CN107739444A - Based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application - Google Patents
Based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application Download PDFInfo
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- CN107739444A CN107739444A CN201711128860.3A CN201711128860A CN107739444A CN 107739444 A CN107739444 A CN 107739444A CN 201711128860 A CN201711128860 A CN 201711128860A CN 107739444 A CN107739444 A CN 107739444A
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- 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
- 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]
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- 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
Abstract
The present invention relates to one kind to be based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application.The technical scheme of use：By Yb (NO3)3, o-fluorobenzoic acid, 2 amino terephthalic acid (TPA)s, N, N dimethylformamides, nitric acid and water are added in container, stirred 30 minutes under normal temperature；It is put into baking oven after container is sealed, is kept for 3 days under temperature 378K；It is slowly cooled to room temperature, obtains khaki octahedral crystal；With N, the washing of N dimethylformamides, filtering, dry, obtain target product.Prepared by the present invention based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units, preparation method is simple, and shows good catalytic performance to deacetalization Knoevenagel condensation reactions.
Description
Technical field
The present invention relates to a kind of metal-organic framework material, is specifically related to a kind of Yb based on amino functionalIIISix
The metal-organic framework material of core molecule construction unit and its catalysis deacetalization-Knoevenagel condensation reactions
In application.
Background technology
Metal-organic framework materials (MOFs) are the hot research necks in current Coordinative Chemistry and material science
Domain.Synthetic modification after MOFs structure has designability and can carried out, aperture size is adjustable and can control activity
The species of functional group so that MOFs plays important role in catalyticing research field.Multi-nuclear metal cluster compound has become mesh
Preceding Disciplinary Frontiers of greatest concern.In recent years, some four discrete cores, five cores, six cores, seven cores, eight cores, nine cores, ten cores, 12
Core, 15 cores etc. are synthesized in succession.Professor Long Lasheng of Xiamen University utilizes threonine part, synthesized four it is chiral
60 core rare earth cluster compounds, this is also the check figure highest rare earth cluster compound having now been found that.In recent years, as multi-kernel rare-earth cluster closes
The fast development of object space face research, molecular structure unit complex functionality rare earth cluster metal organic frame material is used as using rare earth cluster
Material, due to its unique structure, abundant hole and offunctional site, causes the attention of chemist and material scholar,
As the focus of research.
Cascade reaction is a kind of economic, effective and environmentally friendly chemical method, has attracted vast chemical research
The interest of person.Cascade reaction often refers to that reactions more than two steps or two steps is recurred, direct without separating intermediate product
A succession of reaction of final product is obtained, the use of chemical substance and the discharge of pollutant can be efficiently reduced.Therefore, having
Machine catalytic field, the development of cascade reaction will necessarily turn into a new developing direction.
The content of the invention
The purpose of the present invention is by the use of 2- amino terephthalic acid (TPA) as organic ligand, by adjusting synthesis condition, is utilized
The method of solvent heat constructs out a kind of new Yb based on amino functionalIIISix core molecule construction units metal it is organic
Framework, and study its as Lewis acid andBase bifunctional catalyst, to deacetalization-
The catalytic performance of Knoevenagel condensation reactions.
The technical solution adopted by the present invention is：One kind is based on amino functional YbIIIThe metal of six core molecule construction units has
Machine frame frame material, its molecular formula are [(CH3)2NH2][Yb6(μ3-OH)8(BDC-NH2)6(H2O)]·(solv)X, its crystal belongs to
Cubic system, space group Fm-3m, it is by [Yb6(μ3-OH)8(O2C-)12] node is used as, by part BDC-NH2Bridging forms
Three-dimensional structure, include two kinds of polyhedron cages of octahedral and tetrahedral.
One kind is based on amino functional YbIIIThe preparation method of the metal-organic framework material of six core molecule construction units, bag
Include following synthesis step：
1) by 2- amino terephthalic acid (TPA)s (H2BDC-NH2)、Yb(NO3)3, o-fluorobenzoic acid and N,N-dimethylformamide
(DMF) it is added in container, the stirring and dissolving under normal temperature, adds a small amount of nitric acid and water, stir；
Preferably, in molar ratio, 2- amino terephthalic acid (TPA) (H2BDC-NH2):Yb(NO3)3=1:0.8-1.5；
Preferably, by volume, DMF:HNO3=10-15:1.
2) it is put into after container is sealed in baking oven, is heated under 373-383K, is kept for 3 days；Heating rate is 10Kmin-1；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal；Preferably, the rate of temperature fall being slowly cooled to room temperature
For 10Kmin-1；Washed, filtered with DMF, dried, obtain target product.
The present invention based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units, contain in structure
Have abundant unsaturated Yb (III) centers and amino, can be used as Lewis acid andBase bifunctional catalyst, it is right
Deacetalization-Knoevenagel condensation reactions carry out catalytic applications.Method is as follows：Take benzaldehyde dimethyl acetal, third
Dintrile, dimethyl sulfoxide (DMSO) and catalyst are passed through N in reaction tube under conditions of stirring2, react 24h under conditions of 50 DEG C；
Described catalyst is the above-mentioned Yb based on amino functionalIIISix core molecule construction units metal-organic framework material.
Reaction equation is as follows：
The beneficial effects of the invention are as follows：Prepared by the present invention based on amino functional YbIIISix core molecule construction units
Yb (III) ion in metal-organic framework material is nine coordinations, so containing abundant undersaturated Yb (III) in structure
Center, Lewis acid site can be used as, and contain-NH on part2, can conductAlkali site.Therefore, hair can be made
Bright complex as Lewis acid andBase bifunctional catalyst, deacetalization-Knoevenagel is contracted
Close reaction and show good catalytic performance.And the because Yb based on amino functional prepared by the present inventionIIISix core molecules
Construction unit metal-organic framework material synthetic method is simple, has application prospect.
Brief description of the drawings
Fig. 1 is the core clustering architecture units of Yb- six of the 12- connections in metal-organic framework material structure of the present invention.
Fig. 2 a are octahedra cage schematic diagrames in metal-organic framework material structure of the present invention.
Fig. 2 b are tetrahedron cage schematic diagrames in metal-organic framework material structure of the present invention.
Fig. 3 is cage skeleton structure schematic diagram in metal-organic framework material structure of the present invention.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram that the yield that embodiment 2 is reacted changes over time.
Fig. 5 is the catalytic activity that metal-organic framework material of the present invention carries out four-wheel circulation catalytic reaction.
Fig. 6 is the XRD that metal-organic framework material of the present invention carries out four-wheel circulation catalytic reaction.
Embodiment
Embodiment 1 is a kind of to be based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units
By H2BDC-NH2(9.0mg, 0.048mmol), Yb (NO3)3·6H2O (19.3mg, 0.0413mmol), adjacent fluorobenzene first
Sour (48.7mg) is added in the high temperature resistant spiral mouth vial that volume is 5mL, adds 2.2mL DMF, is stirred in normal temperature condition
Dissolved, add H2O (0.5mL) and 3.57M HNO3(0.2mL), stir 20 minutes until metal salt is all dissolved with having
Machine part is well mixed, and is put into after vial is sealed in baking oven, heating rate 10Kmin-1, 378K is warming up to, at this
At a temperature of heat 3 days, with 10Kmin-1Rate of temperature fall be slowly cooled to room temperature, have khaki octahedral crystal generation, use
DMF is washed, and is filtered, and is dried, is obtained target product, i.e., based on amino functional YbIIIThe metal of six core molecule construction units has machine frame
Frame material, yield 63%.
The present invention synthesize based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units, structure
As shown in Fig. 1-Fig. 3, the crystal structure belongs to cubic system, space group Fm-3m.Molecular formula is [(CH3)2NH2][Yb6
(μ3-OH)8(BDC-NH2)6(H2O)]·(solv)X, the compound is by [Yb6(μ3-OH)8(O2C-)12] it is used as node, such as Fig. 1
It is shown, by part BDC-NH2The three-dimensional structure that bridging forms.Cation [(CH3)2NH2]+It is located at the MOF's as counter ion counterionsl gegenions
In duct.Each 2- amino terephthalic acid (TPA) parts and four Yb3+Ion coordination, six Yb3+Ion and six come from 2- ammonia
Oxygen and six μ on the carboxyl of base terephthalic acid (TPA)3- OH is coordinated.Along b- direction of principal axis, the skeleton includes octahedral and tetrahedral
Two kinds of polyhedron cages, as shown in Figure 2 a and 2 b.
Embodiment 2 is a kind of to be based on amino functional YbIIIThe metal-organic framework material pair of six core molecule construction units
The catalysis of deacetalization-Knoevenagel condensation reactions
Method：With the preparation of embodiment 1 based on amino functional YbIIIThe metal organic frame of six core molecule construction units
Material is catalyzed as catalyst to deacetalization-Knoevenagel condensation reactions.
1) activation process of catalyst：Take and a certain amount of be based on amino functional YbIIIThe metal of six core molecule construction units
Organic framework materials, vacuumize and dry 24 hours under 298K heating conditions.
Method：Take after 100mg activation based on amino functional YbIIIThe metal of six core molecule construction units has machine frame
Frame material, 2.0mmol benzaldehyde dimethyl acetal, 2.1mmol malononitrile, 2mL dimethyl sulfoxide (DMSO)s to 10mL reaction tube in,
N is passed through under conditions of stirring2, temperature is 50 DEG C, reaction time 24h.Experimental result is detected with proton nmr spectra.
During the reaction is carried out, amino functional Yb should be based onIIIThe metal of six core molecule construction units has machine frame
Frame material to the experimental result of the catalytic performance of deacetalization-Knoevenagel condensation reactions as shown in figure 4, with
The progress of reaction, the yield of the reaction gradually increase, and when reaction proceeds to 24 hours, the conversion ratio of the reaction has reached
It is up to 97%.
2) in Deacetalization-Knoevenagel condensation reactions catalyst recyclable recycling property
The recovery of catalyst：After reaction terminates, filtering, catalyst is separated with reactant mixture, washed with methanol, then
Soak 4 hours, filter out in methanol, dry.
The concrete operations of circulation experiment：Contracted using the catalyst deacetalization-Knoevenagel of recovery
Reaction is closed, reacts 24h at 50 DEG C.
As shown in Figure 5 and Figure 6, circulation experiment proceeds to the 4th wheel to experimental result, and the activity of catalyst does not still decline.
Illustrate that this is based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units is as catalysis
The catalyst reusable edible of deacetalization-Knoevenagel condensation reactions.
Claims (8)
1. one kind is based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units, it is characterised in that institute
State based on amino functional YbIIIThe molecular formula of the metal-organic framework material of six core molecule construction units is [(CH3)2NH2]
[Yb6(μ3-OH)8(BDC-NH2)6(H2O)]·(solv)X, its crystal belongs to cubic system, space group Fm-3m, is by [Yb6
(μ3-OH)8(O2C-)12] node is used as, by part BDC-NH2The three-dimensional structure that bridging forms, include octahedral and tetrahedral two
Kind polyhedron cage.
2. one kind described in claim 1 is based on amino functional YbIIIThe metal-organic framework material of six core molecule construction units
Preparation method, it is characterised in that comprise the following steps：
1) by 2- amino terephthalic acid (TPA), Yb (NO3)3, o-fluorobenzoic acid and DMF be added in container, in
Stirring and dissolving under normal temperature, a small amount of nitric acid and water are added, is stirred；
2) it is put into after container is sealed in baking oven, is heated under 373-383K, is kept for 3 days；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal；Washed, filtered with DMF, dried, obtain
Target product.
3. preparation method according to claim 2, it is characterised in that：In step 1), in molar ratio, 2- amino terephthaldehydes
Acid:Yb(NO3)3=1:0.8-1.5.
4. preparation method according to claim 2, it is characterised in that：In step 1), by volume, N, N- dimethyl formyls
Amine:HNO3=10-15:1.
5. preparation method according to claim 2, it is characterised in that：In step 2), it is put into after container is sealed in baking oven,
Heating rate is 10Kmin-1。
6. preparation method according to claim 2, it is characterised in that：It is described to be slowly cooled to room temperature in step 3)
Rate of temperature fall is 10Kmin-1。
7. described in claim any one of 1-6 based on amino functional YbIIIThe metal organic frame of six core molecule construction units
Application of the material in deacetalization-Knoevenagel condensation reactions are catalyzed.
8. application according to claim 7, it is characterised in that method is as follows：Take benzaldehyde dimethyl acetal, malononitrile, two
Methyl sulfoxide and catalyst are passed through N in reaction tube under conditions of stirring2, react 24h under conditions of 50 DEG C；Described
Catalyst is based on amino functional Yb described in claim any one of 1-6IIIThe metal of six core molecule construction units has machine frame
Frame material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722488A (en) * | 2018-05-04 | 2018-11-02 | 江苏师范大学 | A kind of bimetallic center metal-organic framework materials and preparation method thereof of enhancing lewis acidity |
| CN109054043A (en) * | 2018-09-19 | 2018-12-21 | 辽宁大学 | Six core rare earth cluster metal-organic framework materials based on Y (III) and its preparation method and application |
| CN110092734A (en) * | 2019-05-22 | 2019-08-06 | 华侨大学 | A kind of 2-(phenylmethylene) malononitrile or derivatives thereof series connection synthetic method |
| CN111001442A (en) * | 2019-12-19 | 2020-04-14 | 辽宁大学 | Metal organic framework MIL-101(Cr) loaded chitosan material and preparation method and application thereof |
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| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
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| CN106397797A (en) * | 2016-08-29 | 2017-02-15 | 山东师范大学 | Gold-MOFs-polymer composite membrane, and production method and application thereof |
| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
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|---|---|---|---|---|
| CN108722488A (en) * | 2018-05-04 | 2018-11-02 | 江苏师范大学 | A kind of bimetallic center metal-organic framework materials and preparation method thereof of enhancing lewis acidity |
| CN108722488B (en) * | 2018-05-04 | 2021-02-12 | 江苏师范大学 | Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof |
| CN109054043A (en) * | 2018-09-19 | 2018-12-21 | 辽宁大学 | Six core rare earth cluster metal-organic framework materials based on Y (III) and its preparation method and application |
| CN109054043B (en) * | 2018-09-19 | 2021-10-01 | 辽宁大学 | Y (III) -based hexanuclear rare earth cluster metal organic framework material and preparation method and application thereof |
| CN110092734A (en) * | 2019-05-22 | 2019-08-06 | 华侨大学 | A kind of 2-(phenylmethylene) malononitrile or derivatives thereof series connection synthetic method |
| CN110092734B (en) * | 2019-05-22 | 2021-12-31 | 华侨大学 | Tandem synthesis method of 2- (phenylmethylene) malononitrile or derivatives thereof |
| CN111001442A (en) * | 2019-12-19 | 2020-04-14 | 辽宁大学 | Metal organic framework MIL-101(Cr) loaded chitosan material and preparation method and application thereof |
| CN111001442B (en) * | 2019-12-19 | 2023-01-17 | 辽宁大学 | Metal organic framework MIL-101 (Cr) loaded chitosan material and preparation method and application thereof |
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