Metal organic complex material as well as preparation method and application thereof
By reacting inorganic metal salts with organic solvents and ligands under normal pressure at room temperature, a multi-metal-organic complex material is quickly prepared, which solves the problems of low preparation efficiency and high energy consumption in the prior art, achieves efficient and low-cost production, and significantly improves the degradation ability of chemical poisons.
Patent Information
- Application Number
- CN202510191741.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-20
- Publication Date
- 2025-06-27
AI Technical Summary
The existing multi-metal-organic complex materials have problems such as low preparation efficiency, high energy consumption and high cost in large-scale production, which is difficult to meet the needs of rapid and efficient production.
By mixing the inorganic metal salt with an organic solvent, adding a regulator and an organic ligand, and carrying out a reaction at room temperature and normal pressure, the polymetal-organic complex material is quickly prepared.
The rapid preparation of multi-metal-organic complex materials (within 10 minutes), reduces production energy consumption and cost, improves preparation efficiency, and significantly improves the degradation ability of chemical poisons.
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of the preparation of organic-inorganic hybrid materials, and specifically relates to a metal-organic complex material, a preparation method thereof, and an application thereof. Background Art
[0002] Pesticides and chemical agents pose great harm to human health. For example, organophosphorus agents can cause damage to the nervous system after entering the human body. Although there are already many materials that can be used to degrade chemical agents, these materials all have certain deficiencies in terms of degradation efficiency and stability, and it is difficult to meet the needs of practical applications. Due to the diversity of the structure of multi-metal-organic complex materials, they have unique stable structures and chemical properties, and show good advantages in the degradation of agents. Therefore, solving problems such as the production efficiency and high degradation efficiency of multi-metal-organic complex materials is the key to promoting their wide application in agent degradation.
[0003] Multi-structured metal-organic complex materials have ultra-high specific surface areas, adjustable pore structures, catalytic activities, and stabilities, and are considered effective catalytic materials for rapidly degrading agents. However, due to defects in large-scale production, they face a series of challenges in practical applications. For example, traditional synthesis techniques such as solvothermal methods and hydrothermal methods require high reaction temperatures (≥80°C), reaction pressures, long reaction times, high energy consumption, and limited yields; while new concept synthesis techniques such as microwave, ultrasound, electrochemistry, and mechanochemistry all require special synthesis equipment and cannot meet the requirements of convenient and efficient production. Therefore, there is an urgent need for a rapid and efficient synthesis method to improve the preparation efficiency of multi-metal-organic complex materials and reduce production requirements and costs. Summary of the Invention
[0004] [Technical Problem]
[0005] The technical problem to be solved by the present invention is: to provide a multi-metal-organic complex material that can be rapidly prepared and can rapidly and efficiently degrade chemical agents.
[0006] [Technical Solution]
[0007] To solve the above technical problem, the present invention provides the following technical solution:
[0008] In the first aspect, the present invention provides a multi-metal-organic complex material, which is a complex formed by multiple metal element centers and organic ligands through coordination bonds; the metal elements include cerium, zirconium, and iron; the organic ligands include one or more of terephthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and dihydroxy-biphenyldicarboxylic acid.
[0009] In one embodiment, the metal elements include cerium, zirconium, and iron.
[0010] In one embodiment, the molar ratio of the metal salts of cerium, zirconium, and iron is (0 - 80):(3 - 80):
[0011] (3 - 6).
[0012] In a second aspect, the present invention also provides a method for preparing a metal-organic complex material, comprising the following steps:
[0013] S1. Mix an inorganic metal salt with an organic solvent and stir to dissolve the inorganic metal salt;
[0014] S2. Add a regulator to the solution obtained in step S1;
[0015] S3. Wait for the solution of S2 to cool to room temperature, add an organic ligand, and stir thoroughly for reaction;
[0016] S4. Wait for the reaction solution of S3 to cool to room temperature, perform solid-liquid separation, collect the precipitate, wash, and dry to obtain the multi-metal-organic complex material;
[0017] The regulator includes hydrogen peroxide.
[0018] In one embodiment, the inorganic metal salts include cerium salts, zirconium salts, and iron salts.
[0019] In one embodiment, the cerium salts include trivalent cerium salts and / or tetravalent cerium salts. The zirconium salts include tetravalent zirconium salts. The iron salts include trivalent iron salts and / or divalent iron salts. Preferably, the inorganic metal salts include cerium trichloride, zirconium tetrachloride, and ferric chloride.
[0020] In one embodiment, the organic solvent in step S1 includes N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).
[0021] In one embodiment, the concentration of the metal salt in step S1 is 0.06 - 6 mol / L.
[0022] In one embodiment, the organic ligand includes one or more of terephthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and dihydroxy-biphenyldicarboxylic acid.
[0023] In one embodiment, the molar ratio of the inorganic metal salt to the organic ligand is (1 - 24):1.
[0024] In one embodiment, the concentration of the hydrogen peroxide is 3% - 30%.
[0025] In one embodiment, the reaction conditions are normal temperature and pressure.
[0026] In a third aspect, the present invention also provides an application of the multi-metal-organic complex material described in the first aspect or the metal-organic complex material prepared by the method described in the second aspect in the degradation of chemical agents.
[0027] In one embodiment, the chemical agent mimic includes dimethyl methylphosphonate (DMMP). The degradation reaction is carried out in a heterogeneous, solvent-free manner.
[0028] It should be understood that within the scope of the present invention, the above technical features of the present invention and the technical features specifically described below (such as in the examples) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be elaborated one by one here.
[0029] Compared with the prior art, the present invention has the following beneficial effects:
[0030] (1) The preparation of unit metal-organic complex materials in the traditional hydrothermal method (comparative example) requires a long reaction time (≥12 hours), a high reaction temperature (≥80 °C), and specific reaction equipment (hydrothermal reaction kettle), which cannot meet the needs of large-scale, efficient continuous production. The preparation of the metal-organic complex of the present invention does not require specific preparation conditions such as heating and pressurization and specific preparation equipment, and can be prepared quickly (within 10 minutes). In the reaction system, cerium, zirconium, and iron metal salts are introduced, and after adding a regulator and an organic ligand, a multi-metal-organic complex material can be prepared extremely quickly, which can meet the needs of low-energy consumption and high-efficiency production preparation.
[0031] (2) In Example 1 of the present invention, the degradation amount of DMMP by the obtained multi-metal-organic complex material reached 67.15 mg / g within 15 minutes. Specific Embodiments
[0032] The present invention will be further described in detail below in conjunction with specific embodiments. The examples given are only for clarifying the present invention, rather than limiting the scope of the present invention. The following examples can be used as a guide for those of ordinary skill in the art to make further improvements, and do not limit the present invention in any way.
[0033] The experimental methods in the following examples are all conventional methods unless otherwise specified, and are carried out according to the techniques or conditions described in the literature in this field or according to the product instructions. The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
[0034] DMMP Degradation Reaction System and Method: Add 100 mg of inorganic metal catalyst powder into a sealed glass bottle containing 10 mg of DMMP. After standing at room temperature for 15 minutes, add 5 mL of acetonitrile for extraction. Take the filtrate and perform gas chromatography test analysis.
[0035] Examples:
[0036] Example 1:
[0037] Preparation of Multimetal-Organic Complex Material:
[0038] (1) Add 4.80 mmol of cerium(III) chloride heptahydrate, 0.30 mmol of zirconium(IV) chloride, and 0.30 mmol of iron(III) chloride hexahydrate into 20 mL of DMF solution.
[0039] (2) Slowly add 1 mL of 30% hydrogen peroxide to the solution obtained in step (1) in batches.
[0040] (3) Wait for the solution obtained in step (2) to cool to room temperature, add 1 mol of dihydroxyterephthalic acid, stir well, and a large amount of precipitate appears within 10 minutes.
[0041] (4) Wait for the reaction in step (3) to cool to room temperature, filter, wash, and dry to obtain a dark brown powder, which is the multimetal-organic complex material.
[0042] Example 2:
[0043] Preparation of Multimetal-Organic Complex Material:
[0044] (1) Add 2.40 mmol of cerium(III) chloride heptahydrate, 0.30 mmol of zirconium(IV) chloride, and 0.30 mmol of iron(III) chloride hexahydrate into 20 mL of DMF solution.
[0045] (2) Slowly add 1 mL of hydrogen peroxide to the solution obtained in step (1) in batches.
[0046] (3) Wait for the solution obtained in step (2) to cool to room temperature, then add 1 mol of dihydroxyterephthalic acid, stir well, and a large amount of precipitate appears within 10 minutes.
[0047] (4) Wait for the reaction solution in step (3) to cool to room temperature, filter, wash, and dry to obtain a dark brown powder, which is the multimetal-organic complex material.
[0048] Example 3:
[0049] Preparation of Multimetal-Organic Complex Material:
[0050] (1) Add 1.20 mmol of cerium(III) chloride heptahydrate, 0.30 mmol of zirconium(IV) chloride, and 0.30 mmol of iron(III) chloride hexahydrate to 20 mL of DMF solution.
[0051] (2) Slowly add 1 mL of 30% hydrogen peroxide to the solution obtained in step (1) in batches.
[0052] (3) After the solution obtained in step (2) is cooled to room temperature, add 1 mmol of dihydroxyterephthalic acid, stir well, and a large amount of precipitate appears within 10 minutes.
[0053] (4) After the reaction solution described in step (3) is cooled to room temperature, filter, wash, and dry to obtain a dark brown powder, which is the multi-metal-organic complex material.
[0054] Example 4:
[0055] Preparation of binary metal-organic complex material:
[0056] (1) Add 0.30 mmol of zirconium(IV) chloride and 0.30 mmol of iron(III) chloride hexahydrate to 20 mL of DMF solution.
[0057] (2) Slowly add 1 mL of 30% hydrogen peroxide to the solution obtained in step (1) in batches.
[0058] (3) After the solution obtained in step (2) is cooled to room temperature, add 1 mmol of dihydroxyterephthalic acid, stir well, and a large amount of precipitate appears within 10 minutes.
[0059] (4) After the reaction solution described in step (3) is cooled to room temperature, filter, wash, and dry to obtain a dark brown powder, which is the binary metal-organic complex material.
[0060] Comparative Example 1:
[0061] Preparation of cerium-based metal-organic complex material:
[0062] (1) Add 1.20 mmol of cerium(III) chloride heptahydrate to 20 mL of DMF solution, stir to dissolve, slowly add 1 mL of 30% hydrogen peroxide in batches, and wait for the solution to cool to room temperature.
[0063] (2) Dissolve 1 mmol of dihydroxyterephthalic acid in 10 mL of DMF.
[0064] (3) Add the solutions in steps (1) and (2) to a hydrothermal reaction kettle and react at 80 °C for 12 hours.
[0065] (4) After the reaction is completed, it is cooled to room temperature, filtered, washed, and dried to obtain the powder, which is the cerium-based metal-organic complex material.
[0066] Comparative Example 2:
[0067] Preparation of zirconium-based metal-organic complex material:
[0068] (1) Add 1.20 mmol of zirconium tetrachloride to 20 mL of DMF solution, stir to dissolve, and slowly add 1 mL of 30% hydrogen peroxide in batches. Wait for the solution to cool to room temperature.
[0069] (2) Dissolve 1 mmol of dihydroxyterephthalic acid in 10 mL of DMF.
[0070] (3) Add the solutions from steps (1) and (2) to a hydrothermal reaction kettle and react at 80 °C for 12 hours.
[0071] (4) After the reaction is completed, it is cooled to room temperature, filtered, washed, and dried to obtain the powder, which is the zirconium-based metal-organic complex material.
[0072] Comparative Example 3:
[0073] Preparation of iron-based metal-organic complex material:
[0074] (1) Add 1.20 mmol of ferric chloride hexahydrate to 20 mL of DMF solution, stir to dissolve, and slowly add 1 mL of 30% hydrogen peroxide in batches. Wait for the solution to cool to room temperature.
[0075] (2) Dissolve 1 mmol of dihydroxyterephthalic acid in 10 mL of DMF.
[0076] (3) Add the solutions from steps (1) and (2) to a hydrothermal reaction kettle and react at 80 °C for 12 hours.
[0077] (4) After the reaction is completed, it is cooled to room temperature, filtered, washed, and dried to obtain the powder, which is the iron-based metal-organic complex material.
[0078] Example 5:
[0079] The DMMP degradation effect of the materials prepared in the examples and comparative examples was tested, and the results are as follows:
[0080] The experimental results are shown in Table 1. It can be seen that the binary metal-organic complex material prepared in Example 4 of the present invention can degrade 18.16 mg of DMMP within 15 minutes, while the iron-based metal-organic complex material in Comparative Example 3 is only 9.36 mg / g. By introducing zirconium metal, the catalytic efficiency of the iron-based structure towards the chemical agent can be improved. And by further introducing cerium metal, the catalytic activity of the complex material is further enhanced. The degradation efficiencies of the catalyst materials obtained in Examples 1-3 are all higher than those of the single-metal-organic complex materials, indicating that the synergistic effect of the ternary metal can improve the activity of the catalyst. And as the proportion of cerium ions increases, the degradation rate of DMMP also increases. The degradation amount of the catalyst material obtained in Example 1 towards DMMP reached 67.15 mg / g within 15 minutes.
[0081] It can be seen that through the regulation of the stoichiometric ratio, not only can the structure and morphology of the complex material be regulated, but also its catalytic degradation performance can be improved. The single-metal-organic complex material prepared in the comparative example has a general degradation ability towards DMMP and cannot meet the actual needs. While the multi-metal-organic material coordinated by cerium-zirconium-iron prepared in the examples is not only prepared quickly, but also can rapidly degrade a large amount of chemical agent simulants, which provides an effective way to rapidly degrade toxic and harmful substances in the real environment.
[0082] Table 1 Comparison of the degradation effects of metal-organic complex materials on DMMP under different preparation conditions
[0083] Metal-organic complex materials Degradation amount within 15 minutes Example 1 Multi-metal-organic complex materials 67.15 mg / g Example 2 Multi-metal-organic complex materials 53.07 mg / g Example 3 Multi-metal-organic complex materials 40.35 mg / g Example 4 Binary metal-organic complex materials 18.16 mg / g Comparative Example 1 Cerium-based metal-organic complex materials 11.55 mg / g Comparative Example 2 Zirconium-based metal-organic complex materials 39.82 mg / g Comparative Example 3 Iron-based metal-organic complex materials 9.36 mg / g
[0084] Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various modifications and decorations without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims.
Claims
1. A multi-metal-organic complex material, characterized in that: The multi-metal-organic complex material is a complex formed by multiple metal element centers and organic ligands through coordination bonds; the metal elements include zirconium and iron; the organic ligands include one or more of terephthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and dihydroxybiphenyl dicarboxylic acid.
2. The multi-metal-organic complex material according to claim 1, characterized in that: The metal elements include cerium, zirconium and iron.
3. The method for preparing the multi-metal-organic complex material according to claim 2, characterized in that: The following steps are involved: S1, mixing an inorganic metal salt with an organic solvent, and stirring to dissolve the inorganic metal salt; S2, adding a regulator to the solution obtained in step S1; S3, after the S2 solution is cooled to room temperature, add the organic ligand and stir the reaction thoroughly; S4, after the reaction liquid in S3 is cooled to room temperature, the solid-liquid separation is performed, and the precipitate is collected, washed, and dried to obtain the multi-metal-organic complex material.
4. The method according to claim 3, characterized in that The inorganic metal salts include cerium salts, zirconium salts and iron salts; preferably, the cerium salts include trivalent cerium salts and / or tetravalent cerium salts, the zirconium salts include tetravalent zirconium salts, and the iron salts include trivalent iron salts and / or divalent iron salts; further preferably, the inorganic metal salts include cerium trichloride, zirconium tetrachloride and ferric chloride.
5. The method according to claim 3, characterized in that: The molar ratio of cerium, zirconium and iron is (0-80): (3-80): (3-6).
6. The method according to claim 3, characterized in that The organic ligand includes one or more of terephthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and dihydroxy-biphenyl dicarboxylic acid.
7. The method according to claim 3, characterized in that The regulator includes hydrogen peroxide, and the concentration of hydrogen peroxide is 3-30%.
8. Use of the metal-organic complex material according to claim 1 or 2 or the multi-metal-organic complex material prepared by the method according to any one of claims 3 to 7 in the degradation of chemical toxic agents.
9. The use according to claim 8, characterized in that: The chemical toxicant includes dimethyl methylphosphonate.