CN109369689B - Copper metal organic framework (Cu-MOF) catalytic material, preparation method and application - Google Patents

Copper metal organic framework (Cu-MOF) catalytic material, preparation method and application Download PDF

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CN109369689B
CN109369689B CN201811500114.7A CN201811500114A CN109369689B CN 109369689 B CN109369689 B CN 109369689B CN 201811500114 A CN201811500114 A CN 201811500114A CN 109369689 B CN109369689 B CN 109369689B
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bpy
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CN109369689A (en
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黄超
米立伟
王丹丹
吴佳瑞
朱开放
李高祥
徐玉培
张苗苗
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Zhongyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • 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
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
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Abstract

A copper metal organic framework (Cu-MOF) catalytic material adopts two organic ligands which are respectively 9- (4-carboxyphenyl-3, 6-carbazole dicarboxylic acid (H)3CPCDC) and 4,4' -Bipyridine (BPY). The catalyst material disclosed by the invention shows good activity in an experiment for catalytically synthesizing the 3-phenyl-propiolic nitrile derivative, the catalytic conversion rate of the obtained aromatic alkyne reaches 100%, the separation yield of a final product reaches more than 95%, and the catalyst material has very high catalytic activity and environmental friendliness.

Description

Copper metal organic framework (Cu-MOF) catalytic material, preparation method and application
Technical Field
The invention belongs to the technical field of heterogeneous catalytic materials, and particularly relates to a copper metal organic framework (Cu-MOF) catalytic material, a preparation method and application thereof.
Technical Field
Since the 20 th century, with the continuous development of industrialization, the chemical industry has become an indispensable part for promoting the economic development of the world, and the catalyst is the core of the chemical industry and the preparation process, is an effective and selective tool for realizing the generation and the breaking of chemical bonds, and realizes the conversion of chemicals or reagents into valuable products. Meanwhile, a large amount of waste materials which are harmful to the environment and generated in the chemical product manufacturing process need to be treated in time, so that from the economic and environmental aspects, a green and efficient heterogeneous catalysis system is developed to have a great driving force to replace a homogeneous catalysis system, thereby reducing the difficulties caused in the chemical/chemical manufacturing industry field in the aspects of wastewater treatment, raw material waste and the like, further relieving the increasingly severe environmental pressure of China and realizing social sustainable development, and having important significance.
Crystalline porous metal-organic framework (MOFs) materials have the advantages of both inorganic units and organic units, and become a novel catalytic material which is widely noticed by the academic community in the last decade. The MOFs material has the advantages of structural diversity and controllability, and can be widely applied to the fields of catalysis, surface chemistry, energy storage, molecular magnetism, biomedical imaging and the like as a solid material. Particularly, the metal core has fixed holes, large specific surface area and tunable physical and chemical properties, is particularly suitable for serving as a molecular catalyst with fixed catalytic sites, forms a uniform catalytic site and an open hole structure, can firstly adsorb a reaction substrate into a hole channel during the catalytic organic reaction, and then participates in catalysis through a metal center and generates special selectivity such as chemistry, size, stereo and the like through the specific hole channel structure. Secondly, the synergistic catalysis effect of multiple coordination centers in the MOFs material can avoid the separation of intermediate products, and the series reaction or the synergistic reaction is realized through a one-pot boiling mode. The crystalline porous MOFs catalyst has the characteristics of high catalytic efficiency, selectivity to a substrate, recyclability and the like, and has a wide development prospect in developing high-efficiency catalytic materials. The invention utilizes 9- (4-carboxyl benzene-3, 6-carbazole dicarboxylic acid [9- (4-carboxyphenyl) -9H-carbazole-3,6-dicarboxylic acid](H3CPCDC) and 4,4 '-dipyridine (4,4' -dipyridine) (BPY) are used as bifunctional organic ligands, and self-assembly with copper ions is carried out to construct a copper metal crystalline anion framework MOF material { [ H ] with good heterogeneous catalytic performance3O][Cu(CPCDC)(BPY)]}n（Cu-MOF）。
Disclosure of Invention
The invention aims to provide a crystalline anion framework copper Metal Organic Framework (MOF) material with high heterogeneous catalytic activity and high recovery rate and a preparation method thereof, and the material has a good catalytic effect in the application of catalyzing direct cyanation reaction of end-group alkyne to synthesize the 3-phenyl-propiolic nitrile derivative.
The purpose of the invention is realized by the following technical scheme:
a copper metal organic framework (Cu-MOF) catalytic material adopts two organic ligands which are respectively 9- (4-carboxyphenyl-3, 6-carbazole dicarboxylic acid (H)3CPCDC) and 4,4' -Bipyridine (BPY).
The structural formula of the catalytic material is { [ H ]3O][Cu(CPCDC)(BPY)]}nEach asymmetric unit comprises a copper ion, a BPY ligand and a CPCDC3-Ligand and one [ H3O]+The catalytic material contains open one-dimensional pore channels with the size of 11.08 Å × 15.35.35 15.35 Å.
The catalytic material is a triclinic system,P-1space group with volume 1982.3(6) Å3Z =2, unit cell parameters a =11.088(2) Å, b =13.556(2) Å, c =14.480(3) Å =66.300 (7), β =77.995 (8), γ =80.839 (8).
The preparation method of the copper metal organic framework (Cu-MOF) catalytic material comprises the following steps:
copper precursor and organic ligand H3Dissolving CPCDC and BPY in a solvent, carrying out closed reaction at 70-100 ℃ for 48-72h, cooling, washing and drying after the reaction is finished to obtain the catalytic material; the copper precursor and H3The molar ratio of CPCDC to BPY is (2-4) to 1: 1.
The copper precursor is copper nitrate, copper chloride, copper acetate or copper trifluoromethanesulfonate, the solvent is water, N-dimethylformamide and nitric acid, and the volume ratio of the water to the N, N-dimethylformamide to the nitric acid is 20:30:1-40:60: 3.
The preparation method of the copper metal organic framework (Cu-MOF) catalytic material specifically comprises the following steps:
(a) dissolving copper nitrate in water solution, and stirring at normal temperature for 10-30 min;
(b) stirring and dissolving BPY in N, N-dimethylformamide, dropwise adding the BPY into the reaction system (a), and stirring at normal temperature for 20-30 min;
(c) h is to be3Dissolving CPCDC in N, N-dimethylformamide under stirring, and dropwise adding into the reaction system (b) under stirring at normal temperature for 20-50 min;
(d) dropwise adding nitric acid into the reaction system (c), and stirring for 10-30 min;
(e) sealing the reaction system, and reacting at 70-100 deg.C for 48-72 h;
(f) after the reaction is finished, cooling to room temperature at the speed of 4-8 ℃/h, then washing with water and acetonitrile in sequence, and drying to obtain the catalytic material.
The application of the copper metal organic framework (Cu-MOF) catalytic material in the synthesis of the 3-phenyl-propiolic nitrile derivative through the direct cyanation reaction of the catalytic terminal alkyne is disclosed.
The cyano group is 2, 2-Azobisisobutyronitrile (AIBN).
According to the application method, the aromatic alkyne, the 2, 2-Azobisisobutyronitrile (AIBN) and the catalytic material are heated and stirred to react for 8 to 10 hours at the temperature of between 80 and 100 ℃, and the 3-phenyl-propiolic nitrile derivative is obtained; the molar ratio of aromatic alkyne, 2-Azobisisobutyronitrile (AIBN) and the catalytic material is 10:10:1-20:30: 1.
The catalytic material provided by the invention can be prepared by a common hydrothermal process, the preparation method is simple and feasible, a new choice is provided for catalytic synthesis of the 3-phenyl-propionitrile derivative, and the application value of the crystalline anion framework MOF material is expanded.
The catalyst material disclosed by the invention shows good activity in an experiment for catalytically synthesizing the 3-phenyl-propiolic nitrile derivative, the catalytic conversion rate of the obtained aromatic alkyne reaches 100%, the separation yield of a final product reaches more than 95%, and the catalyst material has very high catalytic activity and environmental friendliness.
The catalyst material has good stability, can keep stable at 275 ℃ below zero, can keep a perfect crystal state in the whole catalysis process, and lays a foundation for recycling. The excellent catalytic performance of the Cu-MOF is due to the unique crystal structure and the surface of the pore channel. First, MOFs participate in the reaction as heterogeneous catalysts in the reaction, so the substrate needs to enter the cavity of the complex to bind to the active metal site, and the product needs to be released from the crystal interior in a diffused form. Single crystal diffraction analysis shows that Cu-MOF contains open one-dimensional channels with a size of 11.08 a × 15.35 a, which ensures that the alkynyl compound 2, 2-Azobisisobutyronitrile (AIBN) and the product 3-phenyl-propynonitrile derivative participating in the reaction can diffuse freely inside the crystal. Secondly, the special pore channels not only can provide necessary places for the reaction, but also can stabilize the intermediate of the direct cyanation reaction by the cross section of the pore channels, thereby showing good selectivity of catalytic products. And the surface of the pore channel is filled with metal copper ions, and the coordination of copper is unsaturated, so that the active center can be completely exposed, the active center can be effectively contacted with a reaction substrate, and a good catalytic effect is obtained.
Drawings
FIG. 1 shows 9- (4-carboxyphenyl) -9H-carbozole-3, 6-dicarboxylic acid (H) used for the preparation of the material3CPCDC) and 4,4' -dipyridine (bpy) ligand formula.
FIG. 2 is a crystal structure diagram of a Cu-MOF material.
FIG. 3 is a topological structure of a Cu-MOF material.
FIG. 4 is a thermogravimetric analysis of a Cu-MOF material.
FIGS. 5-9 are nuclear magnetic diagrams of the products of direct cyanation reactions catalyzed by Cu-MOF catalysts.
FIG. 10 is a test chart of a Cu-MOF catalyst cycling experiment.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
A copper metal organic framework (Cu-MOF) catalytic material adopts two organic ligands which are respectively 9- (4-carboxyphenyl-3, 6-carbazole dicarboxylic acid (H)3CPCDC) and 4,4' -Bipyridine (BPY); the obtained catalytic material junctionHas the structural formula { [ H ]3O][Cu(CPCDC)(BPY)]}nBelongs to the field of triclinic system,P-1space group, Z is 2, unit cell parameters a =11.088(2) Å, b =13.556(2) Å, c =14.480(3) Å =66.300 (7), β =77.995 (8), gamma =80.839 (8), the catalyst material contains open one-dimensional channels with the size of 11.08 Å × 15.35 Å, each asymmetric unit contains a copper ion, a BPY ligand and a CPCDC C3-Ligand and one [ H3O]+。
The preparation method of the copper metal organic framework (Cu-MOF) catalytic material comprises the following steps:
copper precursor and organic ligand H3Dissolving CPCDC and BPY in a solvent, carrying out closed reaction at 70-100 ℃ for 48-72h, cooling, washing and drying after the reaction is finished to obtain the catalytic material; the copper precursor and H3The molar ratio of CPCDC to BPY is (2-4) to 1: 1.
Preferably, the copper precursor is copper nitrate, copper chloride, copper acetate or copper trifluoromethanesulfonate. The solvent is water, N-dimethylformamide and nitric acid, and the volume ratio of the water to the N, N-dimethylformamide to the nitric acid is (20: 30:1-40:60: 3). The three solvents are selected because the copper nitrate can be well dissolved by water, and the H can be well dissolved by the N, N-dimethylformamide3CPCDC and BPY, the addition of nitric acid prevents the reaction from beginning to precipitate.
The steps are as follows:
(a) dissolving copper nitrate in water solution, and stirring at normal temperature for 10-30 min;
(b) stirring and dissolving BPY in N, N-dimethylformamide, dropwise adding the BPY into the reaction system (a), and stirring at normal temperature for 20-50 min;
(c) h is to be3Dissolving CPCDC in N, N-dimethylformamide under stirring, and dropwise adding into the reaction system (b) under stirring at normal temperature for 20-50 min;
(d) dropwise adding nitric acid into the reaction system (c), and stirring for 10-30 min;
(e) sealing the reaction system, and reacting at 70-100 ℃ for 48-72 h;
(f) after the reaction is finished, cooling to room temperature at the speed of 4-8 ℃/h to obtain blue blocky crystals, then washing with water and acetonitrile in sequence, and drying to obtain the catalytic material.
The prepared copper metal organic framework (Cu-MOF) catalytic material can be applied to direct cyanation reaction of catalyzing end-group alkyne to synthesize a 3-phenyl-propiolic nitrile derivative; preferably, the cyano moiety is 2, 2-Azobisisobutyronitrile (AIBN).
The method comprises the following specific steps: heating and stirring aromatic alkyne, 2-Azobisisobutyronitrile (AIBN) and the catalytic material at 80-100 ℃ for reacting for 8-10h to obtain a 3-phenyl-propiolic nitrile derivative; the ratio of aromatic alkyne and 2, 2-Azobisisobutyronitrile (AIBN) to the catalytic material is 10:10:1 to 20:30: 1.
Example 2: preparation of copper metal organic framework (Cu-MOF) catalytic material
(1) Adding Cu (NO)3)2·3H2Adding O (0.048 g, 0.2mmol) into a 10mL reaction bottle, adding 2mL of water, and magnetically stirring at normal temperature for 20 min;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 100 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 60 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 75% (based on Cu (NO)3)2·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are detailed in a table 1, the Cu-MOF is tested by utilizing single crystal X-ray at room temperature, and the analysis of the test result shows that the Cu-MOFIs a triclinic crystal system, and is characterized in that,P-1space group with volume 1982.3(6) Å3The catalyst material contains open one-dimensional pore channels with the size of 11.08 Å × 15.35 Å. the crystal structure diagram is shown in figure 2, and H is relied on in Cu-MOF3CPCDC and coordination between BPY and copper ions form a structure containing an open one-dimensional pore channel with the size of 11.08 Å × 15.35.15.35 15.35 Å, which is favorable for the transmission of substrates and products, the topological structure diagram is shown in FIG. 3, and for more clearly understanding the connection mode of the structure, BPY can be simplified into a line which is used as two connection points and H3CPCDC is simplified into Y type, and when three connection points are formed, the Schl ä fli topological symbol is finally formed to be (6)98). The thermogravimetric analysis chart is shown in fig. 4, the Cu-MOF material can be kept stable below 275 ℃, and can ensure a perfect crystal state in the whole catalysis process.
Figure DEST_PATH_IMAGE001
Example 3: example 2 Cu-MOF catalytic Material catalytic 2, 2-azobisisobutyronitrile and phenylacetylene
(1) Phenylacetylene (0.102 g, 1mmol) and 2, 2-azobisisobutyronitrile (0.246 g, 1.5 mmol) were weighed into a round bottom flask in sequence, and magneton and acetonitrile (CH) solvent were added3CN，5mL）；
(2) Adding Cu-MOF (0.059 g, 0.1mmol) with an anion framework into the reaction system (1) as a catalyst;
(3) then heating the reaction system (2) to 90 ℃ to react for 9 h;
(4) after the reaction is finished, adding water 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;
(5) and (3) performing column chromatography purification (2) by using ethyl acetate/petroleum ether as a mobile phase, and separating the yield by 96%.1H NMR (400MHz, CDCl3) 7.62-7.66 (m, 2H), 7.53-7.59 (m, 1H), 7.42-7.47 (m, 2H), as shown in FIG. 5.
Example 4: Cu-MOF catalyst prepared in example 2 catalyzes 2, 2-azobisisobutyronitrile and 1-ethynyl-4-fluorobenzene
(1) 1-ethynyl-4-fluorobenzene (0.12 g, 1mmol) and 2, 2-azobisisobutyronitrile (0.246 g, 1.5 mmol) were weighed in sequence into a round bottom flask, and magneton and acetonitrile (CH) solvent were added3CN，5mL）；
(2) Adding Cu-MOF (0.059 g, 0.1mmol) with an anion framework into the reaction system (1) as a catalyst;
(3) then heating the reaction system (2) to 90 ℃ to react for 8 h;
(4) after the reaction is finished, adding water 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;
(5) ethyl acetate/petroleum ether as mobile phase, column chromatography purification (3), isolated yield 97%.1H NMR (400MHz, CDCl3) 7.59-7.69 (m, 2H), 7.09-7.17 (m, 2H), as shown in FIG. 6.
Example 5: Cu-MOF catalyst prepared in example 2 catalyzes 2, 2-azobisisobutyronitrile and 4-ethynyl-toluene
(1) To a round bottom flask were weighed 4-ethynyl-toluene (0.116 g, 1mmol) and 2, 2-azobisisobutyronitrile (0.246 g, 1.5 mmol) in that order, added magneton and acetonitrile (CH) solvent3CN，5mL）；
(2) Adding Cu-MOF (0.059 g, 0.1mmol) with an anion framework into the reaction system (1) as a catalyst;
(3) then heating the reaction system (2) to 90 ℃ to react for 10 h;
(4) after the reaction is finished, adding water 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;
(5) ethyl acetate/petroleum ether as mobile phase, column chromatography purification (3), isolated yield 97%.1H NMR (400MHz, CDCl3) 7.51 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 2.41 (s,3H), as shown in fig. 7.
Example 6: Cu-MOF catalyst prepared in example 2 catalyzes 2, 2-azobisisobutyronitrile and 4-ethynylbenzonitrile
（1) 4-ethynylbenzonitrile (0.127 g, 1mmol) and 2, 2-azobisisobutyronitrile (0.246 g, 1.5 mmol) were weighed in sequence into a round-bottomed flask, and magneton and acetonitrile (CH) solvent were added3CN，5mL）；
(2) Adding Cu-MOF (0.059 g, 0.1mmol) with an anion framework into the reaction system (1) as a catalyst;
(3) then heating the reaction system (2) to 90 ℃ to react for 9 h;
(4) after the reaction is finished, adding water 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;
(5) ethyl acetate/petroleum ether was used as a mobile phase, and column chromatography purification (4) was carried out with an isolated yield of 96%.1H NMR (400MHz, CDCl3) 7.73 (s, 4H), as shown in FIG. 8.
Example 7: example 2 preparation of an anionic skeletal Cu-MOF catalyst for 2, 2-azobisisobutyronitrile and 4-ethynylbiphenyl
(1) To a round bottom flask were weighed 4-ethynylbiphenyl (0.178 g, 1.3 mmol) and 2, 2-azobisisobutyronitrile (0.246 g, 1.5 mmol) in that order, and magneton and acetonitrile (CH) solvent were added3CN，5mL）。
(2) Then adding Cu-MOF (0.059 g, 0.1mmol) of an anionic framework into the reaction system (1) as a catalyst.
(3) Then the reaction system (2) is placed at 90 ℃ for reaction for 9 h.
(4) After the reaction was completed, (3) was quenched by adding water, extracted 3 times with Dichloromethane (DCM), and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and spin-dried.
(5) Ethyl acetate/petroleum ether was used as a mobile phase, and column chromatography purification (5) was carried out with an isolated yield of 96%.1H NMR (400MHz, CDCl3) 7.52-7.65 (m, 4H), 7.41-7.51 (m, 4H), 7.33-7.40 (m, 1H), as shown in FIG. 9. From FIGS. 5-9, all the products were detected by nuclear magnetism and were confirmed to be catalytic products.
Example 8: cyclic utilization of catalyst for cyclic catalysis of direct cyanation reaction
The stability of Cu-MOF as a heterogeneous catalyst was tested using phenylacetylene (0.102 g, 1mmol) and 2, 2-azobisisobutyronitrile as starting materials.
(1) The Cu-MOF isolated by filtration in example 3 was again added as a catalyst to an acetonitrile solvent (CH) containing phenylacetylene (0.102 g, 1mmol) and 2, 2-azobisisobutyronitrile (0.246 g, 1.5 mmol)3CN，5mL）；
(2) Then heating the reaction system (1) to 90 ℃ for reaction for 9 h;
(3) the separated Cu-MOF was then filtered as a catalyst and the experiment in example 2 was repeated for the same amount.
(4) The catalyst was recycled ten times in the same manner as described above, as shown in FIG. 10. During the test process of the cycling experiment, the Cu-MOF can be quickly recovered through simple centrifugation, and meanwhile, the separation yield is not obviously reduced after 10 cycles of the cycling experiment, and the result shows that the framework can still be maintained after at least 10 cycles of the cycling experiment of the Cu-MOF.
Example 9
(1) Adding CuCl2·2H2Adding O (0.034 g, 0.2mmol) into a 10mL reaction bottle, adding 2mL water, and magnetically stirring at normal temperature for 20 min;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 100 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 60 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 55% (based on CuCl)2·2H2O calculationObtained)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 10
(1) Mixing Cu (CH)3COO)2·3H2Adding O (0.040 g, 0.2mmol) into a 10mL reaction bottle, adding 2mL water, and magnetically stirring at normal temperature for 20 min;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 100 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 60 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 51% (based on Cu (CH)3COO)2·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 11
(1) Mixing Cu (OTf)2(0.072 g, 0.2mmol) is added into a 10mL reaction bottle, 2mL water is added, and magnetic stirring is carried out for 20min at normal temperature;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 100 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 60 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 31% (based on Cu (OTf))2Calculated to obtain)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 12
(1) Adding Cu (NO)3)·3H2Adding O (0.048 g, 0.2mmol) into a 10mL reaction bottle, adding 2mL of water, and magnetically stirring at normal temperature for 20 min;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 150 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and placing the reaction system in an oven at 70 ℃ for 60 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 41% (based on Cu (NO)3)·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 13
(1) Adding Cu (NO)3)·3H2Adding O (0.048 g, 0.2mmol) into a 10mL reaction bottle, adding 2mL of water, and magnetically stirring at normal temperature for 20 min;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 50 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 100 ℃ for 60 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 56% (based on Cu (NO)3)·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 14
(1) Adding Cu (NO)3)·3H2O (0.096 g, 0.4mmol) is added into a 10mL reaction bottle, 2mL water is added, and magnetic stirring is carried out for 20min at normal temperature;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 100 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 72 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 53% (based on Cu (NO)3)·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 15
(1) Adding Cu (NO)3)·3H2Adding O (0.061 g, 0.25mmol) into a 10mL reaction bottle, adding 2mL of water, and magnetically stirring at normal temperature for 20 min;
(2) BPY ligand (0.023 g, 0.15mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3CPCDC ligand (0.056 g, 0.15mmol) is dissolved in 2mL DMF under stirring, and is added dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 75 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 72 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 43% (based on Cu (NO)3)·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 16
(1) Adding Cu (NO)3)·3H2O (0.096 g, 0.4mmol) is added into a 10mL reaction bottle, 2mL water is added, and magnetic stirring is carried out for 20min at normal temperature;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3Dissolving CPCDC ligand (0.038 g, 0.1mmol) in 2mL DMF under stirring, and adding dropwise into the solution of the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 150 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 85 ℃ for 72 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 53% (based on Cu (NO)3)·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
Example 17
(1) Adding Cu (NO)3)·3H2O (0.096 g, 0.4mmol) is added into a 10mL reaction bottle, 4mL water is added, and magnetic stirring is carried out for 20min at normal temperature;
(2) BPY ligand (0.016 g, 0.1mmol) is dissolved in 1mL of N, N-Dimethylformamide (DMF) with stirring and is added into the reaction system dropwise;
(3) after the reaction system in the step (2) is stirred for 30min, H is added3CPCDC ligand (0.038 g, 0.1mmol) was dissolved in 5mL DMF under stirring and added dropwise to the solution in the reaction system;
(4) after the reaction system in the step (3) is stirred for 20min, 150 microliters of nitric acid (HNO) is added3) Dropwise adding the mixture into the solution of the reaction system, and stirring for 20 min;
(5) sealing the reaction system, and then placing the reaction system in an oven at 100 ℃ for 72 hours;
(6) cooling to room temperature at the speed of 5 ℃/h to obtain blue blocky crystals, washing with distilled water and acetonitrile, drying to obtain a target product, and weighing. Yield: 33% (based on Cu (NO)3)·3H2Calculated O)
(7) The crystallographic parameters of the obtained Cu-MOF catalytic material are the same as those in Table 1.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (7)

1. A copper metal organic framework (Cu-MOF) catalytic material, characterized in that the catalytic material is a triclinic system,P-1space group with volume 1982.3(6) Å3Z =2, unit cell parameters a =11.088(2) Å, b =13.556(2) Å, c =14.480(3) Å =66.300 (7), β =77.995 (8), and gamma =80.839 (8), wherein the catalytic material is represented by the structural formula { [ H ] }3O][Cu(CPCDC)(BPY)]}nEach asymmetric unit comprises a copper ion, a BPY ligand and a CPCDC3-Ligand and one [ H3O]+The catalytic material contains an open one-dimensional pore channel with the size of 11.08 Å× 15.35.35 15.35 Å, and adopts two organic ligands which are respectively 9- (4-carboxyl benzene) -3, 6-carbazole dicarboxylic acid (H)3CPCDC) and 4,4' -Bipyridine (BPY).
2. A method of preparing a copper metal organic framework (Cu-MOF) catalytic material according to claim 1, characterized by the steps of:
copper precursor and organic ligand H3Dissolving CPCDC and BPY in a solvent, carrying out closed reaction at 70-100 ℃ for 48-72h, cooling, washing and drying after the reaction is finished to obtain the catalytic material; the copper precursor and H3The molar ratio of CPCDC to BPY is (2-4) to 1: 1.
3. The method of claim 2, wherein the copper precursor is cupric nitrate, cupric chloride, cupric acetate or copper trifluoromethanesulfonate and the solvent is water, N-dimethylformamide and nitric acid.
4. A method of preparing a copper metal organic framework (Cu-MOF) catalytic material according to claim 3, characterized in that it comprises in particular the following steps:
(a) dissolving copper nitrate in water solution, and stirring at normal temperature for 10-30 min;
(b) stirring and dissolving BPY in N, N-dimethylformamide, dropwise adding the BPY into the reaction system (a), and stirring at normal temperature for 20-30 min;
(c) h is to be3Dissolving CPCDC in N, N-dimethylformamide under stirring, and dropwise adding into the reaction system (b) under stirring at normal temperature for 20-50 min;
(d) dropwise adding nitric acid into the reaction system (c), and stirring for 10-30 min;
(e) sealing the reaction system, and reacting at 70-100 deg.C for 48-72 h;
(f) after the reaction is finished, cooling to room temperature at the speed of 4-8 ℃/h, then washing with water and acetonitrile in sequence, and drying to obtain the catalytic material.
5. Use of the copper metal organic framework (Cu-MOF) catalytic material of claim 1 for the synthesis of 3-phenyl-propynenitrile derivatives by the direct cyanation of terminal alkynes.
6. Use according to claim 5, characterized in that the catalytic end-group alkyne is provided with 2, 2-Azobisisobutyronitrile (AIBN) in a direct cyanation reaction.
7. The method of claim 6, wherein the 3-phenyl-propynonitrile derivative is prepared by reacting 2, 2-Azobisisobutyronitrile (AIBN) with aromatic alkyne and the catalytic material at 80-100 ℃ for 8-10h under heating and stirring.
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