CN107413385A - A kind of micropore thulium coordination polymer is as heterogeneous catalysis material and preparation method - Google Patents
A kind of micropore thulium coordination polymer is as heterogeneous catalysis material and preparation method Download PDFInfo
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Abstract
It is as heterogeneous catalysis material, its skeleton symbol the invention discloses a kind of micropore thulium coordination polymer：[Tm2(pdc)3] n, wherein containing 3,5 pyridinedicarboxylic acid parts, whole molecular skeleton shows size for 6.3 × 8.52Regular pore space structure, the pyridine groups not being coordinated are distributed in the surrounding of hole, and point to duct center.Its preparation method：By 3,5 pyridinedicarboxylic acid parts（Abbreviation H2pdc）And TmCl3·6H2O adds N, N dimethylformamides（DMF）In solution, mixed liquor is placed in pressure-resistant sleeve pipe afterwards, it is closed after 130 °C in oil bath are heated 24 hours, naturally cool to room temperature, yellow crystals are obtained, then obtained crystal is taken out 24 hours for lower 150 °C in vacuum, obtain a kind of novel microporous thulium coordination polymer [Tm2(pdc)3]n.The present invention provide micropore thulium coordination polymer be used as heterogeneous catalysis, have the characteristics that react reappear, course of reaction be simple and convenient to operate it is high with yield.
Description
Technical field
The present invention relates to group of the lanthanides microporous coordination polymer as heterogeneous catalysis field, and in particular to a kind of micropore thulium is matched somebody with somebody
Position polymer is as heterogeneous catalysis material and preparation method.In the reaction, in micropore thulium coordination polymer Lewis acid and
Lewis base catalysis site shows preferable concerted catalysis and size selectivity catalytic effect.
Background technology
Microporous coordination polymer（PCPs）Also referred to as metal-organic framework material（MOFs）, structure is similar to natural zeolite, because
It has larger specific surface area, very high porosity, the skeleton structure of stiff stability and the functionalization in duct, so PCPs exists
The fields such as absorption, separation, magnetic, optics and catalysis have preferable application prospect, are widely studied in recent years.Micropore is matched somebody with somebody
Position polymer is typically formed by organic ligand with central metallic ions by self assembly.Because organic ligand species is very more, gold
It is also very extensive to belong to ion selection, therefore the microporous coordination polymer of substantial amounts can be prepared.
Microporous coordination polymer is in self assembling process, temperature, solvent, ratio, the pH value of organic ligand and metal ion
There is large effect to the structure of polymer Deng reaction condition.Reasonable selection reaction condition, structure novelty, work(can be prepared
The peculiar PCPs of energy.
Aperture, shape, skeleton art, Spatial Dimension and the chemical environment of microporous coordination polymer can be by selections
Heart metal ion and organic ligand and connected mode between them and carry out accuracy controlling.These features are micropore polycomplexation
Compound provides sufficient condition as heterogeneous catalysis.
Microporous coordination polymer is similar to molecular sieve structure, it is allowed to which guest molecule spreads in its duct, can adsorb, be living
Change guest molecule, the distribution of the transition state and then influence product reacted in duct can be influenceed, it is functional to possess catalyst institute.
Microporous coordination polymer is as three key elements of heterogeneous catalysis：Unsatuated metal center, organic functions active sites
Point, hole.Therefore, microporous coordination polymer catalyst can be divided into three classes by structural element：The first kind is unsatuated metal center
As Lewis acid activities center；In second class organic ligand active function groups directly as catalytic reaction activated centre, or
Moditied processing after being carried out to it, introduce new active function groups center；3rd class be using PCPs surface or cavity as carrier,
Avtive spot is loaded in PCPs surface or duct using physico-chemical processes such as absorption, dipping or precipitations, reaction is existed
Carried out in PCPs surface or duct.
Recent studies indicate that the organic reaction type that microporous coordination polymer can be catalyzed as heterogeneous catalysis
Widely, catalyst is easy to separate from reaction system so that reaction system is simple to operation, green.More attach most importance to
What is wanted is such catalyst so that the reaction of catalysis shows the size and shape selective catalysis effect to substrate.Therefore, this
A little researchs are expected to provide important application support in field of catalytic chemistry and green chemical industry field for microporous coordination polymer material.
The content of the invention
Under the background of the studies above, it is an object of the invention to provide a kind of micropore thulium coordination polymer to urge as heterogeneous
Change material and preparation method, solve micropore thulium coordination polymer emphatically in deacetalization-Knoevenagel reactions
The concerted catalysis of difunctional and the size and shape selective catalysis problem to substrate.
The purpose of the present invention can be adopted the following technical scheme that to realize：
A kind of micropore thulium coordination polymer is as heterogeneous catalysis material, wherein contain 3,5- pyridinedicarboxylic acid parts, polymer
Skeleton symbol is：[Tm2(pdc)3] n, Tm3+For 7 coordinations, be it is a kind of be coordinated unsaturated lanthanide ion, its center thulium ion and 7
O atom is coordinated, and shows five jiaos of double centrum geometric configurations.In the O atom that seven are directly coordinated with thulium ion, there are six O originals
For son respectively from six different 3,5- pyridinedicarboxylic acid parts, one comes from DMF solvent molecule.Along crystalaDirection of principal axis, it is whole
Individual molecular skeleton shows size for 6.3 × 8.52Regular pore space structure, the pyridine groups not being coordinated are distributed in hole
Surrounding, and point to duct center.
The pyridine groups not being coordinated in described hole can be used as Lewis basic actives site, Tm3+Coordination can be used as unsaturated
Lewis acid activities site.
Obtained material belongs to cubic system, and space group isPnma, cell parameter isa=8.4777 (11),b =
28.486 (4),c=15.690 (2),α = β = γ=90 °,V = 3789.1(9) Å3。
The Tm of 7 coordination3+It is a kind of unsaturated ion of coordination in catalytic reaction process, Lewis acid catalysis can be used as
Site.
A kind of micropore thulium coordination polymer heterogeneous catalysis material preparation method：Under condition of no solvent, by 1 ~ 3% mole
Micropore thulium coordination polymer adds the benzaldehyde diformazan acetal and malononitrile of respective amount, stirring reaction, is tracked with thin-layer chromatography
Reaction process.After reaction is complete, a certain amount of ethanol solution is added, solid catalyst, filtrate decompression evaporation are filtered after stirring
Obtain crude product.Crude product is carried out in solution of the ethanol to water again to be recrystallized to give the corresponding preferable product of purity.Catalysis
Agent is reused after ethyl acetate is washed, is dried in vacuo, and can at least circulate 4 catalytic reactions.
A kind of affiliated micropore thulium coordination polymer heterogeneous catalysis method：In deacetalization-Knoevenagel
In reaction, the micropore thulium coordination polymer reacts as bifunctional catalysis' agent, in two stages concerted catalysis, and acetal took off before this
Protection generates corresponding aldehyde and carries out the corresponding product of dehydration generation again.In the reaction, catalyst shows the size to substrate
With shape selective catalytic action.
The invention has the advantages that：
The present invention provide micropore thulium coordination polymer be used as heterogeneous catalysis, have reaction favorable reproducibility, course of reaction simply,
The features such as easy to operate and yield is high.The catalyst shows concerted catalysis and size, shape selective catalytic action.Simultaneously should
Catalyst is environment-friendly, reusable heterogeneous catalysis material, is expected to provide a kind of green catalysis material, is promoted
The development of Green Chemistry.
Brief description of the drawings
Fig. 1 is the coordination contour of micropore thulium coordination polymer prepared by example 1.
Fig. 2 is the pore space structure of micropore thulium coordination polymer prepared by example 1.
Fig. 3 is micropore thulium coordination polymer thermal analysis curue prepared by example 1.
Fig. 4 is micropore thulium coordination polymer powder diagram prepared by example 1.
In Fig. 4：A, the powder diagram of monocrystalline simulation, b, the powder diagram of measuring, powder after c, vacuum activating
Last diffraction pattern, d, catalytic reaction once after powder diagram, after e catalytic cycles 4 times
Powder diagram.
Instantiation mode
The specific embodiment of the present invention is described with reference to the drawings：
Such as Fig. 1, shown in Fig. 2：Described micropore thulium polymer is as heterogeneous catalysis material, wherein contain 3,5- pyridinedicarboxylic acids
Part, polymer architecture skeleton symbol are：[Tm2(pdc)3] n, Tm3+It is coordinated for 7, shows five jiaos of double centrum geometric configurations of distortion.
In the O atom that seven are directly coordinated with thulium ion, there are six O atoms to match somebody with somebody respectively from six different 3,5- pyridinedicarboxylic acids
Body, one comes from DMF solvent molecule.Along crystalaDirection of principal axis, whole molecular skeleton show size for 6.3 × 8.52
Regular pore space structure, the pyridine groups not being coordinated are distributed in the surrounding of hole, and point to duct center.
The pyridine groups being coordinated in the non-hole can be used as Lewis basic actives site, Tm3+Coordination can be used as unsaturated
Lewis acid activities site.Obtained material belongs to cubic system, and space group isPnma, cell parameter isa = 8.4777
(11),b=28.486 (4),c=15.690 (2),α = β=γ=90 °,V = 3789.1(9) Å3.It is described
The Tm of 7 coordinations3+It is a kind of unsaturated ion of coordination in catalytic reaction process, Lewis acid catalysis site can be used as.It is anti-in catalysis
During answering, Lewis basic sites and Lewis acid site can play concerted catalysis effect.In catalytic reaction process, because of hole
The size confinement effect in hole so that the reaction of catalysis shows the size and shape selective catalysis effect to substrate.This is non-
Phase catalyst can be basically unchanged in catalytic process with holding structure, can be recycled at least 4 times.
The specific embodiment of micropore thulium coordination polymer heterogeneous catalysis method of the present invention is as follows：
Embodiment 1：
By 1.0 mmol 3,5- pyridinedicarboxylic acid parts（168 milligrams）With 0.33 mmol TmCl3·6H2O（127 milligrams）Add
Enter in 10 mLDMF solution, be placed in mixed liquor in pressure-resistant sleeve pipe afterwards, it is closed to be heated 24 hours after 130 °C in oil bath
Afterwards, room temperature is naturally cooled to, obtains yellow crystals, then obtained crystal is taken out 24 hours for lower 150 °C in vacuum, is obtained a kind of new
Type micropore thulium coordination polymer（Structural formula：[Tb2(pdc)3]n）.
By the micropore thulium coordination polymer of corresponding 2% mole of aldehyde（10 milligrams）, 0.5 mmol benzaldehyde diformazan acetals
（76 milligrams）With 0.7 mmol malononitrile（47 milligrams）It is added in 15 mL round-bottomed flask, stirring reaction 12 hours, uses thin layer
Chromatogram tracking reaction process.After reaction is complete, 10mL ethanol solutions are added, stirring filters out solid catalyst after 5 minutes, will
Gained filtrate decompression evaporates to obtain crude product.Crude product is recrystallized in the solution of ethanol and water again, obtains product
76.3 milligrams, yield 99%.Product is through nmr analysis, its nuclear magnetic data：1H-NMR (CDCl3): 7.84 (d, J = 6.4
Hz, 2H), 7.71 (s, 1H), 7.57 (t, J=7.0 Hz, 1H), 7.48 (t, J=7.0 Hz, 2H) its
Shown in polymer thermal analysis curue 3.
The sign process of micropore thulium coordination polymer is as follows：
（1）The single crystal structure determination of micropore thulium coordination polymer
Choose good glue with sizeable crystal of quality to be placed on a glass fiber, spread out with Bruker SMART Apex II monocrystalline
Penetrate instrument and carry out single crystal structure determination：At 23 DEG C, using MoK a (λ=0.71073) ray is as light source, and graphite is as monochromatic
Device, detection panel are Bruker Smart CCD, are usedωScan mode is scanned to structure cell and determines and collect diffracted intensity number
According to its powder diagram is as shown in Figure 4.Structure cell essence is carried out to the data being collected using Bruker APEXII programs first
Repair, data absorption corrects and reduction；Then by the XS programs in SHELXTL softwares to the data direct method after reduction
Analytic structure, obtains the starting phase angle of all non-hydrogen atoms, and the refine of anisotropic parameters then passes through SHELXL-97 programs
Operation, using complete matrix least square method, until Data Convergence, is finally determined to non-hydrogen atom coordinate.On aromatic rings
The hydrogen being connected with carbon atom is added by theoretical calculation.Hydrogen atom on hydrone is obtained by difference Fourier synthetic method
To and be fixed on oxygen atom and carry out refine.Detailed crystal test parameter is shown in Table 1.
The crystallographic parameter of the micropore thulium polymer of table 1
Important selective bond distance and bond angle are shown in Table 2.
The selective bond distance of the micropore thulium coordination polymer of table 2 and bond angle
Symmetry operation：i-x+1/2, -y+1, z-1/2; ii -x+1, -y+1, -z+1; iiix+1/2, y, -z+1/2
（2）The elementary analysis test of micropore thulium coordination polymer
Micropore thulium coordination polymer carries out elementary analysis with the Flash EA-2000 elemental analysers of Italy's production, and test shows
C, the measured value of the element of N, H tri- and calculated value are close, and its test result data is as follows：It is C to molecular formula27H23N5O14Tm2
Thulium coordination polymer its theoretical value：C 33.11, H 2.37, N 7.15;Measured value：C 32.92, H 2.41, N
7.02。
Embodiment 2：
By the micropore thulium coordination polymer of corresponding 1% mole of aldehyde（5 milligrams）, 0.5 mmol benzaldehyde diformazan acetals（76 millis
Gram）With 0.7 mmol malononitrile（47 milligrams）It is added in 15 mL round-bottomed flask, stirring reaction 24 hours, uses thin-layer chromatography
Track reaction process.After reaction is complete, 10mL ethanol solutions are added, stirring filters out solid catalyst after 5 minutes, by gained
Filtrate decompression evaporates to obtain crude product.Crude product is recrystallized in the solution of ethanol and water again, obtains 76 milligrams of product,
Yield 99%.
Embodiment 3：
By the micropore thulium coordination polymer of corresponding 3% mole of aldehyde（15 milligrams）, 0.5 mmol benzaldehyde diformazan acetals（76 millis
Gram）With 0.7 mmol malononitrile（47 milligrams）It is added in 15 mL round-bottomed flask, stirring reaction 24 hours, uses thin-layer chromatography
Track reaction process.After reaction is complete, 10mL ethanol solutions are added, stirring filters out solid catalyst after 5 minutes, by gained
Filtrate decompression evaporates to obtain crude product.Crude product is recrystallized in the solution of ethanol and water again, obtains the milli of product 76.2
Gram, yield 99%.
Embodiment 4：
By the micropore thulium coordination polymer of corresponding 2% mole of aldehyde（10 milligrams）, 0.5 mmol p-bromobenzaldehyde diformazan acetals
（116 milligrams）With 0.7 mmol malononitrile（47 milligrams）It is added in 15 mL round-bottomed flask, stirring reaction 12 hours, use is thin
Layer chromatography tracks reaction process.After reaction is complete, 10mL ethanol solutions are added, stirring filters out solid catalyst after 5 minutes,
Gained filtrate decompression is evaporated to obtain crude product.Crude product is recrystallized in the solution of ethanol and water again, obtains product
117 milligrams, yield 99%.Product carries out nmr analysis, its data：1H-NMR (CDCl3):7.77 (d, J = 8.0 Hz,
2H), 7.70 (d, J = 4 Hz, 2H), 7.67 (s, 1H).
Embodiment 5
By the micropore thulium coordination polymer of corresponding 2% mole of aldehyde（10 milligrams）, 0.5 mmol paranitrobenzaldehydes dimethanol contracting
Aldehyde（97 milligrams）With 0.7 mmol malononitrile（47 milligrams）It is added in 15 mL round-bottomed flask, stirring reaction 12 hours, use is thin
Layer chromatography tracks reaction process.After reaction is complete, 10mL ethanol solutions are added, stirring filters out solid catalyst after 5 minutes,
Gained filtrate decompression is evaporated to obtain crude product.Crude product is recrystallized in the solution of ethanol and water again, obtains product
100 milligrams, yield 99%.Product carries out nmr analysis, its data：1H-NMR (CDCl3): 8.39 (d, J = 8.0 Hz,
2H), 8.07 (d, J = 8.0 Hz, 2H), 7.86 (s, 1H)。
Claims (6)
1. a kind of micropore thulium coordination polymer is as heterogeneous catalysis material, it is characterized in that：Its skeleton symbol is：[Tm2(pdc)3]
N, wherein contain 3,5- pyridinedicarboxylic acid parts, Tm3+It is coordinated for seven, five jiaos of double centrum geometric configurations of distortion is showed, seven
In the individual O atom being directly coordinated with thulium ion, there are six O atoms respectively from six different 3,5- pyridinedicarboxylic acid parts,
One comes from DMF solvent molecule, along crystalaDirection of principal axis, whole molecular skeleton show size for 6.3 × 8.52It is regular
Pore space structure, the pyridine groups not being coordinated are distributed in the surrounding of hole, and point to duct center.
2. micropore thulium coordination polymer according to claim 1 is as heterogeneous catalysis material, it is characterized in that：Described hole
In the pyridine groups that are not coordinated can be used as Lewis basic actives site, Tm3+It can be used as and be coordinated undersaturated Lewis acid activities position
Point.
3. micropore thulium coordination polymer according to claim 1 is as heterogeneous catalysis material, it is characterized in that：Obtained
Material belongs to cubic system, and space group isPnma, cell parameter isa=8.4777 (11),b=28.486 (4),c =
15.690 (2),α = β = γ=90 °,V = 3789.1(9) Å3。
4. micropore thulium coordination polymer according to claim 1 is as heterogeneous catalysis material, it is characterized in that：Described seven match somebody with somebody
The Tm of position3+It is a kind of unsaturated ion of coordination in catalytic reaction process, as Lewis acid catalysis site.
5. a kind of micropore thulium coordination polymer as claimed in claim 1 is as heterogeneous catalysis material preparation method, its feature
It is：By 3,5- pyridinedicarboxylic acid parts H2Pdc and TmCl3·6H2O adds N,N-dimethylformamide（DMF）In solution, afterwards will
Mixed liquor is placed in pressure-resistant sleeve pipe, closed after 130 °C in oil bath are heated 24 hours, is naturally cooled to room temperature, is obtained Huang
Color crystal, then obtained crystal is taken out 24 hours for lower 150 °C in vacuum, a kind of novel microporous thulium coordination polymer is obtained, it is tied
Structure formula is：[Tm2(pdc)3]n。
6. micropore thulium coordination polymer according to claim 5 is as heterogeneous catalysis material preparation method, it is characterized in that：
In deacetalization-Knoevenagel reactions, the micropore thulium coordination polymer divides as bifunctional catalysis' agent
Two stage concerted catalysis reactions, before this acetal deprotection generate corresponding aldehyde, then carry out dehydration and generate corresponding product；
In reaction, catalyst shows the size and shape selective catalysis effect to substrate.
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| 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 |
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| CN111905825B (en) * | 2020-08-19 | 2023-01-24 | 中原工学院 | Zinc coordination polymer catalytic material and preparation method and application thereof |
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