阅读说明：本技术 一种含杂多酸和过渡金属配合物的MOFs复合材料及其制备方法和应用 (MOFs composite material containing heteropoly acid and transition metal complex and preparation method and application thereof ) 是由 陈琦 王宁 邱璐 常兆森 于 2019-10-18 设计创作，主要内容包括：本发明公开了一种含杂多酸和过渡金属配合物的MOFs复合材料及其制备方法和应用。该材料在有机溶剂氮氮-二甲基甲酰胺存在下,将金属锆盐溶解并加热,然后加入4,4’-联苯二甲酸、铂金属有机配体、矿化剂苯甲酸与杂多酸,混合搅拌,然后水热反应一段时间,制备获得。首次获得了含杂多酸和过渡金属配合物的MOFs复合材料,并可用于气体吸附、分离与存储、多相催化等领域。(The invention discloses an MOFs composite material containing heteropoly acid and transition metal complex and a preparation method and application thereof. The material is prepared by dissolving and heating metal zirconium salt in the presence of an organic solvent nitrogen-dimethyl formamide, then adding 4,4' -biphenyl dicarboxylic acid, a platinum metal organic ligand, a mineralizer benzoic acid and heteropoly acid, mixing and stirring, and then carrying out hydrothermal reaction for a period of time. The MOFs composite material containing the heteropoly acid and the transition metal complex is obtained for the first time, and can be used in the fields of gas adsorption, separation and storage, heterogeneous catalysis and the like.)

1. A preparation method of MOFs composite material containing heteropoly acid and transition metal complex is characterized by comprising the following steps:

(1) preparing a platinum metal organic ligand from a 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and platinum metal complex through a coordination reaction;

(2) preparing heteropoly acid with keggin structure by coordination and bridging of heteroatom and polyatomic atom through oxygen atom;

(3) dissolving metal zirconium salt in an organic solvent, heating, adding 4,4' -biphenyldicarboxylic acid, a platinum metal organic ligand, a mineralizer and heteropoly acid, mixing and stirring, carrying out hydrothermal reaction for 96 hours, and filtering to obtain solid powder;

(4) and washing the solid powder with anhydrous nitrogen-dimethylformamide and isopropanol in sequence, and drying to obtain the MOFs composite material containing the heteropoly acid and the platinum metal complex.

2. The process for preparing MOFs composite material containing heteropoly acid and transition metal complex according to claim 1, wherein: the hetero atom used for preparing the heteropoly acid is one of phosphorus, silicon, germanium and arsenic.

3. The process for preparing MOFs composite material containing heteropoly acid and transition metal complex according to claim 2, wherein: the polyatomic acid used for preparing the heteropoly acid is one or two of molybdenum, tungsten, vanadium, niobium and tantalum.

4. The process for preparing MOFs composite material containing heteropoly acid and transition metal complex according to claim 3, wherein: the organic solvent is one of water, methanol, ethanol, ethylene glycol, glycerol, nitrogen dimethyl formamide, nitrogen dimethyl acetamide, nitrogen diethyl formamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane and dimethyl sulfoxide.

5. The process for preparing MOFs composite material containing heteropoly acid and transition metal complex according to claim 4, wherein: the mineralizer is one of formic acid, acetic acid, hydrochloric acid and benzoic acid.

6. The preparation method of the MOFs composite material containing heteropoly acid and transition metal complex according to claim 5, wherein the specific steps of the step (1) are as follows: dissolving 201mg of potassium chloroplatinate and 0.4mL of nitric acid with the mass fraction of 65% in 40mL of water, adding 101mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid, heating the reaction, stirring for 40-50 hours under the reflux condition, and then centrifugally drying to obtain a dark brown product, namely the platinum metal organic ligand.

7. The preparation method of the MOFs composite material containing heteropoly acid and transition metal complex according to claim 6, wherein the specific step of the step (2) is: mixing 30-100mL of sodium metavanadate solution with the concentration of 0.06g/mL-0.24g/mL with 30-100mL of disodium hydrogen phosphate dodecahydrate aqueous solution with the concentration of 0.07g/mL-0.17g/mL of water, then adding 1.5-5mL of concentrated sulfuric acid, adding sodium molybdate solution with the concentration of 0.6g/mL-0.65g/mL dissolved in 65-200 mL, adding 28-85mL of concentrated sulfuric acid while stirring the solution, cooling to room temperature, then extracting with diethyl ether, finally blowing off the ether by air, dissolving the residual solid in water, recrystallizing, washing, and air-drying to obtain the heteropoly acid.

8. The preparation method of the MOFs composite material containing the heteropoly acid and the transition metal complex according to claim 7, wherein the step (3) comprises the specific steps of dissolving a metal zirconium salt in nitrogen-dimethyl formamide, heating, adding 4,4 '-biphenyldicarboxylic acid, a platinum metal organic ligand, benzoic acid and the heteropoly acid, mixing and stirring, carrying out hydrothermal reaction at 95 ℃ for 72 ~ 96h, and filtering to obtain solid powder, wherein the molar ratio of the zirconium salt, the 4,4' -biphenyldicarboxylic acid, the platinum metal organic ligand, a mineralizer and the heteropoly acid is 15 (10 ~ 5) to (5 ~ 10) to 75: 3.

9. A MOFs composite containing a heteropoly acid and a transition metal complex, characterized by being obtained by the production method of any one of claims 1 to 8.

10. The use of the MOFs composite containing heteropolyacid and platinum metal complex according to claim 9 for gas adsorption, separation and storage, heterogeneous catalysis.

Technical Field

The invention belongs to the technical field of organic metal framework materials, and particularly relates to an MOFs composite material containing heteropoly acid and platinum metal complexes, and a preparation method and application thereof.

Background

In recent ten years, the metal organic framework material is used as a novel porous material, and the research on the metal organic framework material is more and more, so that the application development of the material is greatly promoted. Metal-organic frameworks (MOFs) are novel porous materials with a spatial porous structure in which metal ions or clusters are used as nodes and organic ligands are used as linkers. The metal organic framework material has the characteristics of high specific surface area, porosity, multifunctional structure, functional adjustability and the like, wherein the porosity is an important property of the material in catalysis, gas adsorption and separation, the specific surface area is another important index for evaluating the catalytic performance and the adsorption capacity of the porous material, and the characteristics of the metal organic framework material are widely applied to the research on gas adsorption, separation and storage, heterogeneous catalysis and the like, but the stability of the metal organic framework is poor, and the defect can be improved by introducing a new component into MOF, and meanwhile, the MOFs can be endowed with more abundant functional characteristics.

The transition metal complex is a transition metal complex generated by a class of transition metal and different molecules or groups, the transition metal has good oxidation-reduction capability and coordination capability, and meanwhile, the transition metal oxide has strong heat resistance and toxicity resistance, and has photosensitive, thermosensitive and impurity sensitivity, which is beneficial to the performance modulation of the catalyst, so the transition metal complex is considered as a catalyst with great prospect, but the recovery of the transition metal is difficult; the heteropoly acid is a metal-oxygen cluster compound which is formed by the coordination and bridging of heteroatoms and polyatomic atoms through oxygen atoms according to a certain structure, has high catalytic activity, not only acid catalytic performance, but also oxidation-reduction catalytic performance, is a multifunctional novel catalyst, but the heteropoly acid is easy to aggregate to form large grains, the catalytic performance of the heteropoly acid is weakened, and the heteropoly acid is easy to dissolve in water and organic solvents, so that the catalytic life of the heteropoly acid is short, and the exertion of the catalytic performance is limited.

Disclosure of Invention

In order to solve the problems, the invention provides a preparation method of MOFs composite material containing heteropoly acid and transition metal complex, and the prepared novel MOFs composite material has large specific surface area, high stability and easy reuse as a heterogeneous catalyst, and has a plurality of potential applications in the aspects of gas adsorption, separation and storage, heterogeneous catalysis and the like.

The purpose of the invention is realized by the following technical scheme:

a preparation method of MOFs composite material containing heteropoly acid and transition metal complex comprises the following steps:

(1) preparing a platinum metal organic ligand from a 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and platinum metal complex through a coordination reaction;

(2) preparing heteropoly acid with keggin structure by coordination and bridging of heteroatom and polyatomic atom through oxygen atom;

(3) dissolving metal zirconium salt in an organic solvent, heating, adding 4,4' -biphenyldicarboxylic acid, a platinum metal organic ligand, a mineralizer and heteropoly acid, mixing and stirring, carrying out hydrothermal reaction for 96 hours, and filtering to obtain solid powder;

(4) and washing the solid powder with anhydrous nitrogen-dimethylformamide and isopropanol in sequence, and drying to obtain the MOFs composite material containing the heteropoly acid and the platinum metal complex.

Further, the hetero atom used for preparing the heteropoly acid is one of phosphorus, silicon, germanium and arsenic.

Further, the polyatomic acid used for preparing the heteropoly acid is one or two of molybdenum, tungsten, vanadium, niobium and tantalum.

Further, the organic solvent is one of water, methanol, ethanol, ethylene glycol, glycerol, nitrogen-nitrogen dimethylformamide, nitrogen-nitrogen dimethylacetamide, nitrogen-nitrogen diethylformamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane and dimethyl sulfoxide.

Further, the mineralizer is one or more of formic acid, acetic acid, hydrochloric acid and benzoic acid.

Further, the specific steps of the step (1) are as follows: dissolving 201mg of potassium chloroplatinate and 65% of nitric acid in mass fraction, namely 0.4mL in 40mL of water, adding 101mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid, heating the reaction, stirring for 40-50 hours under the reflux condition, and then centrifugally drying to obtain a dark brown product, namely the platinum metal organic ligand.

Further, the specific steps of the step (2) are as follows: mixing 30-100mL of sodium metavanadate solution with the concentration of 0.06g/mL-0.24g/mL with 30-100mL of disodium hydrogen phosphate dodecahydrate aqueous solution with the concentration of 0.07g/mL-0.17g/mL of water, then adding 1.5-5mL of concentrated sulfuric acid, adding sodium molybdate solution with the concentration of 0.6g/mL-0.65g/mL dissolved in 65-200 mL, adding 28-85mL of concentrated sulfuric acid while stirring the solution, cooling to room temperature, then extracting with diethyl ether, finally blowing off the ether by air, dissolving the residual solid in water, recrystallizing, washing, and air-drying to obtain the heteropoly acid.

Further, the specific steps of the step (3) are as follows: dissolving metal zirconium salt in nitrogen-dimethyl formamide, heating, adding 4,4' -biphenyldicarboxylic acid, a platinum metal organic ligand, benzoic acid and heteropoly acid, mixing and stirring, and carrying out hydrothermal reaction at 95 ℃ for 72-96 h; filtering to obtain solid powder; the molar ratio of the zirconium salt, the 4,4' -biphenyldicarboxylic acid, the platinum metal organic ligand, the mineralizer and the heteropoly acid is 15 (10-5) to 5-10 to 75 to 3.

Further, the metal zirconium is zirconium tetrachloride or zirconium oxychloride.

The invention also comprises a MOFs composite material containing heteropoly acid and transition metal complex, which is obtained by the preparation method.

The MOFs composite material containing the heteropoly acid and the platinum metal complex is applied to the aspects of gas adsorption, separation and storage and heterogeneous catalysis.

The invention has the beneficial effects that:

the preparation method of the invention prepares the MOFs composite material containing heteropoly acid and transition metal complex for the first time, the pore size of the composite material is in nanometer scale, the pore structure is constructed by ionic bond and coordination bond connection, and the composite material has high porosity, multifunctional structure and functional adjustability. The unique net-shaped chemical structure of the composite material obtained by the preparation method of the invention enables the porous material of the invention to have wide application prospect in the aspect of shape selective catalytic research; the composite material obtained by the preparation method can be used for gas adsorption, separation and storage, heterogeneous catalysis and the like.

Drawings

FIG. 1 is an X-ray photoelectron spectrum of MOFs composite materials prepared in example 1 and example 2;

FIG. 2 is a scanning electron microscope image of the MOFs composite material prepared in example 1;

FIG. 3 is a nitrogen sorption-desorption isotherm plot of the MOFs composite prepared in example 1;

fig. 4 is a pore size distribution diagram of the MOFs composite prepared in example 1.

Detailed Description

In order to better understand the present invention, the following examples are further described, which are only used to explain the present invention and do not limit the present invention.

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available products.