing and treating the generated product, using anhydrous ethanol for multiple cleaning and impurity removal, and the fifth step of drying, curing and grinding the crystal. With divalent copper ions as metal salt ions and trimesic acid as organic ligands, CO2 is allowed to exist in a supercritical state with both gaseous diffusion properties and liquid solubility, ensuring that the ideal solvent supercritical CO2 plays an auxiliary role, and synthesizing a nano-scale Cu-BTC material with high stability through coordination under mild operating conditions.

[0006] CN106120015A discloses a copper-based metal organic framework antibacterial fiber, which is prepared from polyester, copper-based metal organic framework material, and antibacterial agent. The polyester is 80-99.9%, the copper-based metal organic framework material is 0.1-20%, and the antibacterial agent is at least one of a quaternary ammonium salt antibacterial agent with a mass percentage concentration of 5-20% vitamin C and a halamine antibacterial agent with a mass percentage concentration of 5%-20% vitamin C. The method for preparing the antibacterial fiber is: melt-spinning the copper-based metal organic framework material and polyester through a spinning machine to obtain a copper-based metal organic framework polyester composite fiber; immersing the copper-based metal organic framework polyester composite fiber in the antibacterial agent, then rinsing, and drying to obtain the copper-based metal organic framework antibacterial fiber.

[0007] However, the preparation cost of the above-mentioned metal organic framework antibacterial materials is relatively high, and usually requires a large amount of organic solvents and synthesis conditions such as high temperature and high pressure. The antibacterial mechanism still has shortcomings such as over-reliance on ion dissolution and reliance on the external field of active oxygen. Summary of the invention

[0008] In view of the problems existing in the prior art, the present invention provides a copper / iron ion-doped metal-organic framework antibacterial material and a preparation method thereof. Metal sources, organic ligands, soluble copper / iron salts and solvents are used as reaction raw materials. No high-temperature and high-pressure equipment is required. Environmental conditions are mild. The preparation process is simple, safe and controllable. An antibacterial material based on the active oxygen action mechanism is obtained. Active oxygen free radicals can be generated in both light and dark environments. Therefore, the antibacterial material has high bactericidal efficiency, can decompose bacterial metabolites and bacterial toxins, has good killing effects on molds and viruses, has high industrial production prospects, and is suitable for application and promotion.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a method for preparing a copper / iron ion-doped metal-organic framework antibacterial material, the preparation method comprising:

[0011] The metal source, the organic ligand, the soluble copper / iron salt and the solvent are mixed, and the reaction is carried out at a temperature of 20 to 50° C., and the copper / iron ion-doped metal-organic framework antibacterial material is obtained through post-treatment;

[0012] The metal source includes a zinc source and / or a cobalt source; and the organic ligand includes an at least bidentate organic compound.

[0013] In the preparation method of the copper / iron ion doped metal-organic framework antibacterial material of the present invention, the metal source zinc / cobalt source is cheap and easy to obtain; it is mixed with an organic ligand, a soluble copper / iron salt and a solvent, and a reaction is carried out at a temperature of 20 to 50° C. There is heat release during the reaction, and no additional cooling or heating device is required.

[0014] The preparation method provided by the present invention can carry out multi-ion doping while reacting, wherein the ion doping is carried out by synchronously doping soluble copper / iron salts during the synthesis of the metal organic framework, and the metal ions include Cu + , Cu 2+ , Fe 3+ or Fe 2+ Any one or a combination of at least two of the above, these metal ions generate active free radicals through valence changes, and can generate active radicals in a light or dark environment, and can controllably release metal ions to further synergistically kill bacteria, so the bactericidal efficiency is high and the bactericidal effect is good.

[0015] The preparation method provided by the invention can achieve a high product yield, which can reach 95-102% of the theoretical yield, and is mostly 98-101%.

[0016] The reaction in the preparation method provided by the present invention is rapid and complete, and the solvent ratio and reaction time are adjustable, so it can be used as a treatment method for growing zinc / cobalt-based metal-organic frameworks in other systems. For example, a material containing zinc / cobalt ions is added to the membrane material in advance, and the membrane material is post-treated by adding a soluble copper / iron salt solution with a prepared ligand solution, so that the metal-organic framework grows in situ in the membrane material and is doped with copper / iron ions at the same time, and after cleaning and drying, the membrane material can be given excellent antibacterial properties.

[0017] The reaction temperature of the present invention is 20-50°C, for example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] Preferably, the zinc source comprises any one or a combination of at least two of a zinc salt, a zinc-containing oxide or a zinc-containing hydroxide, wherein typical but non-limiting combinations include a combination of a zinc salt and a zinc-containing oxide, a combination of a zinc-containing hydroxide and a zinc salt, or a combination of a zinc-containing oxide and a zinc-containing hydroxide; preferably, a zinc-containing oxide and / or a zinc-containing hydroxide.

[0019] The preferred zinc source of the present invention is zinc oxide and / or zinc hydroxide, and the reaction product is water, which does not cause environmental harm.

[0020] Preferably, the zinc salt comprises any one of zinc carbonate, basic zinc carbonate, zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or zinc oxalate, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of zinc carbonate and basic zinc carbonate, a combination of zinc nitrate and zinc sulfate, a combination of zinc acetate and zinc chloride or a combination of zinc oxalate and zinc nitrate; preferably zinc carbonate and / or basic zinc carbonate.

[0021] The zinc salt of the present invention is preferably zinc carbonate and / or basic zinc carbonate because the reaction products thereof are water and carbon dioxide, which do not cause environmental harm.

[0022] Preferably, the zinc-containing oxide is zinc oxide.

[0023] Preferably, the zinc-containing hydroxide is zinc hydroxide.

[0024] Preferably, the cobalt source comprises any one of a cobalt salt, a cobalt-containing oxide or a cobalt-containing hydroxide, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of a cobalt salt and a cobalt-containing oxide, a combination of a cobalt-containing hydroxide and a cobalt salt, or a combination of a cobalt-containing oxide and a cobalt-containing hydroxide; preferably, the cobalt-containing oxide and / or the cobalt-containing hydroxide.

[0025] In the present invention, the cobalt source is preferably a cobalt-containing oxide and / or a cobalt-containing hydroxide, and the reaction product is water, which does not cause environmental harm.

[0026] Preferably, the cobalt salt comprises any one of cobalt carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate or cobalt chloride, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of cobalt carbonate and cobalt chloride, a combination of cobalt nitrate and cobalt sulfate, or a combination of cobalt acetate and cobalt chloride.

[0027] Preferably, the cobalt-containing oxide is cobalt oxide.

[0028] Preferably, the cobalt-containing hydroxide is cobalt hydroxide.

[0029] Preferably, the organic ligand comprises any one of imidazole, triazole or pyrimidine or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of imidazole and triazole, a combination of pyrimidine and imidazole or a combination of triazole and pyrimidine.

[0030] Preferably, the imidazole comprises any one of 2-methylimidazole, 2-ethylimidazole or benzimidazole or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of 2-methylimidazole and 2-ethylimidazole, a combination of benzimidazole and 2-methylimidazole or a combination of 2-ethylimidazole and benzimidazole, preferably 2-methylimidazole and / or benzimidazole.

[0031] Preferably, the triazole comprises any one of 1,2,4-triazole, 3-amino-1,2,4-triazole or 3,5-diamino-1,2,4-triazole or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of 1,2,4-triazole and 3-amino-1,2,4-triazole, a combination of 3,5-diamino-1,2,4-triazole or 1,2,4-triazole, preferably 1,2,4-triazole.

[0032] Preferably, the pyrimidine comprises 2-hydroxypyrimidine and / or 4-hydroxypyrimidine.

[0033] Preferably, the molar ratio of the metal ion in the metal source to the organic ligand is (1-2):(1-4), for example, it can be 1:1, 1.2:2, 1.5:2, 1.3:2.5, 1.6:3, 1.8:3.5 or 2:3.7, etc., but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable. The stoichiometric ratio of the metal ion and the organic ligand is preferably used.

[0034] Preferably, the organic ligand accounts for 10-80% of the total weight of the solid raw material, for example, it can be 10%, 20%, 30%, 50%, 60%, 70% or 80%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] The total weight of the solid raw materials in the present invention refers to the total weight of the metal source, the organic ligand and the soluble copper / iron salt.

[0036] In the present invention, if the ratio of the soluble copper / iron salt to the total weight of the solid raw material is too small, the reaction speed is slow and the doping concentration is low, resulting in a low yield of active oxygen free radicals and a poor antibacterial effect; if the ratio of the soluble copper / iron salt to the total weight of the solid raw material is too large, the local reaction speed is too fast, the reaction products are uneven, and the copper / iron cannot be fixed in the metal organic framework, resulting in a waste of raw materials and a reduction in antibacterial efficiency.

[0037] Preferably, the soluble copper / iron salt comprises a soluble copper salt or a soluble iron salt.

[0038] Preferably, the soluble copper salt comprises any one of copper nitrate, copper sulfate, copper formate, copper acetate, copper oxalate, copper citrate or copper chloride, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of copper nitrate and copper sulfate, a combination of copper formate and copper acetate, a combination of copper oxalate and copper citrate, or a combination of copper chloride and copper formate.

[0039] Preferably, the soluble iron salt comprises any one of ferric nitrate, ferric sulfate, ferric formate, ferric acetate, ferric oxalate, ferric citrate or ferric chloride, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of ferric nitrate and ferric sulfate, a combination of ferric formate and ferric acetate, a combination of ferric oxalate and ferric citrate, or a combination of ferric chloride and ferric formate.

[0040] Preferably, the soluble copper / iron salt accounts for 0.1-10% of the total weight of the solid raw material, for example, it can be 0.1%, 0.5%, 1%, 3%, 5%, 8% or 10%, etc., but is not limited to the listed values. Other unlisted values ​​within this numerical range are also applicable, preferably 0.2-5%, and more preferably 0.5-4%.

[0041] Preferably, the solvent comprises a mixture of water and an organic solvent.

[0042] Preferably, the volume ratio of water to the organic solvent is (0-100):(100-0), for example, it can be 0:100, 10:90, 20:80, 30:70, 40:60, 50:50, 80:20, 90:10 or 100:0, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably (0-70):(30-100), more preferably (5-50):(50-95), and further preferably (10-30):(70-90).

[0043] Preferably, the organic solvent comprises any one or a combination of at least two of alcohol, dimethyl sulfoxide or amide, wherein typical but non-limiting combinations include a combination of alcohol and dimethyl sulfoxide, a combination of amide and alcohol, or a combination of dimethyl sulfoxide and amide.

[0044] Preferably, the alcohol comprises any one of methanol, ethanol, isopropanol, propanol, ethylene glycol or glycerol, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of methanol and ethanol, a combination of isopropanol and propanol or a combination of ethylene glycol and glycerol, preferably methanol or ethanol.

[0045] Preferably, the amide comprises N,N-dimethylformamide.

[0046] Preferably, before the mixing, the ligand solution and the copper / iron ion solution are prepared first, which can ensure that the metal source is evenly dispersed in the ligand solution, and then reacts synchronously with the synthesis of the metal organic framework. The copper / iron ion solution is mixed and doped more evenly, thereby increasing the reaction rate and shortening the reaction time.

[0047] Preferably, the ligand solution is obtained by mixing an organic ligand and a solvent, and the molar concentration is 2 to 15 mol / L, for example, it can be 2 mol / L, 3 mol / L, 5 mol / L, 8 mol / L, 10 mol / L or 15 mol / L, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0048] Preferably, the copper / iron ion solution is obtained by mixing a soluble copper / iron salt and water, and has a mass percentage concentration of 1 to 50%, for example, 1%, 3%, 5%, 10%, 20%, 30% or 50%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 5 to 25%.

[0049] Preferably, the reaction time is 1 min to 24 h, for example, 1 min, 5 min, 20 min, 50 min, 1 h, 10 h, 20 h or 24 h, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 2 min to 1 h, and more preferably 3 to 30 min.

[0050] Preferably, the post-treatment comprises any one of washing, drying or crushing or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of washing and drying, a combination of crushing and washing, or a combination of drying and crushing.

[0051] The present invention can obtain copper / iron doped metal-organic framework antibacterial powder with good crystal structure after drying and crushing, and can be directly further processed, such as compounding with resin to prepare antibacterial masterbatch or preparing slurry containing antibacterial powder for use.

[0052] Preferably, the washing comprises water washing or alcohol washing.

[0053] In the present invention, if one wants to obtain a copper / iron doped metal-organic framework antibacterial material with higher purity, the obtained metal-organic framework antibacterial material can be washed with alcohol or water to remove a small amount of unreacted substances and free copper / iron ions remaining in the powder, and then further processed and used according to the application field.

[0054] Preferably, the drying method includes any one of room temperature drying, heating evaporation, vacuum drying, freeze drying, spray drying or continuous tunnel kiln drying, or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of room temperature drying and heating evaporation, a combination of vacuum drying and freeze drying, or a combination of spray drying and continuous tunnel kiln drying.

[0055] Preferably, the heating evaporation temperature is 30-200°C, for example, it can be 30°C, 50°C, 100°C, 150°C, 180°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; preferably it is 80-150°C.

[0056] Preferably, the heating evaporation time is 2 to 24 hours, for example, it can be 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours or 24 hours, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 8 to 20 hours.

[0057] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0058] (1) preparing a ligand solution and a copper / iron ion solution;

[0059] The ligand solution is obtained by mixing an organic ligand and a solvent, and the molar concentration is 2 to 15 mol / L; the organic ligand includes any one of imidazole, triazole or pyrimidine or a combination of at least two; the solvent includes a mixture of water and an organic solvent; the volume ratio of water to organic solvent is (0 to 100): (100 to 0);

[0060] The copper / iron ion solution is obtained by mixing a soluble copper / iron salt and water, and the mass percentage concentration is 1-50%; the soluble copper / iron salt includes a soluble copper salt or a soluble iron salt; the soluble copper salt includes any one of copper nitrate, copper sulfate, copper formate, copper acetate, copper oxalate, copper citrate or copper chloride, or a combination of at least two of them; the soluble iron salt includes any one of iron nitrate, iron sulfate, iron formate, iron acetate, iron oxalate, iron citrate or iron chloride, or a combination of at least two of them; the soluble copper / iron salt accounts for 0.1-10% of the total weight of the solid raw material;

[0061] (2) After mixing the metal source and the ligand solution, adding the copper / iron ion solution, reacting at a temperature of 20 to 50° C. for 1 min to 24 h to obtain a solid product, then heating and evaporating the solid product at 30 to 200° C. for 2 to 24 h, and crushing to obtain the copper / iron ion-doped metal-organic framework antibacterial material;

[0062] The metal source includes a zinc source and / or a cobalt source; the zinc source includes any one of a zinc salt, a zinc-containing oxide or a zinc-containing hydroxide, or a combination of at least two of them; the cobalt source includes any one of a cobalt salt, a cobalt-containing oxide or a cobalt-containing hydroxide, or a combination of at least two of them; the molar ratio of the metal ion in the metal source to the organic ligand is (1-2):(1-4).

[0063] In a second aspect, the present invention further provides an antibacterial material prepared by the method for preparing the antibacterial material of a metal-organic framework doped with copper / iron ions as described in the first aspect.

[0064] The copper / iron ion doped metal-organic framework antibacterial material of the present invention is an antibacterial material based on the action mechanism of active oxygen species, has high bactericidal efficiency, can decompose bacterial metabolites and bacterial toxins, and has good effects on molds and viruses.

[0065] In a third aspect, the present invention further provides a use of the copper / iron ion-doped metal-organic framework antibacterial material as described in the second aspect, wherein the antibacterial material kills bacteria, molds and viruses and decomposes bacterial metabolites and bacterial toxins in an illuminated or lightless environment.

[0066] The copper / iron ion doped metal-organic framework antibacterial material described in the present invention is an antibacterial material based on the mechanism of action of active oxygen species. It can generate active oxygen free radicals in a light or lightless environment, and release metal ions for further synergistic sterilization. It can be used alone in the fields of antibacterial and mildew prevention, or prepared into an antibacterial masterbatch and used in combination with organic matter (such as polyester, PP, PE, PVC, etc.), so that the product has broad-spectrum antibacterial / mildew prevention and other effects.

[0067] Compared with the prior art, the present invention has at least the following beneficial effects:

[0068] (1) The preparation method of a copper / iron ion-doped metal-organic framework antibacterial material provided by the present invention does not require high temperature and high pressure equipment, has mild environmental conditions, and has a simple preparation process, which is safe and controllable, greatly reducing the production difficulty, cost and equipment requirements. The preparation method is green and environmentally friendly, and can prepare a copper / iron-doped metal-organic framework with adjustable structure and performance, has a high industrial production prospect, and is suitable for application and promotion.

[0069] (2) The copper / iron ion doped metal-organic framework antibacterial material provided by the present invention is mainly based on the action mechanism of active oxygen species. It can produce active oxygen free radicals in the presence or absence of light. It has high bactericidal efficiency, can decompose bacterial metabolites and bacterial toxins, and has a good killing effect on bacteria, molds and viruses. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1This is the XRD diagram of the copper / iron ion doped metal-organic framework antibacterial material prepared in Example 1 of the present invention.

[0071] Figure 2 This is the XRD diagram of the copper / iron ion doped metal-organic framework antibacterial material prepared in Example 2 of the present invention.

[0072] Figure 3 This is the XRD diagram of the copper / iron ion doped metal-organic framework antibacterial material prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0073] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0074] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0075] The raw materials used in the following examples are all commercially available products and were not further purified during the synthesis process.

[0076] Example 1

[0077] This embodiment provides a method for preparing a copper ion-doped metal-organic framework antibacterial material, the preparation method comprising the following steps:

[0078] (1) preparing a ligand solution and a copper ion solution;

[0079] The ligand solution is prepared by mixing 36.5 g of an organic ligand 2-methylimidazole, the amount of which is 0.44 mol, with 50 mL of a solvent, methanol, and the molar concentration is 8.9 mol / L.

[0080] The copper ion solution is obtained by adding 1g of soluble copper salt copper sulfate into 5mL of deionized water and dissolving it, and the mass percentage concentration is 18.5%;

[0081] (2) After mixing 17.9 g of the metal source zinc oxide and the ligand solution, a copper ion solution was added, and the reaction was carried out at a temperature of 22° C. for 1 h to obtain a solid product, and then the solid product was heated and evaporated at 80° C. for 16 h, and the copper ion-doped metal-organic framework antibacterial material zinc-2-methylimidazole was obtained after crushing;

[0082] The soluble copper salt copper sulfate accounts for 1.8% of the total weight of the solid raw material, the molar ratio of zinc ions in the metal source zinc oxide to the organic ligand 2-methylimidazole is 2:4, and the organic ligand 2-methylimidazole accounts for 65.9% of the total weight of the solid raw material.

[0083] Figure 1 The XRD pattern of the copper ion doped metal-organic framework antibacterial material prepared in this embodiment is shown. It can be seen from the figure that no ZnO characteristic peak is detected in the zinc-based metal-organic framework, indicating that the reaction in the preparation method provided by the present invention is relatively complete. 2+ Almost completely converted into MOF (Metal Organic Framework).

[0084] Example 2

[0085] This embodiment provides a method for preparing an antibacterial material of a metal-organic framework doped with iron ions, the preparation method comprising the following steps:

[0086] (1) preparing a ligand solution and an iron ion solution;

[0087] The ligand solution is obtained by mixing 41.05 g of an organic ligand 2-methylimidazole, the amount of which is 0.5 mol, with 50 mL of ethanol and 50 mL of water as a solvent, and the molar concentration is 5 mol / L;

[0088] The iron ion solution is obtained by adding 3.38g of soluble iron salt FeCl3·6H2O into 20mL of deionized water and dissolving it, and the mass percentage concentration is 14.4%;

[0089] (2) mixing 24.85 g of metal source zinc hydroxide, the amount of which is 0.25 mol, with the ligand solution, and then adding the iron ion solution, reacting at a temperature of 20° C. for 5 min to obtain a solid product, and then heating and evaporating the solid product at 120° C. for 16 h, and crushing to obtain the iron ion-doped metal-organic framework antibacterial material zinc-2-methylimidazole;

[0090] The iron salt FeCl3·6H2O accounts for 4.88% of the total weight of the solid raw materials, the molar ratio of zinc ions in the zinc source zinc hydroxide and the organic ligand 2-methylimidazole is 1:2, and the organic ligand 2-methylimidazole accounts for 59.25% of the total weight of the solid raw materials.

[0091] Figure 2 The XRD pattern of the iron-doped metal-organic framework antibacterial material obtained in this example is shown. It can be seen from the figure that no characteristic peak of zinc hydroxide is detected in the metal-organic framework, indicating that the reaction in the preparation method provided by the present invention is relatively complete.

[0092] Example 3

[0093] This embodiment provides a method for preparing an antibacterial material of a metal-organic framework doped with iron ions, the preparation method comprising the following steps:

[0094] (1) preparing a ligand solution and an iron ion solution;

[0095] The ligand solution is obtained by mixing 32.84 g of an organic ligand 2-methylimidazole, the amount of which is 0.4 mol, with 25 mL of methanol and 25 mL of water as a solvent, and the molar concentration is 6.7 mol / L;

[0096] The iron ion solution is obtained by adding 6.0 g of soluble iron salt FeCl3·6H2O into 20 mL of deionized water and dissolving it, and the mass percentage concentration is 22.9%;

[0097] (2) mixing 21.86 g of metal source zinc hydroxide, the amount of which is 0.25 mol, with the ligand solution, and then adding the iron ion solution, reacting at a temperature of 30° C. for 5 min to obtain a solid product, and then heating and evaporating the solid product at 120° C. for 16 h, and crushing to obtain the iron ion-doped metal-organic framework antibacterial material zinc-2-methylimidazole;

[0098] The iron salt FeCl3·6H2O accounts for 8.71% of the total weight of the solid raw materials, the molar ratio of zinc ions in the zinc source zinc hydroxide and the organic ligand 2-methylimidazole is 1:2, and the organic ligand 2-methylimidazole accounts for 59.57% of the total weight of the solid raw materials.

[0099] Figure 3 The XRD pattern of the iron-doped metal-organic framework antibacterial material obtained in this example is shown. It can be seen from the figure that no characteristic peak of zinc hydroxide is detected in the metal-organic framework, indicating that the reaction in the preparation method provided by the present invention is relatively complete.

[0100] Example 4

[0101] This embodiment provides a method for preparing a copper ion-doped metal-organic framework antibacterial material, the preparation method comprising the following steps:

[0102] (1) preparing a ligand solution and a copper ion solution;

[0103] The ligand solution is obtained by mixing 27.63 g of organic ligand 1,2,4-triazole and 50 mL of solvent, and the molar concentration is 8 mol / L;

[0104] The copper ion solution is obtained by mixing 1g of soluble copper salt copper acetate and 10mL of water, and the mass percentage concentration is 2%;

[0105] (2) After mixing 32.29 g of the metal source zinc sulfate and the ligand solution, a copper ion solution was added, and the reaction was carried out at a temperature of 27° C. for 12 hours to obtain a solid product, and then the solid product was heated and evaporated at 200° C. for 10 hours, and the copper ion-doped metal-organic framework antibacterial material zinc-based triazole was obtained after crushing;

[0106] The soluble copper salt copper acetate accounts for 1.6% of the total weight of the solid raw material, the molar ratio of zinc ions in the zinc source zinc sulfate and the organic ligand 1,2,4-triazole is 1:2, and the organic ligand 1,2,4-triazole accounts for 53.0% of the total weight of the solid raw material.

[0107] Example 5

[0108] This embodiment provides a method for preparing an antibacterial material of a metal-organic framework doped with iron ions, the preparation method comprising the following steps:

[0109] (1) preparing a ligand solution and an iron ion solution;

[0110] The ligand solution is obtained by mixing 28.83 g of organic ligand 4-hydroxypyrimidine and 100 mL of solvent, and the molar concentration is 3 mol / L;

[0111] The iron ion solution is obtained by mixing 1.5 g of soluble iron salt ferric chloride and 3 mL of water, with a mass percentage concentration of 25%;

[0112] (2) After mixing 11.89 g of the metal source cobalt carbonate and the ligand solution, an iron ion solution was added, and the reaction was carried out at a temperature of 23° C. for 6 hours to obtain a solid product, and then the solid product was heated and evaporated at 30° C. for 20 hours, and the iron ion-doped metal-organic framework antibacterial material cobalt-based 4-hydroxypyrimidine was obtained after crushing;

[0113] The soluble iron salt ferric chloride accounts for 3.5% of the total weight of the solid raw material, the molar ratio of cobalt ions in cobalt carbonate to the organic ligand 4-hydroxypyrimidine is 1:3, and the organic ligand 4-hydroxypyrimidine accounts for 68.3% of the total weight of the solid raw material.

[0114] Example 6

[0115] This embodiment provides a method for preparing a copper ion-doped metal-organic framework antibacterial material. The preparation method is the same as that of Example 1 except that the soluble copper salt copper sulfate accounts for 0.1% of the total weight of the solid raw material.

[0116] Example 7

[0117] This embodiment provides a method for preparing a copper ion-doped metal-organic framework antibacterial material. The preparation method is the same as that of Example 1 except that the soluble copper salt copper sulfate accounts for 85% of the total weight of the solid raw materials.

[0118] Example 8

[0119] This embodiment provides a method for preparing a copper ion-doped metal-organic framework antibacterial material. The preparation method is the same as that of Embodiment 1 except that the molar concentration of the ligand solution is 1 mol / L.

[0120] Example 9

[0121] This embodiment provides a method for preparing a copper ion-doped metal-organic framework antibacterial material. The preparation method is the same as that of Embodiment 1 except that the molar concentration of the ligand solution is 20 mol / L.

[0122] Escherichia coli (E. coli) was used as a Gram-negative model bacterium. Specific test steps: First, the bacterial solution was mixed with the antibacterial material prepared in the above embodiment, and the final concentrations of the antibacterial material and bacteria were 10ug / mL and 10 8 CFU / mL, and then the bacterial solution with antibacterial material was cultured at 37°C and 150 rpm for 1 h. After the culture, the solution was diluted with sterile water by 1, 10, and 10 2 , 10 3 , 10 4 , 10 5 and 10 6 Finally, 1 mL of bacterial solution with different dilution concentrations was added to about 15 mL of LB nutrient agar (about 40°C). After the agar solidified, it was cultured in a constant temperature and humidity chamber at 37°C and 70% humidity for 24 hours. The number of colonies was recorded, the agar photos were scanned, and the antibacterial rate was calculated. Sterile water was used instead of antibacterial materials as a blank control. All measurements were performed in triplicate.

[0123] Staphylococcus aureus (S. aureus) was used as a Gram-positive model bacterium. The experimental steps were basically the same as the antibacterial experiment of Escherichia coli, except that the target strain was replaced by Staphylococcus aureus.

[0124] The antibacterial rate is calculated as follows:

[0125] Antibacterial rate = (1-C / C0) × 100%

[0126] Among them, C is the average colony number of the experimental group, and C0 is the average colony number of the control group.

[0127] The product yield is calculated by the ratio of the mass of the obtained antibacterial material to the mass calculated by the molar amount of the metal source added. The yield calculation formula is:

[0128]

[0129] The results of the antibacterial experimental reaction time, product yield, antibacterial rate of Escherichia coli (E. coli) and antibacterial rate of Staphylococcus aureus (S. aureus) of the antibacterial materials prepared in the above examples are shown in Table 1.

[0130] Table 1

[0131]

[0132]

[0133] From Table 1 we can see that:

[0134] (1) Based on Examples 1 to 5, it can be seen that the preparation method of the copper / iron ion-doped metal-organic framework antibacterial material provided by the present invention is simple to operate, and the reaction conditions are mild. The obtained copper / iron ion-doped metal-organic framework antibacterial material has a short reaction time when conducting an antibacterial experiment, and the product yield can reach more than 100.6%. The antibacterial rate against Gram-negative model bacteria and Gram-positive model bacteria is high, and the antibacterial effect is excellent;

[0135] (2) Combining Example 1 with Examples 6 to 7, it can be seen that in Example 6, the ratio of the soluble copper salt copper sulfate to the total weight of the solid raw material is too small, which will lead to a slow reaction rate and a low doping concentration, thereby resulting in a low yield of active oxygen free radicals and a poor antibacterial effect; in Example 7, the ratio of the soluble copper salt copper sulfate to the total weight of the solid raw material is too large, the local reaction rate is too fast, the reaction product is uneven, and copper cannot be fixed in the metal organic framework, resulting in a waste of raw materials and a reduction in antibacterial efficiency;

[0136] (3) Combining Example 1 with Examples 8 to 9, it can be seen that the molar concentration of the ligand solution in Example 8 is relatively low, which will lead to a decrease in the space-time yield and a decrease in the antibacterial performance; the molar concentration of the ligand solution in Example 9 is relatively high, which will result in the inability to completely dissolve the ligand, high system viscosity, uneven reaction, reduced yield and decreased antibacterial performance.

[0137] In summary, the method for preparing the antibacterial material of the copper / iron ion doped metal-organic framework provided by the present invention requires mild environmental conditions, rapid reaction, high product yield, excellent antibacterial effect, and product regulation and multi-metal doping can be performed simultaneously during the synthesis process to achieve the purpose of functionalization of the metal-organic framework. In addition, the synthesis invention does not require special production equipment, has low equipment requirements, has a high industrial production prospect, and is suitable for large-scale application and promotion.

[0138] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing an antibacterial material of a copper / iron ion doped metal-organic framework, It is characterized in that The preparation method comprises: The metal source, the organic ligand, the soluble copper / iron salt and the solvent are mixed, and the reaction is carried out at a temperature of 20 to 50° C., and the copper / iron ion-doped metal-organic framework antibacterial material is obtained through post-treatment; The metal source includes a zinc source and / or a cobalt source; and the organic ligand includes an at least bidentate organic compound.

2. The preparation method according to claim 1, It is characterized in that The zinc source comprises any one of zinc salt, zinc oxide or zinc hydroxide or a combination of at least two thereof, preferably zinc oxide and / or zinc hydroxide; Preferably, the zinc salt comprises any one or a combination of at least two of zinc carbonate, basic zinc carbonate, zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or zinc oxalate, preferably zinc carbonate and / or basic zinc carbonate; Preferably, the zinc-containing oxide is zinc oxide; Preferably, the zinc-containing hydroxide is zinc hydroxide; Preferably, the cobalt source comprises any one of a cobalt salt, a cobalt-containing oxide or a cobalt-containing hydroxide, or a combination of at least two thereof, preferably a cobalt-containing oxide and / or a cobalt-containing hydroxide; Preferably, the cobalt salt includes any one or a combination of at least two of cobalt carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate or cobalt chloride; Preferably, the cobalt-containing oxide is cobalt oxide; Preferably, the cobalt-containing hydroxide is cobalt hydroxide.

3. The preparation method according to claim 1 or 2, It is characterized in that The organic ligand includes any one or a combination of at least two of imidazole, triazole or pyrimidine; Preferably, the imidazole comprises any one of 2-methylimidazole, 2-ethylimidazole or benzimidazole or a combination of at least two thereof, preferably 2-methylimidazole and / or benzimidazole; Preferably, the triazole includes any one of 1,2,4-triazole, 3-amino-1,2,4-triazole or 3,5-diamino-1,2,4-triazole or a combination of at least two thereof, preferably 1,2,4-triazole; Preferably, the pyrimidine comprises 2-hydroxypyrimidine and / or 4-hydroxypyrimidine; Preferably, the molar ratio of the metal ion in the metal source to the organic ligand is (1-2):(1-4), preferably a stoichiometric ratio of the metal ion to the organic ligand; Preferably, the organic ligand accounts for 10-80% of the total weight of the solid raw material.

4. The preparation method according to any one of claims 1 to 3, It is characterized in that The soluble copper / iron salt includes a soluble copper salt or a soluble iron salt; Preferably, the soluble copper salt includes any one or a combination of at least two of copper nitrate, copper sulfate, copper formate, copper acetate, copper oxalate, copper citrate or copper chloride; Preferably, the soluble iron salt comprises any one of ferric nitrate, ferric sulfate, ferric formate, ferric acetate, ferric oxalate, ferric citrate or ferric chloride, or a combination of at least two thereof; Preferably, the soluble copper / iron salt accounts for 0.1-10% of the total weight of the solid raw material, preferably 0.2-5%, and more preferably 0.5-4%.

5. The preparation method according to any one of claims 1 to 4, It is characterized in that The solvent includes a mixture of water and an organic solvent; Preferably, the volume ratio of water to the organic solvent is (0-100):(100-0), preferably (0-70):(30-100), more preferably (5-50):(50-95), more preferably (10-30):(70-90); Preferably, the organic solvent comprises any one or a combination of at least two of alcohol, dimethyl sulfoxide or amide; Preferably, the alcohol comprises any one of methanol, ethanol, isopropanol, propanol, ethylene glycol or glycerol, or a combination of at least two thereof, preferably methanol or ethanol; Preferably, the amide comprises N,N-dimethylformamide.

6. The preparation method according to any one of claims 1 to 5, It is characterized in that Before the mixing, a ligand solution and a copper / iron ion solution are prepared; Preferably, the ligand solution is obtained by mixing an organic ligand and a solvent, and the molar concentration is 2 to 15 mol / L; Preferably, the copper / iron ion solution is obtained by mixing soluble copper / iron salt and water, and the mass percentage concentration is 1 to 50%, preferably 5 to 25%.

7. The preparation method according to any one of claims 1 to 6, It is characterized in that The reaction time is 1 min to 24 h, preferably 2 min to 1 h, and more preferably 3 to 30 min; Preferably, the post-treatment method includes any one of washing, drying or crushing, or a combination of at least two thereof; Preferably, the drying method includes any one or a combination of at least two of room temperature drying, heating evaporation, vacuum drying, freeze drying, spray drying or continuous tunnel kiln drying; Preferably, the heating evaporation temperature is 30 to 200°C, preferably 80 to 150°C; Preferably, the heating evaporation time is 2 to 24 hours, preferably 8 to 20 hours.

8. The preparation method according to any one of claims 1 to 7, It is characterized in that The preparation method comprises the following steps: (1) preparing a ligand solution and a copper / iron ion solution; The ligand solution is obtained by mixing an organic ligand and a solvent, and the molar concentration is 2-15 mol / L; the organic ligand includes any one of imidazole, triazole or pyrimidine or a combination of at least two; the organic ligand accounts for 10-80% of the total weight of the solid raw material; the solvent includes a mixture of water and an organic solvent; the volume ratio of water to organic solvent is (0-100):(100-0); The copper / iron ion solution is obtained by mixing a soluble copper / iron salt and water, and the mass percentage concentration is 1-50%; the soluble copper / iron salt includes a soluble copper salt or a soluble iron salt; the soluble copper salt includes any one of copper nitrate, copper sulfate, copper formate, copper acetate, copper oxalate, copper citrate or copper chloride, or a combination of at least two of them; the soluble iron salt includes any one of iron nitrate, iron sulfate, iron formate, iron acetate, iron oxalate, iron citrate or iron chloride, or a combination of at least two of them; the soluble copper / iron salt accounts for 0.1-10% of the total weight of the solid raw material; (2) After mixing the metal source and the ligand solution, adding the copper / iron ion solution, reacting at a temperature of 20 to 50° C. for 1 min to 24 h to obtain a solid product, then heating and evaporating the solid product at 30 to 200° C. for 2 to 24 h, and crushing to obtain the copper / iron ion-doped metal-organic framework antibacterial material; The metal source includes a zinc source and / or a cobalt source; the zinc source includes any one of a zinc salt, a zinc-containing oxide or a zinc-containing hydroxide, or a combination of at least two of them; the cobalt source includes any one of a cobalt salt, a cobalt-containing oxide or a cobalt-containing hydroxide, or a combination of at least two of them; the molar ratio of the metal ion in the metal source to the organic ligand is (1-2):(1-4).

9. An antibacterial material prepared by the method for preparing an antibacterial material of a metal-organic framework doped with copper / iron ions as claimed in any one of claims 1 to 8.

10. Use of the antibacterial material according to claim 9, It is characterized in that The antibacterial material kills bacteria, molds and viruses and decomposes bacterial metabolites and bacterial toxins in a light or dark environment.

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