CN109369689A - A kind of copper metal organic frame (Cu-MOF) catalysis material, preparation method and application - Google Patents
A kind of copper metal organic frame (Cu-MOF) catalysis material, preparation method and application Download PDFInfo
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- CN109369689A CN109369689A CN201811500114.7A CN201811500114A CN109369689A CN 109369689 A CN109369689 A CN 109369689A CN 201811500114 A CN201811500114 A CN 201811500114A CN 109369689 A CN109369689 A CN 109369689A
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 61
- 239000010949 copper Substances 0.000 title claims abstract description 56
- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- TVIZMJJYAYGZPG-UHFFFAOYSA-N C1=CC(=CC=2C3=CC(=CC=C3NC12)C(=O)O)C(=O)O.C(=O)(O)C1=CC=CC=C1 Chemical class C1=CC(=CC=2C3=CC(=CC=C3NC12)C(=O)O)C(=O)O.C(=O)(O)C1=CC=CC=C1 TVIZMJJYAYGZPG-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 106
- 238000003756 stirring Methods 0.000 claims description 79
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 30
- 229910017604 nitric acid Inorganic materials 0.000 claims description 30
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 29
- 239000003446 ligand Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- -1 Aromatic alkyne Chemical class 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000002474 experimental method Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 25
- 239000013078 crystal Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000011097 chromatography purification Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000007210 heterogeneous catalysis Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical compound CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical compound FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- BPBNKCIVWFCMJY-UHFFFAOYSA-N 1-ethynyl-4-phenylbenzene Chemical group C1=CC(C#C)=CC=C1C1=CC=CC=C1 BPBNKCIVWFCMJY-UHFFFAOYSA-N 0.000 description 1
- UXBLZMYPTHYXIK-UHFFFAOYSA-N 9-(4-carboxyphenyl)carbazole-3,6-dicarboxylic acid Chemical compound C(=O)(O)C1=CC=C(C=C1)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(=O)O)C(=O)O UXBLZMYPTHYXIK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 230000000069 prophylactic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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 Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of copper metal organic frame (Cu-MOF) catalysis material, the catalysis material use two organic ligands, respectively 9- (4- carboxyl benzene -3,6- carbazole dicarboxylic acids (H3) and 4,4 '-bipyridyls (BPY) CPCDC.Catalyst material of the invention shows good activity in catalyzing and synthesizing 3- phenyl-propine carbonitrile derivatives experiment, the fragrant alkynes catalytic conversion of acquisition reaches 100%, the separation yield of final products reaches 95% or more, shows there is very high catalytic activity and the feature of environmental protection.
Description
Technical field
The invention belongs to heterogeneous catalysis field of material technology, and in particular to a kind of copper metal organic frame (Cu-
MOF) catalysis material, preparation method and application.
Technical background
Since 20th century, with industrialized continuous development, chemical industry, which has become, pushes development of world economy can not
Or scarce a part, and catalyst is the core of chemical industry and preparation process, is effective and selectable realization chemical bond
Generation and fracture tool, realize that chemicals or reagent are transformed into value product.Chemical products manufacture at the same time
It generates a large amount of environmentally hazardous waste material to need timely to handle, therefore, consider under economy and the angle of environment, exploitation has
Green and efficient heterogeneous catalysis system replaces homogeneous catalysis system for having very big driving force, to reduce at waste water
Reason, wastage of material etc. the predicament caused by chemistry/chemical industry manufacture field, and then alleviate the increasingly serious environment pressure in China
Power and realization social sustainable development are significant.
Crystalline state porous organo-metallic skeleton compound (MOFs) material has both inorganic unit and organo units advantage in one
Body becomes a kind of new catalytic material that academia nearly ten years widely attractes attention.It is the diversity of MOFs material structure, controllable
Property, and the neck such as catalysis, surface chemistry, energy storage, molecular magnetism, biomedical imaging is widely applied to as solid material
Domain.Especially they have fixed hole, big specific surface area and tunable physical and chemical properties, particularly suitable as
Molecular catalyst with fixed catalytic site forms unified catalytic site and open hole configurations, organic being catalyzed
It when reaction, tends in adsorption reaction substrate to duct first, then participates in being catalyzed and by its specific hole by metal center
Road structure generates the selectivity such as special chemistry, size, solid.Secondly, the centrical concerted catalysis of polygamy is made in MOFs material
With by the mode of " treating different things alike ", can realizing tandem reaction or concerted reaction to avoid the separation of intermediate products.Due to crystalline state
Porous MOFs catalyst has high catalytic efficiency, selective to substrate, the features such as can recycling, efficiently urges in exploitation
Changing material has vast potential for future development.The present invention utilizes 9- (4- carboxyl benzene -3,6- carbazole dicarboxylic acids [9- (4-
carboxyphenyl)-9H-carbazole-3,6-dicarboxylic acid](H3CPCDC) and 4,4 '-bipyridyls (4,
4'-Bipyridine) the organic ligand of (BPY) as difunctionalization has constructed a kind of tool by the self assembly with copper ion
There is copper metal crystalline state anion frame MOF the material { [H of good heterogeneous catalysis performance3O][Cu(CPCDC)(BPY)]}n(Cu-
MOF).
Summary of the invention
The crystalline state yin that the purpose that the present invention solves is high there is provided a kind of heterogeneous catalysis activity and recovery utilization rate is high from
Sub- skeleton copper metal MOF material and preparation method, the direct cyanalation reaction which is catalyzed end-group alkyne synthesize 3- phenyl-propine
There is preferable catalytic effect in the application of carbonitrile derivatives.
The purpose of the present invention is what is realized with following technical proposals:
A kind of copper metal organic frame (Cu-MOF) catalysis material, the catalysis material use two organic ligands, respectively 9-
(4- carboxyl benzene -3,6- carbazole dicarboxylic acids (H3) and 4,4 '-bipyridyls (BPY) CPCDC.
The catalysis material structural formula is { [H3O][Cu(CPCDC)(BPY)]}n, each asymmetric cell includes a copper
Ion, a BPY ligand, a CPCDC3-Ligand and [a H3O]+；The catalysis material contains open one-dimensional channels,
Size is 11.08 × 15.35.
The catalysis material is anorthic system,P-1Space group, volume are 1982.3 (6)3, Z=2, cell parameter a=
11.088 (2), b=13.556 (2), c=14.480 (3), α=66.300(7), β=77.995(8), γ=80.839(8).
The preparation method of copper metal organic frame (Cu-MOF) catalysis material as described above, comprising the following steps:
By copper presoma and organic ligand H3CPCDC, BPY dissolve in a solvent, the confined reaction 48-72h at 70-100 DEG C, instead
It is cooling after the completion of answering, it washs, it is dry, obtain the catalysis material；The copper presoma and H3The molar ratio of CPCDC, BPY is
(2-4):1:1。
The copper presoma is copper nitrate, copper chloride, and copper acetate or trifluoromethayl sulfonic acid copper, the solvent are water, N, N-
Dimethylformamide and nitric acid, the water and n,N-Dimethylformamide and the volume ratio of nitric acid are 20:30:1-40:60:3.
The preparation method of copper metal organic frame (Cu-MOF) catalysis material as described above, specifically includes the following steps:
(a) copper nitrate is dissolved in aqueous solution, stirring at normal temperature 10-30min；
(b) it by BPY stirring and dissolving in n,N-Dimethylformamide, and is added dropwise in reaction system (a), stirring at normal temperature 20-
30min；
(c) by H3Stirring at normal temperature in reaction system (b) is added dropwise in n,N-Dimethylformamide in CPCDC stirring and dissolving
20-50min；
(d) nitric acid is added dropwise in reaction system (c), and stirs 10-30min；
(e) by above-mentioned reaction system it is closed after, be placed at 70-100 DEG C and react 48-72h；
(f) after having reacted, room temperature is down to the rate of 4-8 DEG C/h, is then successively washed with water and acetonitrile, it is dry, obtain institute
State catalysis material.
A kind of copper metal organic frame (Cu-MOF) catalysis material as described above is direct cyanalation catalysis end-group alkyne
Application in reaction synthesis 3- phenyl-propine carbonitrile derivatives.
The cyano member is 2,2- azodiisobutyronitrile (AIBN).
Application method as described above, fragrant alkynes and 2,2- azodiisobutyronitrile (AIBN) and the catalysis material exist
At 80-100 DEG C, heating stirring reacts 8-10h to get 3- phenyl-propine carbonitrile derivatives；Fragrant alkynes, two isobutyl of 2,2- azo
The molar ratio of nitrile (AIBN) and the catalysis material is 10:10:1-20:30:1.
Catalysis material provided by the invention can be prepared by common hydro-thermal method technique, and preparation method is simple, is
It catalyzes and synthesizes 3- phenyl-propine carbonitrile derivatives and provides new selection, while having expanded answering for crystalline state anion frame MOF material
With value.
Catalyst material of the invention shows good work in catalyzing and synthesizing 3- phenyl-propine carbonitrile derivatives experiment
Property, the fragrant alkynes catalytic conversion of acquisition reaches 100%, and the separation yield of final products reaches 95% or more, shows have very
High catalytic activity and the feature of environmental protection.
Catalyst material stability of the invention is good, stablizes in 275 DEG C or less holdings, and can protect in entire catalytic process
Intact crystal state is held, is laid the foundation for circulation and stress recycling.The Cu-MOF has so excellent catalytic performance should
Derived from its unique crystal structure and channel surfaces.Firstly, MOFs is participated in instead in the form of heterogeneous catalysis in the reaction
It answers, therefore substrate needs to enter complex cavity inside in conjunction with active metal sites, product is also required to diffusion mode from crystalline substance
Internal portion dissociates away.Single crystal diffraction analysis shows Cu-MOF contains open one-dimensional channels, size is 11.08 ×
15.35, it is ensured that participate in the alkynyl compounds 2 of reaction, 2- azodiisobutyronitrile (AIBN) and product 3- phenyl-cyanoacetylene
Derivative can be in crystals free diffusing.Secondly, duct special so not only can provide necessary place for reaction,
Its duct section can more stablize the intermediate of direct cyanalation reaction, to show good catalysate selectivity.
Again, channel surfaces have been full of metal copper ion, and the coordination of copper be it is unsaturated, can guarantee that activated centre is completely naked in this way
Expose, to effectively contact with reaction substrate, obtains good catalytic effect.
Detailed description of the invention
Fig. 1 is that material prepares 9- (the 4-carboxyphenyl) -9H-carbazole-3,6-dicarboxylic used
acid (H3CPCDC) and 4,4'-Bipyridine(BPY) ligand molecular formula.
Fig. 2 is the crystal structure figure of Cu-MOF material.
Fig. 3 is the topology diagram of Cu-MOF material.
Fig. 4 is the thermogravimetric analysis figure of Cu-MOF material.
Fig. 5-9 is the product nuclear-magnetism figure of the directly cyanalation reaction of Cu-MOF catalyst.
Figure 10 is Cu-MOF catalyst circulation experiment test chart.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
A kind of copper metal organic frame (Cu-MOF) catalysis material, using two organic ligands, respectively 9- (4- carboxyl benzene -3,
6- carbazole dicarboxylic acids (H3) and 4,4 '-bipyridyls (BPY) CPCDC；Obtained catalysis material structural formula is { [H3O][Cu(CPCDC)
(BPY)]}n, belong to anorthic system,P-1Space group, Z 2, cell parameter a=11.088 (2), b=13.556 (2), c=
14.480 (3), α=66.300(7), β=77.995(8), γ=80.839(8)；Contain open one-dimensional hole in catalysis material
Road, size are 11.08 × 15.35.Each asymmetric cell include a copper ion, a BPY ligand, one
CPCDC3-Ligand and [a H3O]+。
The preparation method of copper metal organic frame (Cu-MOF) catalysis material as described above, comprising the following steps:
By copper presoma and organic ligand H3CPCDC, BPY dissolve in a solvent, the confined reaction 48-72h at 70-100 DEG C, instead
It is cooling after the completion of answering, it washs, it is dry, obtain the catalysis material；The copper presoma and H3The molar ratio of CPCDC, BPY is
(2-4):1:1。
It is preferred that copper presoma is copper nitrate, copper chloride, copper acetate or trifluoromethayl sulfonic acid copper.The solvent is water, N, N-
Dimethylformamide and nitric acid, the water and n,N-Dimethylformamide and the volume ratio of nitric acid are (20:30:1-40:60:3).
These three solvents are selected, are that can be very good dissolution copper nitrate due to water, n,N-Dimethylformamide good can dissolve
H3CPCDC and BPY, addition nitric acid can prophylactic response start to precipitate.
Above-mentioned steps specifically:
(a) copper nitrate is dissolved in aqueous solution, stirring at normal temperature 10-30min；
(b) it by BPY stirring and dissolving in n,N-Dimethylformamide, and is added dropwise in reaction system (a), stirring at normal temperature 20-
50min；
(c) by H3Stirring at normal temperature in reaction system (b) is added dropwise in n,N-Dimethylformamide in CPCDC stirring and dissolving
20-50min；
(d) nitric acid is added dropwise in reaction system (c), and stirs 10-30min；
(e) by above-mentioned reaction system it is closed after, be placed in 70-100 DEG C of reaction 48-72h；
(f) after having reacted, room temperature is down to the rate of 4-8 DEG C/h, obtains blue bulk crystals, then successively use water and acetonitrile
Washing, it is dry, obtain the catalysis material.
Copper metal organic frame (Cu-MOF) catalysis material being prepared can be applied to the direct cyano of catalysis end-group alkyne
Change reaction synthesis 3- phenyl-propine carbonitrile derivatives；It is preferred that the cyano member is 2,2- azodiisobutyronitrile (AIBN).
Specific steps are as follows: by fragrant alkynes and 2,2- azodiisobutyronitrile (AIBN) and the catalysis material at 80-100 DEG C
Under, heating stirring reacts 8-10h to get 3- phenyl-propine carbonitrile derivatives；Fragrant alkynes and 2,2- azodiisobutyronitrile (AIBN)
Ratio with the catalysis material is 10:10:1-20:30:1.
Embodiment 2: the preparation of copper metal organic frame (Cu-MOF) catalysis material
(1) by Cu (NO3)2·3H2O (0.048 gram, 0.2mmol) is added in 10mL reaction flask, and 2mL water, room temperature magnetic force is added
Stir 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 100 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 60h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 75%(is based on Cu (NO3)2·3H2O is calculated)
(7) see Table 1 for details for obtained Cu-MOF catalysis material crystallographic parameter, and Cu-MOF is to utilize single crystal X-ray at room temperature
Test, test result analysis show that Cu-MOF is anorthic system,P-1Space group, volume are 1982.3 (6)3, in catalysis material
Containing open one-dimensional channels, size is 11.08 × 15.35.Crystal structure figure is shown in Fig. 2, relies in Cu-MOF
H3Coordination between CPCDC and BPY and copper ion is constructed and is formd containing open one-dimensional channels, size 11.08
× 15.35, conducive to the transmission of substrate and product.Topology diagram is shown in Fig. 3, is the clearer connection side for understanding structure
Formula can be simplified to BPY be a line, treat as two tie points, H3CPCDC is simplified to Y type, treats as three tie points, finally
Forming Schl fli topology symbol is (698).Thermogravimetric analysis figure is shown in that Fig. 4, Cu-MOF material can keep steady at 275 DEG C or less
Fixed, can ensure has intact crystal state in entire catalytic process.
Embodiment 3: Cu-MOF catalysis material catalysis 2,2- azodiisobutyronitrile and phenylacetylene prepared by embodiment 2
(1) phenylacetylene (0.102 gram, 1mmol) and 2 are successively weighed into round-bottomed flask, 2- azodiisobutyronitrile (0.246 gram,
1.5mmol), magneton and solvent acetonitrile (CH is added3CN, 5mL)；
(2) it is added Cu-MOF(0.059 grams of anion frame to (1) reaction system again, 0.1mmol) it is used as catalyst；
(3) reaction system (2) are then heated into 90 DEG C of reaction 9h；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 96% as mobile phase, column Chromatographic purification (2).1H NMR (400 MHz,
CDCl3) δ: 7.62-7.66 (m, 2H), 7.53-7.59 (m, 1H), 7.42-7.47 (m, 2H), as shown in Figure 5.
Embodiment 4: Cu-MOF catalyst 2,2- azodiisobutyronitrile and 1- acetenyl -4- fluorine prepared by embodiment 2
Benzene
(1) 1- acetenyl -4- fluorobenzene (0.12 gram, 1mmol) and 2,2- azodiisobutyronitrile are successively weighed into round-bottomed flask
Magneton and solvent acetonitrile (CH is added in (0.246 gram, 1.5mmol)3CN, 5mL)；
(2) it is added Cu-MOF(0.059 grams of anion frame to (1) reaction system again, 0.1mmol) it is used as catalyst；
(3) reaction system (2) are then heated into 90 DEG C of reaction 8h；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 97% as mobile phase, column Chromatographic purification (3).1H NMR (400 MHz,
CDCl3) δ: 7.59-7.69 (m, 2H), 7.09-7.17 (m, 2H), as shown in Figure 6.
Embodiment 5: Cu-MOF catalyst 2,2- azodiisobutyronitrile and 4- acetenyl-toluene prepared by embodiment 2
(1) 4- acetenyl-toluene (0.116 gram, 1 mmol) and 2,2- azodiisobutyronitrile are successively weighed into round-bottomed flask
Magneton and solvent acetonitrile (CH is added in (0.246 gram, 1.5mmol)3CN, 5mL)；
(2) it is added Cu-MOF(0.059 grams of anion frame to (1) reaction system again, 0.1mmol) it is used as catalyst；
(3) reaction system (2) are then heated into 90 DEG C of reaction 10h；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 97% as mobile phase, column Chromatographic purification (3).1H NMR (400 MHz,
CDCl3) δ: 7.51 (d, J=8.0 Hz, 2H), 7.22 (d, J=8.0 Hz, 2H), 2.41 (s, 3H), such as
Shown in Fig. 7.
Embodiment 6: Cu-MOF catalyst 2,2- azodiisobutyronitrile and 4- acetenyl cyanophenyl prepared by embodiment 2
(1) 4- acetenyl cyanophenyl (0.127 gram, 1 mmol) and 2,2- azodiisobutyronitrile are successively weighed into round-bottomed flask
Magneton and solvent acetonitrile (CH is added in (0.246 gram, 1.5mmol)3CN, 5mL)；
(2) it is added Cu-MOF(0.059 grams of anion frame to (1) reaction system again, 0.1mmol) it is used as catalyst；
(3) reaction system (2) are then heated into 90 DEG C of reaction 9h；
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, and it is dry with anhydrous sodium sulfate to merge organic phase
Dry, filtering is spin-dried for；
(5) ethyl acetate/petroleum ether separates yield 96% as mobile phase, column Chromatographic purification (4).1H NMR (400 MHz,
CDCl3) 7.73 (s, 4H), as shown in Figure 8.
Embodiment 7: anion frame Cu-MOF catalyst 2,2- azodiisobutyronitrile and 4- second prepared by embodiment 2
Alkynyl biphenyl
(1) 4- acetenyl biphenyl (0.178 gram, 1.3mmol) and 2,2- azodiisobutyronitrile are successively weighed into round-bottomed flask
Magneton and solvent acetonitrile (CH is added in (0.246 gram, 1.5mmol)3CN, 5mL).
(2) it is added Cu-MOF(0.059 grams of anion frame to (1) reaction system again, 0.1mmol) it is used as catalyst.
(3) then reaction system (2) is placed at 90 DEG C and reacts 9h.
(4) after completion of the reaction, it goes out to (3) plus water quenching, methylene chloride (DCM) extracts 3 times, merges organic phase anhydrous slufuric acid
Sodium dries, filters, and is spin-dried for.
(5) ethyl acetate/petroleum ether separates yield 96% as mobile phase, column Chromatographic purification (5).1H NMR (400
MHz, CDCl3) δ: 7.52-7.65 (m, 4H), 7.41-7.51 (m, 4H), 7.33-7.40 (m, 1H), such as Fig. 9
It is shown.From Fig. 5-9 it is found that all products are detected by nuclear-magnetism, it was demonstrated that be catalysate.
Embodiment 8: it recycles catalyst circulation and is catalyzed directly cyanalation reaction
Using phenylacetylene (0.102 gram, 1mmol) and 2,2- azodiisobutyronitrile is raw material, and detection Cu-MOF is urged as heterogeneous
The stability of agent.
(1) by the Cu-MOF filtered to isolate in embodiment 3 be used as again catalyst be added to containing phenylacetylene (0.102 gram,
1mmol) and the acetonitrile solvent (CH of 2,2- azodiisobutyronitrile (0.246 gram, 1.5mmol)3CN, 5mL)；
(2) then reaction system (1) is heated and reacts 9h at 90 DEG C；
(3) Cu-MOF then filtered to isolate continues to repeat same amount of experiment in embodiment 2 as catalyst.
(4) catalyst recycles ten times according to the above method, and specific method is same as above, as shown in Figure 10.It is surveyed in circulation experiment
During examination, Cu-MOF can be by being simply centrifuged quick recovery, while separating yield and dividing after 10 wheel circulation experiments
It does not significantly decrease from yield, the results show that Cu-MOF at least 10, which takes turns circulation experiment back skeleton, can still keep.
Embodiment 9
(1) by CuCl2·2H2O (0.034 gram, 0.2mmol) is added in 10mL reaction flask, and 2mL water is added, and room temperature magnetic force stirs
Mix 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 100 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 60h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 55%(is based on CuCl2·2H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 10
(1) by Cu (CH3COO)2·3H2O (0.040 gram, 0.2mmol) is added in 10mL reaction flask, and 2mL water, room temperature is added
Magnetic agitation 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 100 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 60h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 51%(is based on Cu (CH3COO)2·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 11
(1) by Cu (OTf)2(0.072 gram, 0.2mmol) is added in 10mL reaction flask, and 2mL water, room temperature magnetic agitation is added
20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 100 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 60h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 31%(is based on Cu (OTf)2It is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 12
(1) by Cu (NO3)·3H2O (0.048 gram, 0.2mmol) is added in 10mL reaction flask, and 2mL water, room temperature magnetic force is added
Stir 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 150 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 70 DEG C of baking oven 60h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 41%(is based on Cu (NO3)·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 13
(1) by Cu (NO3)·3H2O (0.048 gram, 0.2mmol) is added in 10mL reaction flask, and 2mL water, room temperature magnetic force is added
Stir 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 50 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 100 DEG C of baking oven 60h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 56%(is based on Cu (NO3)·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 14
(1) by Cu (NO3)·3H2O (0.096 gram, 0.4mmol) is added in 10mL reaction flask, and 2mL water, room temperature magnetic force is added
Stir 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 100 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 72h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 53%(is based on Cu (NO3)·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 15
(1) by Cu (NO3)·3H2O (0.061 gram, 0.25mmol) is added in 10mL reaction flask, and 2mL water, normal temperature magnetic is added
Power stirs 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.023 gram, 0.15mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.056 gram, 0.15mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 75 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 72h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 43%(is based on Cu (NO3)·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 16
(1) by Cu (NO3)·3H2O (0.096 gram, 0.4mmol) is added in 10mL reaction flask, and 2mL water, room temperature magnetic force is added
Stir 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 2mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 150 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 85 DEG C of baking oven 72h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 53%(is based on Cu (NO3)·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment 17
(1) by Cu (NO3)·3H2O (0.096 gram, 0.4mmol) is added in 10mL reaction flask, and 4mL water, room temperature magnetic force is added
Stir 20min；
(2) in 1mL N,N-dimethylformamide (DMF) and dropwise by BPY ligand (0.016 gram, 0.1mmol) stirring and dissolving
It is added in above-mentioned reaction system；
(3) after reaction system stirring 30min in step (2), by H3CPCDC ligand (0.038 gram, 0.1mmol) stirring and dissolving
In 5mL DMF, and it is added dropwise in the solution of reaction system；
(4) after reaction system stirring 20min in step (3), by 150 microlitres of nitric acid (HNO3) the molten of reaction system is added dropwise
In liquid, and stir 20min；
(5) by above-mentioned reaction system it is closed after, be placed in 100 DEG C of baking oven 72h；
(6) room temperature is down to the rate of 5 DEG C/h, obtains blue bulk crystals, washed with distilled water, acetonitrile, it is dry, obtain target
Product, weighing.Yield: 33%(is based on Cu (NO3)·3H2O is calculated)
(7) obtained Cu-MOF catalysis material crystallographic parameter and table 1 are identical.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (9)
1. a kind of copper metal organic frame (Cu-MOF) catalysis material, it is characterised in that the catalysis material organic is matched using two
Body, respectively 9- (4- carboxyl benzene -3,6- carbazole dicarboxylic acids (H3) and 4,4 '-bipyridyls (BPY) CPCDC.
2. copper metal organic frame (Cu-MOF) catalysis material as described in claim 1, it is characterised in that the catalysis material
Structural formula is { [H3O][Cu(CPCDC)(BPY)]}n, each asymmetric cell include a copper ion, a BPY ligand, one
CPCDC3-Ligand and [a H3O]+；The catalysis material contains open one-dimensional channels, and size is 11.08 ×
15.35 Å。
3. copper metal organic frame (Cu-MOF) catalysis material as claimed in claim 2, it is characterised in that the catalysis material
It is anorthic system,P-1Space group, volume are 1982.3 (6)3, Z=2, cell parameter a=11.088 (2), b=13.556 (2)
, c=14.480 (3), α=66.300(7), β=77.995(8), γ=80.839(8).
4. the preparation method of copper metal organic frame (Cu-MOF) catalysis material as described in any one of claims 1-3, special
Sign be the following steps are included:
By copper presoma and organic ligand H3CPCDC, BPY dissolve in a solvent, the confined reaction 48-72h at 70-100 DEG C, instead
It is cooling after the completion of answering, it washs, it is dry, obtain the catalysis material；The copper presoma and H3The molar ratio of CPCDC, BPY is
(2-4):1:1。
5. the preparation method of copper metal organic frame (Cu-MOF) catalysis material as claimed in claim 4, it is characterised in that institute
Stating copper presoma is copper nitrate, copper chloride, and copper acetate or trifluoromethayl sulfonic acid copper, the solvent are water, N, N- dimethyl formyl
Amine and nitric acid, the water and n,N-Dimethylformamide and the volume ratio of nitric acid are 20:30:1-40:60:3.
6. the preparation method of copper metal organic frame (Cu-MOF) catalysis material as claimed in claim 5, it is characterised in that tool
Body the following steps are included:
(a) copper nitrate is dissolved in aqueous solution, stirring at normal temperature 10-30min；
(b) it by BPY stirring and dissolving in n,N-Dimethylformamide, and is added dropwise in reaction system (a), stirring at normal temperature 20-
30min；
(c) by H3Stirring at normal temperature in reaction system (b) is added dropwise in n,N-Dimethylformamide in CPCDC stirring and dissolving
20-50min；
(d) nitric acid is added dropwise in reaction system (c), and stirs 10-30min；
(e) by above-mentioned reaction system it is closed after, be placed at 70-100 DEG C and react 48-72h；
(f) after having reacted, room temperature is down to the rate of 4-8 DEG C/h, is then successively washed with water and acetonitrile, it is dry, obtain institute
State catalysis material.
7. a kind of if described in any item copper metal organic frame (Cu-MOF) catalysis materials of claim 1-2 are in catalysis end-group alkyne
It is direct it is cyanalation reaction synthesis 3- phenyl-propine carbonitrile derivatives in application.
8. the use as claimed in claim 7, it is characterised in that the cyano member is 2,2- azodiisobutyronitrile (AIBN).
9. application method as claimed in claim 8, it is characterised in that by fragrant alkynes and 2,2- azodiisobutyronitrile (AIBN)
With the catalysis material at 80-100 DEG C, heating stirring reacts 8-10h to get 3- phenyl-propine carbonitrile derivatives；Aromatic alkyne
The molar ratio of hydrocarbon, 2,2- azodiisobutyronitrile (AIBN) and the catalysis material is 10:10:1-20:30:1.
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| GB2598654A (en) * | 2020-09-08 | 2022-03-09 | Hangzhou Jingshu New Mat Co Ltd | A catalyst for furfural selective hydrogenation |
| CN112961294A (en) * | 2021-02-05 | 2021-06-15 | 河南大学 | Water-soluble MOF composite polymer material and preparation method and application thereof |
| CN113750971A (en) * | 2021-09-27 | 2021-12-07 | 中原工学院 | Adsorbing material based on zinc complex and preparation method and application thereof |
| CN113750971B (en) * | 2021-09-27 | 2023-07-21 | 中原工学院 | Adsorption material based on zinc complex and preparation method and application thereof |
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