CN111905825B - Zinc coordination polymer catalytic material and preparation method and application thereof - Google Patents

Zinc coordination polymer catalytic material and preparation method and application thereof Download PDF

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CN111905825B
CN111905825B CN202010837488.9A CN202010837488A CN111905825B CN 111905825 B CN111905825 B CN 111905825B CN 202010837488 A CN202010837488 A CN 202010837488A CN 111905825 B CN111905825 B CN 111905825B
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coordination polymer
catalyst
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CN111905825A (en
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黄超
米立伟
张莹莹
秦娜
张电波
邵志超
卢贵珍
韩素贞
王丹丹
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Zhongyuan University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691Coordination polymers, e.g. metal-organic frameworks [MOF]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J35/40
    • B01J35/51
    • B01J35/612
    • B01J35/613
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00Formation or introduction of functional groups containing oxygen
    • C07B41/08Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/30Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/097Preparation of carboxylic acids or their salts, halides or anhydrides from or via nitro-substituted organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008Supramolecular polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26Zinc
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The invention belongs to the field of heterogeneous catalytic materials, relates to preparation of a crystalline coordination polymer, and particularly relates to a zinc coordination polymer catalytic material as well as a preparation method and application thereof. When the catalyst material prepared by the invention is used for catalyzing nitro to be converted into carboxyl to synthesize benzoic acid derivatives, the large-particle crystalline Zn-CP (1) material and the nano-graded Zn-CP (1 a) material have the advantages that the conversion rate can reach 100% and the separation yield can reach over 84% under the monitoring of TLC; meanwhile, the catalytic reaction utilizes water as a reaction solvent, meets the requirements of modern green chemistry, the catalyst can be recovered through simple centrifugal filtration after the reaction is finished, the recovered catalyst can continuously catalyze the reaction, and the catalytic activity is not reduced after the reaction is circulated for 20 times, so that good catalytic activity is shown, and the catalytic reaction shows good activity in experiments and has high catalytic activity and environmental protection.

Description

Zinc coordination polymer catalytic material and preparation method and application thereof
Technical Field
The invention belongs to the field of heterogeneous catalytic materials, relates to preparation of a crystalline coordination polymer, and particularly relates to a zinc coordination polymer catalytic material as well as a preparation method and application thereof.
Background
Since the 20 th century, with the continuous development of industrialization, the chemical industry faces challenges from energy and environment, and has become an indispensable part for promoting the development of the world economy, and chemical researchers are prompted to find alternative catalysts to solve the problem. In this diverse field, catalysts are key elements and are efficient and selective tools for effecting the formation and breaking of chemical bonds, effecting the transformation of chemicals or reagents into valuable products. Meanwhile, the homogeneous catalyst has short service life, poor thermal stability and repeatability, and a large amount of waste materials which are harmful to the environment and are not easy to separate after reaction need to be treated in time, so that under the economic and environmental aspects, a green and efficient heterogeneous catalytic system is developed to have great driving force to replace the homogeneous catalytic system, thereby reducing the difficulties in the chemical/chemical manufacturing industry in the aspects of wastewater treatment, raw material waste and the like, further relieving increasingly severe environmental pressure in China and realizing social sustainable development, and having important significance.
Crystalline Coordination Polymer (CPs) materials have the advantages of both organic structural units and inorganic structural units, and become a novel catalytic material which is widely concerned by academia in the last two decades. Due to the diversity and controllability of the CPs material structure, the structure and the appearance of the CPs material are endowed with tunability, and particularly, large granular crystalline CPs can be controllably prepared into nano-scale sizes by the synthesis technology of nano materials, so that the CPs material is widely applied to the fields of catalysis, energy storage, molecular magnetism, biomedical imaging and the like. In patent CN201710350275.1, a microporous thulium coordination polymer as a heterogeneous catalytic material and a preparation method thereof are disclosed, wherein under a solvent-free condition, 1-3% mol of microporous thulium coordination polymer is added with corresponding amount of benzaldehyde dimethanol acetal and malononitrile, and then stirred for reaction, and a thin layer chromatography is used for tracking the reaction process. And after the reaction is completed, adding a certain amount of ethanol solution, stirring, filtering the solid catalyst, and evaporating the filtrate under reduced pressure to obtain a crude product. And recrystallizing the crude product in a solution of ethanol and water to obtain a product with relatively good purity. The catalyst is washed by ethyl acetate and dried in vacuum for repeated use, and can be used for at least 4 times of catalytic reaction. The catalytic effect of the catalyst is as follows: as a bifunctional catalyst, the method comprises two stages of concerted catalytic reaction, wherein acetal is firstly deprotected to generate corresponding aldehyde, and then dehydration reaction is carried out to generate corresponding products. Different catalysts have different catalytic reaction types, and CPs catalysts for catalyzing direct conversion of nitro groups into carboxyl groups to synthesize benzoic acid derivatives are rarely available in the field, and the catalytic effect of a common nano material catalyst is poor.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a zinc coordination polymer catalytic material, and a preparation method and application thereof, and provides a preparation method of a nano-grade structured CP material with high heterogeneous catalytic activity and high recycling rate.
The technical scheme of the invention is realized as follows:
the preparation method of the zinc coordination polymer catalytic material comprises the following steps:
(1) Zn (SO) 4 ) 2 ·7H 2 O plusAdding into water, magnetically stirring at normal temperature for 5-20min to obtain a reaction system a;
(2) Will H 4 DBTP is stirred and dissolved in an organic solvent, and then is dropwise added into the reaction system a in the step (1), and after stirring is carried out for 5-20min, a reaction system b is obtained;
(3) Dropwise adding acetonitrile into the reaction system b in the step (2), stirring for 5-10min, and then placing in an oven at 160-170 ℃ for reaction;
(4) And (4) cooling the product obtained after the reaction in the step (3) to room temperature at the speed of 5 ℃/h to obtain colorless large-particle crystals, washing the large-particle crystals with distilled water and acetonitrile in sequence, and drying to obtain the target product, namely the zinc coordination polymer catalytic material.
Zn (SO) in the reaction system a in the step (1) 4 ) 2 ·7H 2 The concentration of O is 0.05-0.1 mol/L.
H in the step (2) 4 DBTP is 2,6-di (1H,2 'H- [3,3' -bi (1,2,4-triazol)]-5' -yl) pyridine; the organic solvent is DMF or CTAB in DMF, wherein the concentration of CTAB in DMF solution of CTAB is 0.18-0.36 mol/L.
Said H 4 DBTP and Zn (SO) 4 ) 2 ·7H 2 The molar ratio of O added is 1 4 The molar ratio of DBTP to CTAB is 1: (27-54).
The volume ratio of the added acetonitrile in the step (3) to the added water in the step (1) is 3: (2-4).
The zinc coordination polymer catalytic material prepared by the method.
The zinc coordination polymer catalytic material is applied to synthesis of benzoic acid derivatives by catalyzing nitro-carboxyl conversion reaction with high catalytic conversion rate.
The method comprises the following steps: putting an aromatic nitro compound serving as a reaction substrate into a container, adding a zinc coordination polymer catalytic material, heating and stirring at 80-90 ℃ for reaction for 10-20h, and finishing the catalytic reaction.
The invention has the following beneficial effects:
1. the catalyst material prepared by the invention is a large-particle crystalline Zn-CP (1) material and a nano-grade Zn-CP (1 a) material, when the nitro group is catalyzed and converted into carboxyl to synthesize the benzoic acid derivative, the conversion rate can reach 100 percent through TLC monitoring, and the separation yield can reach over 84 percent; meanwhile, the catalytic reaction utilizes water as a reaction solvent, the modern green chemical requirements are met, the catalyst can be recovered through simple centrifugal filtration after the reaction is finished, the recovered catalyst can be used for continuously catalyzing the reaction, the catalytic activity is not reduced after the reaction is circulated for 20 times, the good catalytic activity is shown, the good activity is shown in the experiment, and the high catalytic activity and the environmental protection are shown.
2. The catalyst material has good stability, is kept stable below 280 ℃ through thermogravimetric analysis, and is used for catalyzing nitro conversion to form carboxyl to synthesize benzoic acid derivatives in aqueous solution at the temperature of 80-90 ℃; and SEM images after 20 times of catalytic cyclic reaction show that the catalyst keeps a good appearance in the catalytic process, which proves that the catalyst can be recycled.
3. Zn-CP (1) prepared herein is a colorless crystal in the form of a rod having a crystal size of about 0.12X 0.11X 0.09 cm 3 Its specific surface area is 5.64 m 2 g −1 (ii) a And Zn-CP (1 a) is a nano-grade flower-like sphere, the sphere size is about 300nm, the flake shape is about a few nanometers, and the specific surface area is 14.25m 2 g −1 . Compared with Zn-CP (1), the specific surface area of the nano-grade Zn-CP (1 a) is increased by nearly 3 times, so that more catalytic activity centers which are easy to approach are exposed and participate in catalytic reaction, and the catalytic activity is further improved.
4. The invention discloses a preparation method of a zinc coordination polymer material with a nano hierarchical structure as a heterogeneous catalyst material, wherein the catalyst material can catalyze nitro conversion in water to form carboxyl to synthesize a benzoic acid derivative. After the reaction is finished, the catalyst can be repeatedly used for at least 20 times after being subjected to simple centrifugal filtration and washing, and the appearance and the size of the catalyst are not obviously changed; after the filtrate is treated by dilute hydrochloric acid, dichloromethane is used for extraction to obtain a corresponding pure product. Meanwhile, the catalytic process uses water as a reaction solvent, and accords with the advantages of modern green chemistry. The catalyst has the effects that: the zinc coordination polymer catalyst with the nano hierarchical structure prepared by the method is subjected to two-stage concerted catalytic reaction, wherein nitro is catalyzed and converted to generate a corresponding aldehyde intermediate, and then the hydrolysis reaction of aldehyde is carried out to form a corresponding benzoic acid derivative product. Different catalysts have different catalytic reaction types, CPs catalysts for catalyzing nitro to be directly converted into carboxyl to synthesize benzoic acid derivatives rarely appear in the field, and the catalytic effect of the common nano material catalyst is poor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is 2,6-di (1H,2 'H- [3,3' -bi (1, 2, 4-triazol) from the preparation of the material]-5'-yl)pyridine)(H 4 DBTP) ligand formula.
FIG. 2 shows the crystal morphology of Zn-CP (1) material.
FIG. 3 is a crystal structure diagram of Zn-CP (1) material.
FIG. 4 is an SEM image of Zn-CP (1) material.
FIG. 5 is a thermogravimetric analysis of the Zn-CP (1) material.
FIG. 6 is SEM image of the nano-scale structure of Zn-CP (1 a) material.
FIG. 7 is a powder XRD comparison of Zn-CP (1) and Zn-CP (1 a) materials.
FIGS. 8-16 are nuclear magnetic diagrams of products of synthesizing benzoic acid derivatives by catalyzing nitro-group to convert carboxyl with nano-grade Zn-CP (1 a) catalyst.
FIG. 17 is a chart of a cycle experimental test of a nano-graded structure Zn-CP (1 a) catalyst.
FIG. 18 is an SEM image of a nanoscopic structure Zn-CP (1 a) after a catalyst cycling experiment.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the large-grain crystalline Zn-CP (1) material comprises the following steps:
(1) Zn (SO) 4 ) 2 ·7H 2 O (0.057 g,0.2 mmol) was added to the inner liner of a 25 mL Teflon reactor, 3 mL water (H) 2 O), magnetically stirring at normal temperature;
(2) Mixing 2,6-di (1H,2 'H- [3,3' -bi (1, 2, 4-triazol)]-5'-yl)pyridine)(H 4 DBTP) (structural formula shown in figure 1) (0.035 g, 0.1 mmol) was dissolved in 3 mL of N, N-Dimethylformamide (DMF) with stirring and added dropwise to the above reaction system;
(3) After the reaction system in the step (2) is stirred for 5-20min, adding acetonitrile (2-4 mL) into the solution of the reaction system drop by drop, and stirring for 5-10 min;
(4) Sealing the reaction system, and placing the reaction system in an oven at 160-170 ℃ for 48-72h;
(5) Cooling to room temperature at the speed of 5 ℃/h to obtain colorless large-particle crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 61% (based on Zn (SO) 4 ) 2 ·7H 2 Calculated as O).
The crystal morphology of the Zn-CP (1) material prepared in the example is shown in FIG. 2, and the analysis of a single crystal X-ray test shows that the Zn-CP (1) is tetragonal,I-4space group, in which ligand H is relied upon 4 Coordination bonds formed between N atoms in triazole rings and Zn in DBTP are connected with each other to form a three-dimensional (3D) structure (the structure diagram of the crystal is shown in figure 3), and an SEM (the SEM diagram is shown in figure 4) illustrates that the morphology and the size of the formed Zn-CP (1) material are uniform, and the specific surface area of the Zn-CP material is 5.64 m 2 g −1
The crystallographic parameters of the material are detailed in the following table:
Figure DEST_PATH_IMAGE001
example 2
The preparation method of the nano hierarchical structure Zn-CP (1 a) material comprises the following steps:
(1) Zn (SO) 4 ) 2 ·7H 2 O (0.057 g,0.2 mmol) was added to the inner liner of a 25 mL Teflon reactor, 3 mL water (H) 2 O), magnetically stirring at normal temperature;
(2) Cetyl Trimethyl Ammonium Bromide (CTAB) (0.1-0.2 g,0.27-0.54 mmol) is dissolved in 1.5mL DMF under stirring, and is added into the solution of the reaction system drop by drop, and is stirred for 5-20min at normal temperature;
(3) H is to be 4 DBTP (0.035 g, 0.1 mmol) was dissolved in 1.5mL of DMF with stirring and added dropwise to the above reaction system;
(4) After the reaction system in the step (3) is stirred for 5-20min, adding acetonitrile (2-4 mL) dropwise into the solution of the reaction system, and stirring for 5-10 min;
(5) Sealing the reaction system, and then placing the reaction system in an oven at 160-170 ℃ for 48-72h;
(6) Cooling to room temperature at the speed of 5 ℃/h to obtain colorless large-particle crystals, washing with distilled water and acetonitrile, and drying to obtain the Zn-CP (1 a) with the nano hierarchical structure.
The SEM image of the Zn-CP (1 a) material is shown in FIG. 6, and FIG. 6 shows that: zn-CP (1 a) is a flower-like spherical nano-grade structure with uniform distribution of morphology and size, the flower-like spherical size is about 300nm, the flake shape is about 10 nm, and the specific surface area is 14.25m 2 g −1
The XRD pattern is shown in FIG. 7, and it can be known from FIG. 7 that: the nano-graded structure Zn-CP (1 a) and Zn-CP (1) materials are completely consistent with simulated XRD, further illustrating that Zn-CP (1 a) is pure phase and has the same internal structure as Zn-CP (1).
Application example 1
Nitrotoluene was catalyzed using the nano-graded Zn-CP (1 a) catalyst prepared in example 2:
(1) Nitro toluene (0.137 g, 1 mmol) was weighed into a round bottom flask in turn, TBAI, magneton and solvent water (H) were added 2 O,10 mL);
(2) Then adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with anion skeleton nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 12 h;
(4) After the reaction is finished, adding 2M HCl into the mixture obtained in the step (3) for quenching, extracting the mixture for 3 times by using Dichloromethane (DCM), combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering and spin-drying the organic phases; the isolated yield was 92%.
1 H NMR (400 MHz, d 6 -DMSO) delta 7.94-7.96 (m, 2H), 7.57-7.61 (m, 1H), 7.45-7.49 (m, 2H), as shown in FIG. 8.
Application example 2
4-methyl-nitrotoluene was catalyzed using the nano-graded structure Zn-CP (1 a) catalyst prepared in example 2:
(1) Nitro toluene (0.151 g, 1 mmol) was weighed into a round bottom flask in sequence, TBAI, magneton and solvent water (H) were added 2 O,10 mL)。
(2) And then adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with an anion skeleton nano hierarchical structure into the reaction system (1) as a catalyst.
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 10 h.
(4) After the reaction was complete, 2M HCl was added to (3) and quenched, extracted 3 times with Dichloromethane (DCM), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 85%.
1 H NMR (400 MHz, d 6 -DMSO) δ: 7.83 (d, J = 8.0 Hz, 2H), 7.27 (d, J= 8.0 Hz, 2H), 2.34 (s, 3H), as shown in fig. 9.
Application example 3
4-cyano-nitrotoluene was catalyzed using the nano-graded Zn-CP (1 a) catalyst prepared in example 2:
(1) To a round bottom flask was weighed 4-cyano-nitrotoluene (0.162 g, 1 mmol) in that order, added TBAI, magneton and solvent water (H) 2 O,10 mL);
(2) Adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with an anion framework nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 18 h;
(4) After the reaction was complete, 2M HCl was added to (3) and quenched, extracted 3 times with Dichloromethane (DCM), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 91%.
1 H NMR (400 MHz, d 6 -DMSO) δ: 8.07 (d, J = 8.0 Hz, 2H), 7.97 (d, J= 8.0 Hz, 2H) as shown in fig. 10.
Application example 4
4-chloro-nitrotoluene was catalyzed using the nano-graded Zn-CP (1 a) catalyst prepared in example 2:
(1) 4-chloro-nitrotoluene (0.171 g, 1 mmol) was weighed into a round bottom flask, followed by TBAI, magneton, and solvent water (H) 2 O,10 mL);
(2) Adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with an anion framework nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 16 h;
(4) After the reaction was complete, 2M HCl was added to (3) and quenched, extracted 3 times with Dichloromethane (DCM), the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 88%.
1 H NMR (400 MHz, d 6 -DMSO) delta 7.92-7.96 (m, 2H), 7.54-7.58 (m, 2H), as shown in FIG. 11.
Application example 5
3-methyl-nitrotoluene was catalyzed using the nano-graded Zn-CP (1 a) catalyst prepared in example 2:
(1) Sequentially weighing into a round-bottom flask3-methyl-nitrotoluene (0.151 g, 1 mmol) was taken and added with TBAI, magneton and solvent water (H) 2 O,10 mL);
(2) Adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with an anion framework nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 18 h;
(4) After the reaction is finished, adding 2M HCl into the mixture (3) for quenching, extracting the mixture for 3 times by Dichloromethane (DCM), combining organic phases, drying the organic phases by anhydrous sodium sulfate, filtering and spin-drying; the isolated yield was 87%.
1 H NMR (400 MHz, d 6 DMSO). Delta.10.93 (s, 1H), 9.85 (s, 1H), 7.72-7.75 (m, 2H), 7.34-7.42 (m, 2H), 2.34 (s, 3H) as shown in FIG. 12.
Application example 6
3-chloro-nitrotoluene was catalyzed using the nano-graded structure Zn-CP (1 a) catalyst prepared in example 2:
(1) To a round bottom flask was weighed 3-chloro-nitrotoluene (0.171 g, 1 mmol) in that order, added TBAI, magneton and solvent water (H) 2 O,10 mL);
(2) Then adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with anion skeleton nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 20 h;
(4) After the reaction was complete, 2M HCl was added to (3) and quenched, extracted 3 times with Dichloromethane (DCM), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 90%.
1 H NMR (400 MHz, d 6 -DMSO) delta 13.36 (s, 1H), 7.90-7.92 (m, 2H), 7.70-7.73 (m, 1H), 7.54-7.58 (m, 1H), as shown in FIG. 13.
Application example 7
3-fluoro-nitrotoluene was catalyzed using the nano-graded structure Zn-CP (1 a) catalyst prepared in example 2:
(1) 3-fluoro-nitrotoluene is weighed in turn into a round-bottom flask(0.155 g, 1 mmol), TBAI, magneton and solvent water (H) were added 2 O,10 mL);
(2) Adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with an anion framework nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 15 h;
(4) After the reaction was complete, 2M HCl was added to (3) and quenched, extracted 3 times with Dichloromethane (DCM), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 84%.
1 H NMR (400 MHz, d 6 -DMSO) delta 13.33 (s, 1H), 7.79-7.82 (m, 1H), 7.65-7.69 (m, 1H), 7.55-7.61 (m, 1H), 7.47-7.53 (m, 1H), as shown in FIG. 14.
Application example 8
2-methyl-nitrotoluene was catalyzed using the nano-graded Zn-CP (1 a) catalyst prepared in example 2:
(1) 2-methyl-nitrotoluene (0.165 g, 1 mmol) was weighed into a round bottom flask in sequence, TBAI, magneton and solvent water (H) were added 2 O,10 mL);
(2) Then adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with anion skeleton nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 17 h;
(4) After the reaction is finished, adding 2M HCl into the mixture obtained in the step (3) for quenching, extracting the mixture for 3 times by using Dichloromethane (DCM), combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering and spin-drying the organic phases; the isolated yield was 89%.
1 H NMR (400 MHz, d 6 -DMSO) δ: 12.81 (s, 1H), 7.82 (d, J= 8.0 Hz, 1H), 7.43-7.47 (m, 1H), 7.27-7.31 (m, 2H), 2.51 (s, 3H), as shown in fig. 15.
Application example 9
2, 6-difluoro-nitrotoluene was catalyzed using the nano-graded Zn-CP (1 a) catalyst prepared in example 2:
(1) Into a round-bottom flask in turn2, 6-difluoro-nitrotoluene (0.173 g, 1 mmol) was weighed out and TBAI, magneton and solvent water (H) were added 2 O,10 mL);
(2) Adding Zn-CP (1 a) (0.053 g, 0.1 mmol) with a nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 20 h;
(4) After the reaction was complete, 2M HCl was added to (3) and quenched, extracted 3 times with Dichloromethane (DCM), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 84%. 1 H NMR (400 MHz, d 6 -DMSO) delta 7.55-7.64 (m, 1H), 7.19-7.25 (m, 2H), as shown in FIG. 16.
Application example 10
The catalyst is recycled to catalyze the nitro group to convert the carboxyl group to synthesize the benzoic acid derivative:
(1) The nano-sized Zn-CP separated by filtration in example 2 was added again as a catalyst to a mixture containing nitrotoluene (0.151 g, 1 mmol), TBAI, magnetons and solvent water (H) 2 O,10 mL);
(2) Then heating the reaction system (1) to 80-90 ℃ for reaction for 10 h;
(3) Then, the Zn-CP with the nano-grade structure separated by filtration is taken as a catalyst to continue repeating the experiment with the same amount in the example 2;
(4) The catalyst was recycled 20 times according to the above method, and the test chart of catalytic efficiency of the recycling was shown in fig. 17; as can be seen from fig. 17: the catalyst still shows good catalytic activity after being recycled for 20 times, and the separation yield after the catalysis is kept above 90%. Meanwhile, the morphology and the size of the alloy are not obviously changed after 20 cycles, and the morphology after the cycles is shown in FIG. 18: the shape of the cycle is still a flower-like spherical nano hierarchical structure, the shape and the size of the cycle are uniformly distributed, and the size of the flower ball is about 300nm.
Application example 11
Nitrotoluene was catalyzed using the large particle crystalline Zn-CP (1) catalyst prepared in example 1:
(1) To the direction ofNitrobenzene (0.137 g, 1 mmol) was weighed in turn in a round bottom flask, and TBAI, magneton and solvent water (H) were added 2 O,10 mL);
(2) Then adding Zn-CP (1) (0.053 g, 0.1 mmol) with an anion framework nano hierarchical structure into the reaction system (1) as a catalyst;
(3) Then heating the reaction system (2) to 80-90 ℃ to react for 12 h;
(4) After the reaction is finished, adding 2M HCl into the mixture obtained in the step (3) for quenching, extracting the mixture for 3 times by using Dichloromethane (DCM), combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering and spin-drying the organic phases; the isolation yield is 34%;
1 H NMR (400 MHz, d 6 -DMSO) δ: 7.94-7.96 (m, 2H), 7.57-7.61 (m, 1H), 7.45-7.49 (m, 2H)。
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. A preparation method of a zinc coordination polymer catalytic material is characterized by comprising the following steps:
(1) Adding Zn (SO) 4 ) 2 ·7H 2 Adding O into the lining of the polytetrafluoroethylene reaction kettle, adding water, and magnetically stirring at normal temperature for 5-20min to obtain a reaction system a;
(2) Will H 4 DBTP is stirred and dissolved in an organic solvent, and then is dropwise added into the reaction system a in the step (1), and after stirring is carried out for 5-20min, a reaction system b is obtained; h in the step (2) 4 DBTP is 2,6-di (1H,2 'H- [3,3' -bi (1,2,4-triazol)]-5' -yl) pyridine; the organic solvent is DMF or CTAB DMF solution, wherein the concentration of CTAB in the CTAB DMF solution is 0.18-0.36 mol/L; said H 4 DBTP and Zn (SO) 4 ) 2 ·7H 2 The molar ratio of O added is 1 4 The molar ratio of DBTP to CTAB is 1: (27-54);
(3) Dropwise adding acetonitrile into the reaction system b in the step (2), stirring for 5-10min, and then placing in an oven at 160-170 ℃ for reaction; the volume ratio of the added acetonitrile in the step (3) to the added water in the step (1) is 3: (2-4);
(4) And (4) cooling the product obtained after the reaction in the step (3) to room temperature at the speed of 5 ℃/h to obtain colorless large-particle crystals, washing the crystals with distilled water and acetonitrile in sequence, and drying to obtain the target product, namely the zinc coordination polymer catalytic material.
2. The method of claim 1, wherein the zinc coordination polymer catalytic material comprises: zn (SO) in the reaction system a in the step (1) 4 ) 2 ·7H 2 The concentration of O is 0.05-0.1 mol/L.
3. A zinc coordination polymer catalytic material prepared according to the method of any one of claims 1-2.
4. The use of the zinc coordination polymer catalytic material of claim 3 in catalyzing the reaction of converting nitro groups into carboxyl groups for synthesizing benzoic acid derivatives.
5. Use according to claim 4, characterized in that the steps are as follows: putting an aromatic nitro compound serving as a reaction substrate into a container, adding a zinc coordination polymer catalytic material, heating and stirring at 80-90 ℃ to react for 10-20h, and finishing the catalytic reaction.
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