CN110606959B - MOFs composite material containing heteropoly acid and transition metal complex and preparation method and application thereof - Google Patents
MOFs composite material containing heteropoly acid and transition metal complex and preparation method and application thereof Download PDFInfo
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Abstract
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.
Description
Technical Field
The invention belongs to the technical field of organic metal framework materials, and particularly relates to a 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 in 0.4mL of water in 40mL of water, adding 101mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid, heating the reaction, stirring for 40-50 hours under a reflux condition, and then carrying out centrifugal 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.
Example 1
A preparation method of MOFs composite material containing heteropoly acid and platinum metal complex comprises the following steps: dissolving and heating metal zirconium salt in the presence of an organic solvent nitrogen-dimethyl formamide, then adding 4,4' -biphenyldicarboxylic 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 to prepare the MOFs composite material containing the heteropoly acid and a platinum metal complex, wherein the specific steps are as follows:
(1) the preparation method of the platinum metal organic ligand comprises the following steps: 201mg of potassium chloroplatinate and 65% of 0.4mL nitric acid were dissolved in 40mL water in a 100mL round-bottomed flask, and 101mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid was added and suspended only in an acidic solution due to its poor solubility in the solution. The reaction was heated and stirred at reflux for 40 hours (reaction was vermillion), the precipitated red powder was isolated by filtration, washed three times with water, once with 2-propanol (isopropanol), and the powder was dried in air at 60 ℃ to give a dark brown product. (ii) a
(2) Boiling 8.12g sodium metavanadate in 34mL water to dissolve, then adding 5.969g disodium hydrogen phosphate dodecahydrate aqueous solution mixed in 34mL water, cooling, then adding 1.67mL concentrated sulfuric acid, the solution is red (deep red-black), adding 40.325g sodium molybdate solution dissolved in 66.67mL water, slowly adding 28.34mL concentrated sulfuric acid while vigorously stirring the solution, cooling the hot solution to room temperature (bright red), then extracting with 166.7mL diethyl ether, (three layers, the first layer is orange yellow, the second layer is red black, the third layer is orange red), finally blowing off ether by air, dissolving the remaining solid in water, recrystallizing, washing, and air drying;
(3) dissolving 0.86mol of zirconium tetrachloride in 34mL of nitrogen-dimethyl formamide, heating, adding 4,4' -biphenyldicarboxylic acid in an amount of 0.645mmol, platinum metal organic ligand in an amount of 0.215mmol, a mineralizer in an amount of 4.3mol and heteropoly acid in an amount of 0.172mol, 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 MOF-Z-1 containing the heteropoly acid and platinum metal complex.
Example 2
A preparation method of MOFs composite material containing heteropoly acid and platinum metal complex comprises the following steps: dissolving and heating metal zirconium salt in the presence of an organic solvent N, N-dimethylformamide, then adding 4,4' -biphenyldicarboxylic acid, a transition metal organic ligand, a mineralizer benzoic acid and heteropoly acid, mixing and stirring, and carrying out hydrothermal reaction for a period of time to prepare the MOFs composite material containing the heteropoly acid and a transition metal complex, wherein the specific steps are as follows:
(1) 201mg of potassium chloroplatinate and 65% of 0.4mL nitric acid were dissolved in 40mL water in a 100mL round-bottomed flask, and 101mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid was added and suspended only in an acidic solution due to its poor solubility in the solution. The reaction was heated and stirred at reflux for 42 hours (reaction was vermillion), the precipitated red powder was isolated by filtration, washed three times with water, once with 2-propanol (isopropanol), and the powder was dried in air at 60 ℃ to give a dark brown product. (ii) a
(2) Boiling 6.1g of sodium metavanadate in 100mL of water to dissolve the sodium metavanadate, adding 7.1g of disodium hydrogen phosphate dodecahydrate aqueous solution mixed in 100mL of water, cooling, adding 5mL of concentrated sulfuric acid to obtain a red solution, adding 133g of sodium molybdate solution dissolved in 200mL of water, slowly adding 85mL of concentrated sulfuric acid while vigorously stirring the solution, cooling the hot solution to room temperature (turning bright red), extracting with 400mL of diethyl ether, blowing off the ether by air, dissolving the remaining solid in water, recrystallizing, washing, and air-drying;
(3) dissolving 0.86mol of zirconium tetrachloride in 34mL of nitrogen-dimethyl formamide, heating, then adding 0.645mmol of 4,4' -biphenyldicarboxylic acid, 0.215mmol of platinum metal organic ligand, 4.3mol of mineralizer and 0.143mmol of heteropoly acid, mixing and stirring, then 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 MOF-Z-2 containing heteropoly acid and transition metal complexes.
In the above examples 1 and 2, the chemical reaction formula for preparing the transition metal organic ligand by compounding the pyridyl group-containing monomer with the platinum metal is as follows: as shown in the formula 1,
in the above examples 1 and 2, heteropoly acids having keggin structure were prepared from hetero atoms and polyatomic atoms in a certain structure through coordination bridging of oxygen atoms (the upper one was prepared in example 1, and the lower one was prepared in example 2); as shown in the formula 2 below,
in the above example 1, the MOFs composite containing heteropoly acid and platinum metal complex is prepared according to the following chemical reaction formula:
in the above example 2, the MOFs composite containing heteropoly acid and platinum metal complex is prepared according to the following chemical reaction formula:
the performance test analysis of the MOFs composite material containing heteropoly acid and platinum metal complex:
referring to FIG. 1, the MOF-Z-1 obtained in example 1 and the MOF-Z-2 obtained in example 2 of the present invention were analyzed by X-ray photoelectron spectroscopy, and it can be seen that vanadium has a binding energy of 976 eV, oxygen has a binding energy of 531 eV, nitrogen has a binding energy of 400 eV, platinum has a binding energy of 333 eV, carbon has a binding energy of 285 eV, molybdenum has a binding energy of 233 eV, zirconium has a binding energy of 183 eV, and phosphorus has a binding energy of 131 eV. Therefore, X-ray photoelectron spectroscopy tests prove the successful synthesis of the MOFs composite material containing the keggin type heteropoly acid and the platinum transition metal complex.
Referring to the attached figure 2, the surface morphology of the solid UiO-67-Z is tested by a high-resolution field emission scanning electron microscope, and the MOF-Z is composed of particles, the particle size distribution is between 200nm and 1000nm, and the pore size distribution is relatively uniform.
Referring to the attached figure 3, a full-automatic specific surface area and porosity analyzer (Micromeritics ASAP 2460) is used for detecting the specific surface area and the porosity of the solid MOF-Z, the nitrogen adsorption-desorption isothermal curve of the composite material MOF-Z prepared according to the embodiment 1 of the invention is the combination of type I and type IV, and an isothermal line shows high adsorption capacity under lower relative pressure, which indicates the existence of micropores (type I), the adsorption capacity is slightly increased in a relative pressure range of 0.5 to 0.8, and a small hysteresis loop appears on the curve, which indicates the existence of mesoporous distribution; the specific surface area value is 446m2g-1。
Referring to FIG. 4, the pore size distribution of MOF-Z, calculated by the delocalized density functional theory, is mainly in the range of 0.8-2 nm.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are also included in the scope of the present invention.
Claims (3)
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 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and potassium chloroplatinate through a coordination reaction;
(2) 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, 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 ether by air, dissolving the rest solid in water, recrystallizing, washing, and air-drying to obtain heteropoly acid;
(3) 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 benzoic acid and the heteropoly acid is 15 (10-5) to 5-10 to 75: 3;
(4) and washing the solid powder with anhydrous nitrogen-dimethylformamide and isopropanol in sequence, and drying to obtain the MOFs composite material containing heteropoly acid and potassium chloroplatinate.
2. The preparation method of the MOFs composite material containing heteropoly acid and transition metal complex according to claim 1, wherein the specific steps of 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.
3. 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 2.
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| CN113083371B (en) * | 2021-04-24 | 2022-11-15 | 太原理工大学 | Phosphotungstic acid loaded iron-based MOF material and preparation and application thereof |
| CN113368900B (en) * | 2021-05-26 | 2022-11-25 | 长春工业大学 | Preparation method and application of zirconium-based microporous coordination polymer composite material loaded by heteropoly acid or heteropoly acid salt |
| CN113307981A (en) * | 2021-06-11 | 2021-08-27 | 海南大学 | Sulfonyl bridged calix [4] arene iron-based porous complex for extracting uranium from seawater and preparation method thereof |
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