CN106883422B - Metal organic framework based on imidazole sulfonic acid, preparation method and application - Google Patents

Metal organic framework based on imidazole sulfonic acid, preparation method and application Download PDF

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CN106883422B
CN106883422B CN201710097293.3A CN201710097293A CN106883422B CN 106883422 B CN106883422 B CN 106883422B CN 201710097293 A CN201710097293 A CN 201710097293A CN 106883422 B CN106883422 B CN 106883422B
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organic framework
imidazole
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姚丙建
丁罗刚
范琪
毕延雪
刘慧�
马坤玉
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Shandong Normal University
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Abstract

The invention provides an imidazole sulfonic acid-based metal organic framework, a preparation method and application thereof, wherein the imidazole sulfonic acid-based metal organic framework is obtained by synthesizing and modifying an imidazole ligand-based metal organic framework by adopting a sulfonic compound, and the chemical structural formula of the imidazole ligand-based metal organic framework is [ Zr ]6O4(OH)4L6]nWherein n is a natural number greater than 0, L is an organic ligand L, and the chemical structural formula is as follows:
Figure DDA0001230670290000011
the synthesis method of the organic ligand L comprises the steps of firstly reacting 3-methyl-terephthalic acid to obtain an intermediate A, secondly reacting the intermediate A and bromosuccinimide as raw materials to obtain an intermediate B, thirdly reacting the intermediate B and imidazole as raw materials to obtain an intermediate C, and finally hydrolyzing the intermediate C to obtain the organic ligand L. The metal organic framework based on the imidazole sulfonic acid has the characteristics of catalytic effect on benzaldehyde under normal pressure, mild reaction conditions, short reaction time, small catalyst consumption, recoverability and reutilization.

Description

Metal organic framework based on imidazole sulfonic acid, preparation method and application
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to an imidazole sulfonic acid-based metal organic framework, and a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) materials are hybrid materials with a repeating network structure formed by self-assembly of organic ligands and metal ions, and are new materials that have developed relatively rapidly in the field of coordination chemistry in recent decades. Compared with the traditional inorganic porous material, the MOFs material has larger void ratio and specific surface area, especially adjustable pore size and variable functional groups, so the application of the MOFs material as a porous functional material in the aspects of gas separation and storage represents great advantage. At present, MOFs materials have been applied to hydrogen storage, drug delivery, catalytic reactions, biosensors, gas adsorption and separation, and the like. The research on metal organic frame materials relates to the latest results of organic chemistry, inorganic chemistry, coordination chemistry, material chemistry, life science, computer science and other disciplines, so in recent years, the MOFs are receiving more and more attention from research teams.
The existing metal organic framework material is used as a catalyst, the catalytic center of the metal organic framework material is mostly limited to unsaturated metal sites of the metal organic framework material, specifically, due to the existence of small solvent molecules such as Dimethylformamide (DMF), water, ethanol and the like, unsaturated metal centers are combined with the unsaturated metal centers to meet the coordination requirement, and the solvent molecules can be removed after heating or vacuum treatment, so that the unsaturated metal sites are exposed. The metal sites exposed after removal of the axial ligands can act as lewis acid catalytic centers to accelerate the reaction. However, the existing metal organic framework material is used as a catalyst, and the metal sites are only used as catalytic centers of lewis acid, so that the catalytic effect is poor. Meanwhile, the organic strong acid molecular catalyst can efficiently catalyze reactions such as condensation, esterification and the like. However, the use of such molecular catalysts is disadvantageous for catalyst recovery and product separation.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an imidazole sulfonic acid-based metal organic framework, which fixes strong acid type ionic liquid on a metal organic framework material, greatly improves the catalytic effect of the metal organic framework, and can be recycled for multiple times when the metal organic framework is adopted for catalysis.
In order to fix the strong acid type ionic liquid on the metal organic framework, the invention provides an organic ligand L for synthesizing the metal organic framework based on the imidazole sulfonic acid, and the chemical structural formula is as follows:
Figure BDA0001230670270000021
named 2- (1-imidazolyl) -terephthalic acid
In order to obtain the organic ligand L, the invention also provides a synthetic method of the organic ligand L. Firstly, 2-methyl-terephthalic acid is reacted to obtain an intermediate A (namely 2-methyl-terephthalic acid diester), secondly, the intermediate A and bromosuccinimide are used as raw materials to react to obtain an intermediate B, thirdly, the intermediate B and imidazole are used as raw materials to react to obtain an intermediate C, and finally, the intermediate C is subjected to hydrolysis reaction to obtain the organic ligand L.
Wherein the structural formula of the intermediate A is as follows:
Figure BDA0001230670270000022
wherein R is an alkyl group having less than 3 carbon atoms, such as methyl, ethyl, propyl, and the like.
The structural formula of the intermediate B is as follows:
Figure BDA0001230670270000023
wherein R is an alkyl group having less than 3 carbon atoms, such as methyl, ethyl, propyl, and the like.
The structural formula of the intermediate C is as follows:
Figure BDA0001230670270000024
wherein R is an alkyl group having less than 3 carbon atoms, such as methyl, ethyl, propyl, and the like.
For the preparation of the imidazolesulfonic acid based metal-organic framework, the present invention also provides a precursor of the imidazolesulfonic acid based metal-organic framework, i.e., an imidazole ligand based metal-organic framework, having the chemical structure [ Zr ]6O4(OH)4L6]nWherein L is the organic ligand L, and n is a natural number more than 0.
The invention provides an imidazole sulfonic acid-based metal organic framework, which is obtained by synthesizing and modifying the imidazole ligand-based metal organic framework by using a sulfonic compound.
The synthesis formula is as follows:
Figure BDA0001230670270000031
wherein the content of the first and second substances,
Figure BDA0001230670270000032
is a structural formula of a metal organic framework based on imidazole ligand,
Figure BDA0001230670270000033
is a structural simple formula of a metal organic framework based on imidazole sulfonic acid, R1Is an alkyl group or an alkyl group in which a H atom is substituted with a F atom.
The invention also provides an application of the metal-organic framework based on the imidazole sulfonic acid in nano catalysis. The imidazole sulfonic acid-based metal organic framework is used as the catalyst, so that the reaction condition is mild, the reaction time is short, the catalyst dosage is small, and the catalyst can be recycled.
In order to reduce the condensation reaction condition of benzaldehyde, the invention provides a benzaldehyde condensation reaction method, which takes benzaldehyde and ethylene glycol as substrates, takes the imidazole sulfonic acid-based metal organic framework as a catalyst, and takes toluene as a solvent to carry out condensation reaction at 90 ℃ and 1 atm.
The invention has the beneficial effects that:
(1) the invention introduces the characteristic structure of strong acid type polyion liquid into the metal organic framework nano porous material, widens the variety of polyion liquid materials and realizes the function integration of the two materials.
(2) The imidazole sulfonic acid-based metal organic framework has an obvious catalytic effect on benzaldehyde under normal pressure, and has the characteristics of relatively mild reaction conditions, short reaction time, small catalyst consumption, and recyclability and reutilization.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a drawing of intermediate A1H-NMR spectrum;
FIG. 2 is a drawing of intermediate B1H-NMR spectrum;
FIG. 3 is a drawing of intermediate C1H-NMR spectrum;
FIG. 4 shows an organic ligand L1H-NMR spectrum;
FIG. 5 is a schematic representation of the reaction of intermediate C directly with propyl sultone to produce product D1H-NMR spectrum;
FIG. 6 is an SEM image of a metal organic framework based on imidazole ligands;
FIG. 7 is a PXRD spectrum of an imidazole ligand-based metal organic framework;
FIG. 8 is a schematic representation of a digested imidazole ligand-based metal organic framework1H-NMR spectrum;
FIG. 9 is a diagram of the imidazole ligand-based metal-organic framework N at 77K2An adsorption curve;
FIG. 10 is a PXRD spectrum of an imidazolesulfonic acid-based metal organic framework;
FIG. 11 is an infrared spectrum of post-synthesis modification of an imidazole ligand-based metal organic framework;
FIG. 12 is of a digested imidazole sulfonic acid based metal organic framework1H-NMR spectrum;
FIG. 13 is a graph monitoring the yield of a metal organic framework catalyzed condensation reaction based on imidazole sulfonic acid;
FIG. 14 is a graph of the catalytic condensation reaction yield for 5 repetitions of an imidazole sulfonic acid-based metal organic framework;
fig. 15 is a PXRD pattern of an imidazole sulfonic acid based metal organic framework catalyzed repeatedly 5 times.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The synthesis modification in the invention refers to a process of synthesizing a sulfonic acid group compound and a metal organic framework so that the metal organic framework is modified by the sulfonic acid group compound.
Described in the invention1The H-NMR spectrum is a nuclear magnetic resonance hydrogen spectrum, wherein,1H-NMR is English abbreviation of hydrogen spectrum of nuclear magnetic resonance.
The SEM image in the present invention is a scanning electron microscope photograph, wherein SEM is an english abbreviation of a scanning electron microscope (abbreviated as scanning electron microscope).
The PXRD spectrogram is a polycrystalline powder X-ray diffraction spectrogram, wherein the X-ray diffraction of the PXRD polycrystalline powder is abbreviated as English.
As described in the background art, the metal organic framework material in the prior art has the defect that the strong acid type ionic liquid cannot be fixed, and in order to solve the technical problems, the application provides an organic ligand L for synthesizing the metal organic framework based on the imidazole sulfonic acid.
In one exemplary embodiment of the present application, there is provided an organic ligand L for the synthesis of an imidazolesulfonic acid based metal-organic framework, designated 2- (1-imidazolyl) -terephthalic acid, having the chemical formula:
Figure BDA0001230670270000051
the organic ligand not only contains carboxyl capable of forming a coordination bond with metal ions, the organic ligand and the metal can be centrifuged to form a metal organic framework through two carboxyl, but also tertiary amine nitrogen in imidazole groups in the organic ligand can fix the strong acid type ionic liquid, so that the metal organic framework containing the organic ligand L can fix the strong acid type ionic liquid.
In order to obtain the organic ligand L, the invention also provides a synthetic method of the organic ligand L. Firstly, 2-methyl-terephthalic acid is reacted to obtain an intermediate A (namely 2-methyl-terephthalic acid diester), secondly, the intermediate A and bromosuccinimide are used as raw materials to react to obtain an intermediate B, thirdly, the intermediate B and imidazole are used as raw materials to react to obtain an intermediate C, and finally, the intermediate C is subjected to hydrolysis reaction to obtain the organic ligand L.
Wherein the structural formula of the intermediate A is as follows:
Figure BDA0001230670270000052
wherein R is an alkyl group having less than 3 carbon atoms, such as methyl, ethyl, propyl, and the like.
The structural formula of the intermediate B is as follows:
Figure BDA0001230670270000053
wherein R is an alkyl group having less than 3 carbon atoms, such as methyl, ethyl, propyl, and the like.
The structural formula of the intermediate C is as follows:
Figure BDA0001230670270000054
wherein R is an alkyl group having less than 3 carbon atoms, such as methyl, ethyl, propyl, and the like.
The reaction of the intermediate a can be carried out by esterification of 2-methyl-terephthalic acid and alcohol to synthesize the intermediate a in one step, or by reacting 2-methyl-terephthalic acid with halogenated reagents (such as phosphorus trichloride, phosphorus pentachloride, thionyl chloride and the like) to convert carboxyl in 3-methyl-terephthalic acid into acyl halide, and then adding alcohol to carry out alcoholysis reaction to obtain the intermediate a. The esterification reaction has less steps, short time and easy operation, and is suitable for research and application in laboratories. Although the steps of firstly carrying out acyl halide and then carrying out alcoholysis are more, the conversion rate and the product yield are higher, and the production cost can be reduced, so that the method is more suitable for industrial production.
The alcohol is a compound having a side chain of an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon in which a hydrogen atom is substituted with a hydroxyl group. Since the above reaction for synthesizing the intermediate a involves esterification and alcoholysis reactions, the lower alcohol having a relatively small carbon chain is in a liquid state, which facilitates the reaction, and thus the preferred alcohol is methanol, ethanol or propanol.
The esterification reaction comprises the steps of adding methanol and concentrated sulfuric acid into 3-methyl-terephthalic acid, heating and refluxing the mixture by using the concentrated sulfuric acid as a catalyst, adjusting the pH value to be neutral, filtering, and washing to obtain an intermediate A.
Preferably, the intermediate B is synthesized by taking the intermediate A and bromosuccinimide as raw materials, adding an initiator, heating and refluxing, and then purifying to obtain the intermediate B.
The purification is a process of purifying the product.
Further preferably, the purification step includes cooling the refluxed liquid, distilling under reduced pressure to obtain a crude product, and then performing column chromatography separation on the crude product to obtain the intermediate B.
The crude product is a product with lower purity. The purity of the product separated by column chromatography is more than 99 percent.
The initiator is organic peroxide initiator or azo initiator (such as azobisisobutyronitrile), and the like.
The molar ratio of the intermediate A, bromosuccinimide and the initiator is 1 (1-1.5) to 0.1-0.2.
Preferably, the reaction starting from intermediate B and imidazole is carried out in acetonitrile. The acetonitrile has better solubility to the intermediate B and the imidazole, and can ensure that the intermediate B and the imidazole are fully contacted, thereby improving the reaction rate and the conversion rate of reactants.
Preferably, the synthesis reaction conditions of the intermediate C are heating to 80 ℃ and refluxing for 2 hours.
The purification procedure for intermediate C was: and (4) carrying out reduced pressure distillation on the liquid after the reflux reaction, and then recrystallizing to obtain an intermediate C.
Preferably, the molar ratio of the intermediate B to the imidazole is 1 (1.2-2). Because the organic synthesis reactions are all reversible reactions, the conversion rate of the materials can not reach 100 percent basically, and the conversion rate of the intermediate B can be greatly improved by increasing the input molar weight of imidazole. Thereby greatly reducing the loss of raw materials and energy resources caused by step synthesis.
The hydrolysis reaction of the present invention is the hydrolysis of an ester.
Preferably, the hydrolysis reaction comprises the steps of adding the intermediate C, lithium hydroxide and a solvent respectively, stirring at room temperature, adjusting pH, and removing the solvent by reduced pressure distillation to obtain the organic ligand L.
Further preferably, the solvent is a mixture of methanol and water. Wherein the volume ratio of the methanol to the water is 3: 1.
More preferably, the stirring time is 10-14 h. Ensuring the full progress of the hydrolysis reaction.
More preferably, the pH is adjusted to 2 to 3 using hydrobromic acid.
More preferably, the molar ratio of intermediate C to lithium hydroxide is 1: 10.
For the preparation of the imidazolesulfonic acid based metal-organic framework, the present invention also provides a precursor of the imidazolesulfonic acid based metal-organic framework, i.e., an imidazole ligand based metal-organic framework, having the chemical structure [ Zr ]6O4(OH)4L6]nWherein L is the organic ligand L, and n is a natural number more than 0.
In order to synthesize the metal organic framework based on the imidazole ligand, the invention also provides a preparation method of the metal organic framework based on the imidazole ligand, which comprises the steps of dissolving the organic ligand L, acid and zirconium salt in a polar solvent, heating to 120 +/-5 ℃, keeping the temperature for 24-48 h, and reacting to obtain the metal organic framework.
In the present invention, the acid may be an organic acid such as glacial acetic acid, benzoic acid, etc., preferably glacial acetic acid; inorganic acids such as hydrochloric acid and the like are also possible.
Preferably, the polar solvent is a solvent having high polarity and a high dielectric constant. Such as N, N-Dimethylformamide (DMF), methanol, ethanol, diethyl ether, and the like. Preferably DMF.
Preferably, the zirconium salt is zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide or zirconium nitrate. Zirconium tetrachloride is preferred.
Preferably, the temperature is reduced to room temperature after the reaction.
The room temperature in the invention is 15-25 ℃.
Preferably, the adding amount ratio of the organic ligand L, the zirconium salt, the acid and the polar solvent is 0.01:0.01:0.3 (3-5), and the mol ratio is mol: mol: L.
Specifically, taking zirconium tetrachloride as an example, the synthesis formula is as follows:
Figure BDA0001230670270000071
the invention provides an imidazole sulfonic acid-based metal organic framework, which is obtained by synthesizing and modifying the imidazole ligand-based metal organic framework by using a sulfonic compound.
The synthesis formula is as follows:
Figure BDA0001230670270000072
wherein the content of the first and second substances,
Figure BDA0001230670270000081
is a structural formula of a metal organic framework based on imidazole ligand,
Figure BDA0001230670270000082
is a structural simple formula of a metal organic framework based on imidazole sulfonic acid, R1Is an alkyl group or an alkyl group in which a H atom is substituted with a F atom.
Preferably, the step of synthetic modification is to place the metal organic framework based on the imidazole ligand in a nonpolar solvent, add the compound with sulfonic acid group at 50 ℃ +/-5 ℃, stir for 24 h-36 h, and dry in vacuum at 60 ℃ +/-5 ℃ for 12 h-24 h.
In the present invention, the sulfonic acid group compound may be trifluoromethanesulfonic acid, methanesulfonic acid, sultone, etc., and propyl sultone is preferred.
Preferably, the nonpolar solvent is a solvent having low polarity and a small dielectric constant. Such as acetone, dichloromethane, chloroform, benzene, carbon tetrachloride, and the like. Acetone is preferred.
The invention also provides an application of the metal-organic framework based on the imidazole sulfonic acid in nano catalysis. The imidazole sulfonic acid-based metal organic framework is used as the catalyst, so that the reaction condition is mild, the reaction time is short, the catalyst dosage is small, and the catalyst can be recycled.
In order to improve the catalytic effect of the metal organic framework based on the imidazole sulfonic acid, the invention provides an activation method of the metal organic framework based on the imidazole sulfonic acid, which comprises the specific steps of soaking and activating the metal organic framework in absolute ethyl alcohol for 24-48 h, and drying in vacuum at 60 ℃ for 12-24 h.
Preferably, the activation method is that the metal organic framework is soaked and activated in absolute ethyl alcohol for 36 hours, and is dried in vacuum at 60 ℃ for 12 hours.
In order to reduce the condensation reaction condition of benzaldehyde, the invention provides a benzaldehyde condensation reaction method, which takes benzaldehyde and ethylene glycol as substrates, takes the imidazole sulfonic acid-based metal organic framework as a catalyst, and takes toluene as a solvent to carry out condensation reaction at 90 ℃ and 1 atm.
"atm" is short for atmosphere and refers to standard atmospheric pressure at sea level on earth, and in the present invention, "atm" is pressure unit, 1[ atm ] ═ 1.01325Bar ═ 760 mmHg.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific examples and comparative examples.
Example 1: preparation of organic ligand L
(1) 2-methyl-p-phenylene bisFormic acid (0.9g,5mmol) was mixed with methanol (50mL) and reacted under catalysis of concentrated sulfuric acid (5mL) under reflux for 12 h. Cooling, and vacuum filtering to obtain white solid as intermediate A in 95.0% yield1The H-NMR spectrum is shown in FIG. 1.
(2) A100 mL round bottom flask was charged with dimethyl 2-methyl-terephthalate (1.04g,5mmol), bromosuccinimide (1.335g,7.5mmol), AIBN (0.246g,1.5mmol), and benzene (45mL) before heating to 80 deg.C and refluxing for 12 hours. Cooling, and evaporating the solvent under reduced pressure to obtain a crude product. Dissolving with dichloromethane, filtering to obtain filtrate, removing solvent under reduced pressure, and separating by column chromatography (petroleum ether: dichloromethane 1: 1) to obtain pale yellow semisolid 1.45g as intermediate B with yield of 45.0% and intermediate B1The H-NMR spectrum is shown in FIG. 2.
(3) Under the protection of nitrogen, imidazole (0.136g,2mmol), sodium hydride (0.048g,2mmol) and tetrahydrofuran (45mL) are added into a 100mL three-neck round-bottom flask, heated to 65 ℃ and refluxed for 2 hours, then intermediate B (0.285g,1mmol) is added, refluxed for 2.5 hours, cooled, and the solvent is evaporated under reduced pressure to obtain a product, namely intermediate C, namely yellow oily matter, the yield is 85%, and the intermediate C is obtained1The H-NMR spectrum is shown in FIG. 3.
(4) To a 100mL round bottom flask was added intermediate C, lithium hydroxide (10equiv), methanol: stirring for 12h at room temperature with water (3: 1), cooling, adjusting pH to 2-3 with hydrobromic acid, removing the solvent by reduced pressure evaporation, and precipitating a white product, namely the organic ligand L with the yield of 90%, the organic ligand L1The H-NMR spectrum is shown in FIG. 4.
Example 2: reactivity of ligand with sulfonic acid Compound
Intermediate C (0.274g,1mmol) obtained in example 1 was refluxed with an equimolar amount of propylsultone (0.112g,1mmol) in 30mL of acetone for 5h, and the solvent was removed by rotary evaporation to give product D1The H-NMR spectrum is shown in FIG. 5.
Example 3: preparation of metal organic frameworks based on imidazole ligands
Reacting ZrCl4(28.8mg,0.12mmol) and glacial acetic acid (0.342mL) were dissolved in 4.8mL of DMF by sonication (20 min). The organic ligand L (29.52mg, 0.1) was then added2mmol) is added into an autoclave and the solution is sonicated for 10-30 min. And then heating the mixture to 120 ℃ and maintaining the temperature for 24-48 h. Cooling to room temperature, centrifuging to obtain white crystal powder, sequentially washing with fresh DMF (10-20 ml multiplied by 3) and organic solvent (10-20 ml multiplied by 3), centrifuging, and vacuum drying at 40-80 ℃ to obtain the powdery metal organic framework crystal material, wherein SEM pictures are shown in figure 6, PXRD spectra are shown in figure 7, and the digested crystals are1The H-NMR spectrum is shown in FIG. 8.
Wherein ". about.10-20 ml. times.3" means about 10-20 ml for 3 washes.
Example 4: gas adsorption properties of metal organic frameworks
The metal organic framework in example 3 was soaked in absolute ethanol for activation for 48h, vacuum dried at 60 ℃ for 12h, and subjected to a gas adsorption test: 200mg of the sample was placed in a pre-weighed sample tube, degassed at 120 ℃ for 10h, and then subjected to gas adsorption and desorption tests, testing N at 77K2The adsorption curve and the adsorption data are shown in FIG. 9.
Example 5: preparation of metal organic frameworks based on imidazole sulfonic acids
Refluxing the metal organic framework crystal material obtained in the embodiment 3 and 1, 3-propyl sultone (20 mu L) in acetone (10mL), centrifuging, and then drying in vacuum at 40-80 ℃ to obtain a post-modified powdery metal organic framework crystal material, wherein a PXRD spectrogram is shown in figure 10, and infrared spectrograms before and after reaction are shown in figure 11(1190 cm)-1Characteristic absorption peak of sulfonic acid group appears), digested crystal1The H-NMR spectrum is shown in FIG. 12.
Example 6: catalytic properties of metal-organic frameworks based on metal-organic frameworks of imidazole sulfonic acid
The imidazole sulfonic acid-based metal organic framework in example 5 is soaked and activated in absolute ethyl alcohol for 48h, vacuum drying is carried out at 60 ℃ for 12h, toluene (2mL), benzaldehyde (20 μ L), ethylene glycol (120 μ L) and post-modified metal organic framework of imidazole salt ligand L (1.0 wt.%) are added into a 10mL round-bottomed flask, reflux is carried out at 90 ℃, samples are respectively taken according to the time periods of 15min, 30min, 45min, 60min, 90min, 120min, 180min and 240min, gas phase characterization is carried out, the characterization result is shown in FIG. 13, and the yield can reach 99.9%. The metal organic framework in example 5 is further soaked and activated in absolute ethyl alcohol for 48h, vacuum drying is carried out for 12h at 60 ℃, the reaction is repeated for five times, the catalytic effect is still obvious, the characterization results are shown in fig. 14, and the yield is over 96%. PXRD characterization of the imidazole sulfonic acid-based metal organic framework, which was repeatedly catalyzed 5 times, showed that the framework structure remained intact, and the results are shown in fig. 15.
Example 7: catalytic performance of metal organic frameworks based on imidazole ligands
The imidazole ligand-based metal organic framework in example 3 was placed in absolute ethanol for immersion activation for 48h, vacuum dried at 60 ℃ for 12h, and in a 10mL round bottom flask, toluene (2mL), benzaldehyde (20 μ L), ethylene glycol (120 μ L), imidazole ligand-based metal organic framework (1.0 wt.%), 90 ℃, refluxed, and subjected to gas phase characterization after 4h of reaction, with a yield of only 58%.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive faculty, based on the technical solutions of the present invention.

Claims (21)

1. An organic ligand L for the synthesis of an imidazolesulfonic acid-based metal-organic framework, characterized by the chemical formula:
Figure FDA0002179930910000011
2. the process for the synthesis of an organic ligand L according to claim 1, characterized in that, first, 2-methyl-terephthalic acid is reacted to obtain an intermediate a: 2-methyl-terephthalic acid diester; secondly, reacting the intermediate A and bromosuccinimide as raw materials to obtain an intermediate B; and thirdly, taking the intermediate B and imidazole as raw materials to react to obtain an intermediate C, and finally, carrying out hydrolysis reaction on the intermediate C to obtain the organic ligand L.
3. The process of claim 2, wherein the intermediate A is synthesized in a single step by esterification of 3-methyl-terephthalic acid with an alcohol.
4. The process according to claim 2, wherein the intermediate A is prepared by reacting 2-methyl-terephthalic acid with a halogenating agent to convert the carboxyl group of 3-methyl-terephthalic acid to an acid halide, and then adding an alcohol to conduct alcoholysis.
5. A process according to claim 4, wherein the halogenating agent is selected from the group consisting of phosphorus trichloride, phosphorus pentachloride and thionyl chloride.
6. The synthetic method of claim 2, wherein the intermediate B is synthesized by taking the intermediate A and bromosuccinimide as raw materials, adding an initiator, heating and refluxing, and purifying to obtain the intermediate B.
7. The method according to claim 6, wherein the molar ratio of the intermediate A, bromosuccinimide and the initiator is 1: 1-1.5: 0.1-0.2.
8. The synthesis process as claimed in claim 2, wherein the reaction of intermediate B with imidazole as raw material to obtain intermediate C is carried out in acetonitrile under conditions of heating to 80 ℃ and refluxing for 2 hours; the molar ratio of the intermediate B to the imidazole is 1: 1.2-2.
9. The method of claim 2, wherein the hydrolysis reaction comprises the steps of adding the intermediate C, lithium hydroxide and a solvent, stirring at room temperature, adjusting pH, and distilling under reduced pressure to remove the solvent to obtain the organic ligand L.
10. The method of claim 9, wherein the solvent is a mixture of methanol and water.
11. The synthesis method of claim 9, wherein the stirring time is 10-14 h to ensure the hydrolysis reaction to be fully performed.
12. The method of claim 9, wherein the pH is adjusted to 2-3 with hydrobromic acid.
13. The process of claim 9, wherein the molar ratio of intermediate C to lithium hydroxide is 1: 10.
14. The metal organic framework based on the imidazole ligand is characterized in that the chemical structural formula is [ Zr ]6O4(OH)4L6]nWherein L is the organic ligand L of claim 1, and n is a natural number greater than 0.
15. The preparation method of the metal organic framework based on the imidazole ligand is characterized in that the organic ligand L, acid and zirconium salt in claim 1 are dissolved in a polar solvent, heated to 120 +/-5 ℃, kept at the temperature for 24-48 h and reacted to obtain the metal organic framework.
16. The method according to claim 15, wherein the organic ligand L, the zirconium salt, the acid and the polar solvent are added in an amount of 0.01:0.01:0.3:3 to 5 mol: mol: L.
17. An imidazole sulfonic acid-based metal organic framework, which is obtained by synthetically modifying the imidazole ligand-based metal organic framework of claim 14 with a sulfonic acid group compound;
the step of synthesis modification is that the metal organic framework based on imidazole ligand in claim 14 is placed in a non-polar solvent, a compound with sulfonic acid group is added into the solvent, stirred for 24-36 h at 50 ℃ +/-5 ℃, and dried for 12-24 h under vacuum at 60 ℃ +/-5 ℃.
18. Use of the imidazolesulfonic acid based metal-organic framework of claim 17 in nanocatalysis.
19. The method for activating the metal organic framework based on the imidazole sulfonic acid as claimed in claim 17, which comprises the steps of immersing the metal organic framework in absolute ethyl alcohol for 24-48 hours, and vacuum-drying at 60 ℃ for 12-24 hours.
20. The activation method as claimed in claim 19, wherein the metal organic framework is soaked in absolute ethanol for activation for 36h, and vacuum dried at 60 ℃ for 12 h.
21. A benzaldehyde condensation reaction method, which is characterized in that benzaldehyde and ethylene glycol are used as substrates, the imidazole sulfonic acid-based metal organic framework of claim 7 is used as a catalyst, and toluene is used as a solvent for condensation reaction at 90 ℃ and 1 atm.
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