CN111905825A - 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 PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 239000011701 zinc Substances 0.000 title claims abstract description 30
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 14
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- -1 nitro-carboxyl Chemical group 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- IZGAXCMEDCEJJP-UHFFFAOYSA-N 2,6-bis[5-(1H-1,2,4-triazol-5-yl)-1H-1,2,4-triazol-3-yl]pyridine Chemical compound N1N=C(N=C1)C=1NN=C(N=1)C1=NC(=CC=C1)C=1N=C(NN=1)C1=NNC=N1 IZGAXCMEDCEJJP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 53
- 238000001914 filtration Methods 0.000 abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 238000002474 experimental method Methods 0.000 abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 63
- 239000012074 organic phase Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 239000002086 nanomaterial Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JLDKNVUJLUGIBQ-UHFFFAOYSA-N 1-chloro-3-methyl-2-nitrobenzene Chemical compound CC1=CC=CC(Cl)=C1[N+]([O-])=O JLDKNVUJLUGIBQ-UHFFFAOYSA-N 0.000 description 2
- JSXAJLMUBSEJFF-UHFFFAOYSA-N 1-fluoro-3-methyl-2-nitrobenzene Chemical compound CC1=CC=CC(F)=C1[N+]([O-])=O JSXAJLMUBSEJFF-UHFFFAOYSA-N 0.000 description 2
- WMAINSDGLPRZIA-UHFFFAOYSA-N 1-methyl-2-(nitromethyl)benzene Chemical compound CC1=CC=CC=C1C[N+]([O-])=O WMAINSDGLPRZIA-UHFFFAOYSA-N 0.000 description 2
- XTNHKWZXMCOJSB-UHFFFAOYSA-N 1-methyl-3-(nitromethyl)benzene Chemical compound CC1=CC=CC(C[N+]([O-])=O)=C1 XTNHKWZXMCOJSB-UHFFFAOYSA-N 0.000 description 2
- XWJSTCOIIBMVDX-UHFFFAOYSA-N 4-(nitromethyl)benzonitrile Chemical compound [O-][N+](=O)CC1=CC=C(C#N)C=C1 XWJSTCOIIBMVDX-UHFFFAOYSA-N 0.000 description 2
- SQFLFRQWPBEDHM-UHFFFAOYSA-N 4-chloro-1-methyl-2-nitrobenzene Chemical compound CC1=CC=C(Cl)C=C1[N+]([O-])=O SQFLFRQWPBEDHM-UHFFFAOYSA-N 0.000 description 2
- XZDZONVWXHEMSQ-UHFFFAOYSA-N CC1C(F)=CC=CC1([N+]([O-])=O)F Chemical compound CC1C(F)=CC=CC1([N+]([O-])=O)F XZDZONVWXHEMSQ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SCLRUEQYJQUIJT-UHFFFAOYSA-N 1-methyl-4-(nitromethyl)benzene Chemical compound CC1=CC=C(C[N+]([O-])=O)C=C1 SCLRUEQYJQUIJT-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts 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
- B01J31/1805—Catalysts 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic 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—
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- B01J35/51—
-
- B01J35/612—
-
- B01J35/613—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/097—Preparation of carboxylic acids or their salts, halides or anhydrides from or via nitro-substituted organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling 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 large-particle crystalline Zn-CP (1) material and the nano-grade Zn-CP (1a) material of the catalyst material prepared by the invention catalyze the conversion of nitro groups into carboxyl groups to synthesize benzoic acid derivatives, 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, 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
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 achieving the formation and breaking of chemical bonds, enabling the conversion of chemicals or reagents into valuable products. Meanwhile, the homogeneous catalyst has short service life, poor thermal stability and poor 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 processed in time, so that from the aspects of economy and environment, the development of a green and efficient heterogeneous catalysis system has great driving force to replace the homogeneous catalysis system, thereby reducing the difficulties caused in the fields of wastewater treatment, raw material waste and the like in the chemical/chemical industry manufacturing industry, 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 is disclosed as a heterogeneous catalytic material and its preparation method, under the condition of no solvent, 1-3% mol of microporous thulium coordination polymer is added with corresponding amount of benzaldehyde dimethanol acetal and malononitrile, stirred for reaction, and the reaction process is followed by thin layer chromatography. 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, 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.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a zinc coordination polymer catalytic material, 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) adding Zn (SO)4)2·7H2Adding O into water, magnetically stirring at normal temperature for 5-20min to obtain a reaction system a;
(2) h is to be4Stirring and dissolving DBTP in an organic solvent, dropwise adding the DBTP into the reaction system a in the step (1), and stirring for 5-20min to obtain a reaction system b;
(3) dropwise adding acetonitrile into the reaction system b in the step (2), stirring for 5-10min, and then placing in an oven at 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 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)2·7H2The concentration of O is 0.05-0.1 mol/L.
H in the step (2)4DBTP 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 H4DBTP and Zn (SO)4)2·7H2O is added in a molar ratio of 1:2, H4The molar ratio of DBTP to CTAB is 1: (27-54).
The ratio of the volume of acetonitrile added in the step (3) to the volume of water added 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 10-20 h, 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 (1a) 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, 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.
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 cycle 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 rod-like colorless crystal having a crystal size of about 0.12X 0.11X 0.09 cm3Having a specific surface area of 5.64 m2 g−1(ii) a And Zn-CP (1a) 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 14.25m2 g−1. Compared with Zn-CP (1), the specific surface area of nano-grade Zn-CP (1a) is increased by nearly 3 times, which is beneficial to more accessible catalytic activityThe center is exposed and participates in catalytic reaction, thereby improving the catalytic activity.
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 reused 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 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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows 2,6-di (1H,2'H- [3,3' -bi (1,2,4-triazol) used for the preparation of the material]-5'-yl)pyridine)（H4DBTP) 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 nano-scale structure of Zn-CP (1a) material.
FIG. 7 is a powder XRD comparison of Zn-CP (1) and Zn-CP (1a) 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 (1a) catalyst.
FIG. 17 is a chart of a cycle experimental test of a nano-graded structure Zn-CP (1a) catalyst.
FIG. 18 is an SEM image of a nanoscopic structure Zn-CP (1a) after a catalyst cycling experiment.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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) adding Zn (SO)4)2·7H2O (0.057 g, 0.2 mmol) was added to the inner liner of a 25 mL Teflon reactor, 3 mL water (H)2O), magnetically stirring at normal temperature;
(2) mixing 2,6-di (1H,2'H- [3,3' -bi (1,2,4-triazol)]-5'-yl)pyridine)（H4DBTP) (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 then placing the reaction system in an oven at the temperature of 160-170 ℃ for 48-72 h;
(5) cooling to room temperature at a rate of 5 ℃/h to obtain colorless large-particle crystals, washing with distilled water and acetonitrile, and drying to obtain the targetThe product was weighed. Yield: 61% (based on Zn (SO)4)2·7H2Calculated 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 upon4Coordination 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 m2 g−1。
The crystallographic parameters of the material are detailed in the following table:
example 2
The preparation method of the nano hierarchical structure Zn-CP (1a) material comprises the following steps:
(1) adding Zn (SO)4)2·7H2O (0.057 g, 0.2 mmol) was added to the inner liner of a 25 mL Teflon reactor, 3 mL water (H)2O), 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 be4DBTP (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 the temperature of 160-170 ℃ for 48-72 h;
(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 (1a) with the nano hierarchical structure.
The SEM image of the Zn-CP (1a) material is shown in FIG. 6, and FIG. 6 shows that: Zn-CP (1a) 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 14.25m2 g−1。
The XRD pattern is shown in FIG. 7, and it can be seen from FIG. 7 that: the nano-graded structure Zn-CP (1a) and Zn-CP (1) materials are completely consistent with simulated XRD, further illustrating that Zn-CP (1a) 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 (1a) catalyst prepared in example 2:
(1) nitro-toluene (0.137 g, 1 mmol) was weighed into a round bottom flask, followed by TBAI, magneton and solvent water (H)2O，10 mL）；
(2) Adding Zn-CP (1a) (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 (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 92%.
1H NMR (400 MHz, d6DMSO) 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 Zn-CP (1a) catalyst prepared in example 2:
(1) nitro-toluene (0.151 g, 1 mmol) was weighed into a round bottom flask, followed by TBAI, magneton and solvent water (H)2O，10 mL）。
(2) And then adding Zn-CP (1a) (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%.
1H NMR (400 MHz, d6-DMSO) : 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 (1a) 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)2O，10 mL）；
(2) Adding Zn-CP (1a) (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%.
1H NMR (400 MHz, d6-DMSO) : 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 (1a) catalyst prepared in example 2:
(1) to a round bottom flask was weighed 4-chloro-nitrotoluene (0.171 g, 1 mmol) in that order, added TBAI, magneton and solvent water (H)2O，10 mL）；
(2) Adding Zn-CP (1a) (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), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin dried. The isolated yield was 88%.
1H NMR (400 MHz, d6DMSO) 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 (1a) catalyst prepared in example 2:
(1) to a round bottom flask was weighed 3-methyl-nitrotoluene (0.151 g, 1 mmol) in that order, added TBAI, magneton and solvent water (H)2O，10 mL）；
(2) Adding Zn-CP (1a) (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%.
1H NMR (400 MHz, d6DMSO). sub.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 Zn-CP (1a) 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)2O，10 mL）；
(2) Adding Zn-CP (1a) (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 ℃ for reaction 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%.
1H NMR (400 MHz, d6DMSO) 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 Zn-CP (1a) catalyst prepared in example 2:
(1) to a round bottom flask was weighed 3-fluoro-nitrotoluene (0.155 g, 1 mmol) in that order, added TBAI, magneton and solvent water (H)2O，10 mL）；
(2) Adding Zn-CP (1a) (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 ℃ for reaction 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%.
1H NMR (400 MHz, d6DMSO) 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 (1a) catalyst prepared in example 2:
(1) 2-methyl-nitrotoluene (0.165 g, 1 mmol) was weighed into a round bottom flask, followed by TBAI, magneton and solvent water (H)2O，10 mL）；
(2) Adding Zn-CP (1a) (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 17 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 89%.
1H NMR (400 MHz, d6-DMSO) : 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 (1a) catalyst prepared in example 2:
(1) 2, 6-difluoro-nitrotoluene (0.173 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 (1a) (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 ℃ for reaction 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%.1H NMR (400 MHz, d6DMSO) 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)2O, 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 is recycled 20 times according to the method, and a test chart of the catalytic efficiency of the recycling is shown in figure 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 300 nm.
Application example 11
Nitrotoluene was catalyzed using the large particle crystalline Zn-CP (1) catalyst prepared in example 1:
(1) nitro-toluene (0.137 g, 1 mmol) was weighed into a round bottom flask, followed by TBAI, magneton and solvent water (H)2O，10 mL）；
(2) 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 (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 34%;
1H NMR (400 MHz, d6-DMSO) : 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 (8)
1. The preparation method of the zinc coordination polymer catalytic material is characterized by comprising the following steps:
(1) adding Zn (SO)4)2·7H2Adding O into water, magnetically stirring at normal temperature for 5-20min to obtain a reaction system a;
(2) h is to be4Stirring and dissolving DBTP in an organic solvent, dropwise adding the DBTP into the reaction system a in the step (1), and stirring for 5-20min to obtain a reaction system b;
(3) dropwise adding acetonitrile into the reaction system b in the step (2), stirring for 5-10min, and then placing in an oven at 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 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)2·7H2The concentration of O is 0.05-0.1 mol/L.
3. The method of claim 1, wherein the zinc coordination polymer catalytic material comprises: h in the step (2)4DBTP 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.
4. The method of claim 3, wherein the zinc coordination polymer catalytic material is prepared by: said H4DBTP and Zn (SO)4)2·7H2O is added in a molar ratio of 1:2, H4The molar ratio of DBTP to CTAB is 1: (27-54).
5. The method of claim 1, wherein the zinc coordination polymer catalytic material comprises: the ratio of the volume of acetonitrile added in the step (3) to the volume of water added in the step (1) is 3: (2-4).
6. A zinc coordination polymer catalytic material prepared by the process of any of claims 1 to 5.
7. The zinc coordination polymer catalytic material of claim 6, applied to synthesis of benzoic acid derivatives by using nitro-carboxyl conversion reaction catalyzed by high catalytic conversion rate.
8. Use according to claim 7, 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 ℃ for reaction for 10-20 h, and finishing the catalytic reaction.
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