CN106748994A - Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application - Google Patents
Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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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
- 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
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—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
Abstract
Yb is based on the present invention relates to one kindIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application.The technical scheme of use：By Yb (NO3)3, part 5, the substitution of 5'(4 carboxyl pyridines base 2,5 two) and 1,3 phthalic acids, solvent is N, and N dimethylformamides add water, add in high temperature resistant spiral mouth vial, in stirring 30 minutes under normal temperature；It is put into baking oven after container is sealed, in holding 4 days under temperature 378K；It is slowly cooled to room temperature, obtains water white transparency bulk crystals；With N, the washing of N dimethylformamides, filtering, drying obtain target product.Prepared by the present invention based on YbIIIFive core rare earth clusters metal-organic framework material preparation method it is simple, and carbon dioxide cycloaddition reaction to epoxides shows good size selectivity catalytic performance.
Description
Technical field
Yb is based on the present invention relates to one kindIIIFive core molecule construction units metal-organic framework material, specifically
Say, be related to a kind of carbon dioxide cycloaddition reaction to epoxides show size selection catalysis activity with cage modle vestibule
Metal-organic framework material preparation and its application.
Background technology
Metal-organic framework materials (MOFs) are a hot research in current Coordinative Chemistry and material science research
Field.The structure of MOFs have superior designability and it is convenient after modified, can facilitate adjustment aperture size and
Control the species of active function groups so that MOFs plays important role in catalyticing research field.Multi-nuclear metal cluster compound is
Through as Disciplinary Frontiers of greatest concern at present, because it can develop into nano-scale, synthesizing a series of electronics, optics
, magnetics and the new function material of catalysis have great application prospect.But current research is most to concentrate
On multinuclear transition metal cluster compound, the research of multi-kernel rare-earth cluster compound is started late.In recent years, some discrete four cores, five
Core, six cores, seven cores, eight cores, nine cores, ten cores, 12 cores, 15 cores etc. are synthesized in succession.The Long Lasheng religions of Xiamen University
Award using threonine part, synthesized four 60 core rare earth cluster compounds of chirality, this is also the check figure highest having now been found that
Rare earth cluster compound.In recent years, with the fast development of multi-kernel rare-earth cluster compound aspect research, using rare earth cluster as molecular structure list
First complex functionality rare earth cluster metal organic frame, due to its unique structure, abundant hole and offunctional site draw
The attention of chemist and material scholar is played, the focus as research.
In recent years, the fixation of carbon dioxide causes the extensive concern of countries in the world researcher.On the one hand it is as cheap
Carbon resource-carbon dioxide can be used to prepare various additional chemical products high in organic synthesis；Another reason is
In the protection to environment, carbon dioxide is one of the predominant gas for causing greenhouse effects.The ring of carbon dioxide and epoxides adds
It is one of successful example of carbon dioxide fixation into reaction.Its product be cyclic carbonate be medicine with fine chemistry industry it is important in
The polar solvent of mesosome, the presoma of makrolon, or aprotic, so being synthesized using carbon dioxide and epoxides
Cyclic carbonate is constantly subjected to extensive concern.
The content of the invention
The purpose of the present invention is using 5,5'- (substitutions of 4- carboxy-pyrid bases-the 2,5- two) -1,3- benzene containing pyridine radicals
Diacid (H5DDIA) as organic ligand, by adjusting synthesis condition, a kind of new base is constructed out using the method for solvent heat
In YbIIIFive core molecule construction units metal-organic framework material, and study it as Lewis acid catalysts to titanium dioxide
The catalytic performance of carbocyclic ring addition reaction.
The technical solution adopted by the present invention is：One kind is based on YbIIIFive core molecule construction units metal organic frame material
Material, including following synthesis step：
1) by 5,5'- (substitutions of 4- carboxy-pyrid bases -2,5- two) -1,3- phthalic acids (H5DDIA)、Yb(NO3)3, N, N- bis-
NMF, in adding container, under normal temperature, stirring and dissolving；
2) deionized water is added, is stirred, be put into baking oven after container is sealed, in holding 4-5 days under 373-383K,
Heating rate is 10Kmin-1；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains white chunks crystal；Preferably, it is slowly cooled to room temperature
Rate of temperature fall be 10Kmin-1, and at least 24 hours are stood at room temperature.Washed with DMF, filtered, done
It is dry, obtain target product.
It is above-mentioned based on YbIIIFive core molecule construction units metal-organic framework material, in molar ratio, 5,5'- (4-
The substitutions of carboxy-pyrid base -2,5- two) -1,3- phthalic acids (H5DDIA):Yb(NO3)3=1:1.0-1.5.
It is of the invention based on YbIIIFive core molecule construction units metal-organic framework material, containing abundant in structure
Unsaturated Yb (III) center, can carry out catalytic applications as Lewis acid catalysts to carbon dioxide cycloaddition reaction.Method is such as
Under：Epoxides and catalyst are taken in container, co-catalyst is added or be added without, under conditions of stirring, CO is passed through2Gas
Body, reacts 3-6h under high pressure；Described catalyst is above-mentioned based on YbIIIFive core molecule construction units metal it is organic
Frame material.Reaction equation is as follows：
Described epoxides be expoxy propane, epoxy butane, allyl glycidyl ether, n-butyl glycidyl ether or
Styrene oxide.
The consumption of described catalyst, is in molar ratio the 0.03-0.05% of epoxides
Described co-catalyst is TBAB (TBAB).
Described is passed through CO2Gas, makes pressure reach 1.0Mpa, and temperature is to react 3-6h under 363-413K.
The beneficial effects of the invention are as follows：Prepared by the present invention based on YbIIIFive core molecule construction units metal it is organic
Yb (III) ion in frame material is seven coordinations or eight-coordinate, so containing abundant undersaturated Yb (III) in structure
Center, can make the complex of invention can be as a kind of Lewis acid catalysts, to the dioxy of epoxides as Lewis acid site
Change carbocyclic ring addition reaction and show good catalytic performance.Again because the present invention prepared by based on YbIIIFive core molecule structures
Vestibule containing cage modle in the structure of the metal-organic framework material of unit, when catalytic reaction is carried out, on the vestibule of cage modle
" window " has interception effect to larger-size reactant, therefore complex of the invention shows the titanium dioxide to epoxides
The good size selectivity catalytic performance of carbocyclic ring addition reaction.Synthetic method is simple, with application prospect.
Brief description of the drawings
Fig. 1 a are the core Yb cluster molecule construction units of trigonal biyramid type five in metal-organic framework material structure of the present invention.
Fig. 1 b are the coordination environments of Yb (III) ion in metal-organic framework material structure of the present invention.
Fig. 2 a are H in metal-organic framework material structure of the present invention5A kind of coordination mode of DDIA parts.
Fig. 2 b are H in metal-organic framework material structure of the present invention5Another coordination mode of DDIA parts.
Fig. 3 is each molecular structure unit [Yb in metal-organic framework material structure of the present invention5(μ3-OH)6(O2C-)8] letter
Double cap triangular prism cylinder building blocks of chemical conversion.
Fig. 4 is the three-dimensional apertures cavity configuration simplification figure of metal-organic framework material of the present invention.
Fig. 5 is the structural representation of cage modle vestibule configuration in metal-organic framework material structure of the present invention.
Fig. 6 is that the carbon dioxide that the differential responses time is catalyzed to metal-organic framework material of the present invention and expoxy propane ring add
Into the influence of reaction.
Fig. 7 is that metal organic frame financial resources of the present invention carry out the catalysis activity that five wheels circulate catalytic reaction.
Specific embodiment
Embodiment 1 is a kind of to be based on YbIIIFive core molecule construction units metal-organic framework material
By H5DDIA (0.012g, 0.025mmol) and Yb (NO3)3·5H2O (0.015g, 0.03mmol) is added to volume
In the high temperature resistant spiral mouth vial of 5mL, to add 1.5mL DMF, dissolved in normal temperature condition stirring, added 1.5ml
H2O, up to slaine, all dissolving is well mixed with part within 20 minutes for stirring, is put into after vial is sealed in 378K baking ovens,
Heating rate is 10Kmin-1, heat 4 days at such a temperature, with 10Kmin-1Rate of temperature fall be slowly cooled to room temperature, have
Colourless bulk crystals generation, is washed with DMF, is filtered, and is dried, and obtains target product, i.e., based on YbIIIFive core molecule construction units
Metal-organic framework material, yield is 50%.
The present invention synthesis based on YbIIIThe metal-organic framework material of five core molecule construction units be one by containing
The pentacarboxylic acid part H of pyridine groups5Five cores Yb cluster molecules construction unit (Fig. 1 a) of DDIA and trigonal biyramid type be built into three
The porous metals organic frame of dimension.Five core Yb clusters [Yb in structure5(μ3-OH)6(O2C-)8], it is have a kind of eight as shown in Figure 1 b
The molecular structure unit of connection.Three kinds of different Yb are included in each five core Yb oxygen cluster3+Center, one of Yb1 and two
Yb3 ions are located on the equatorial plane of trigonal biyramid, and also two Yb2 ions occupy the axial vertex position of trigonal biyramid.
Yb1 and Yb3 are eight-coordinates, and Yb1 is and four μ3- OH groups and four oxygen atom ligands, wherein four oxygen atoms come respectively
From in four carboxyls of independent L1 parts；Yb3 and four μ 3-OH group and four oxygen atom ligands, two of which oxygen atom
Come from two hydrones of coordination, two oxygen atoms come from two carboxyls of independent L1 parts.The coordination of Yb1 and Yb3
Pattern is presented a kind of anti-cubic prism geometric configuration, wherein a plane of anti-four directions prism is by from four independent L1 parts
Four carboxyl oxygen atoms (Yb1), or by two oxygen atoms and two oxygen atoms of hydrone on two independent L1 parts
Constitute (Yb3)；Another plane is then by four μ3The oxygen atom composition of-OH.Yb2 and three μ3- OH oxygen atoms, three independences
The carboxyl oxygen atom of L1 parts and an oxygen atom for water of coordination form seven and are coordinated, and show single cap octahedral coordination geometry structure
Type.In the structure of metal organic frame, two kinds of connection modes are showed respectively between DDIA parts and Yb (III) ion, such as
Fig. 2 a and 2b.
Yb should be based onIIIFive core molecule construction units metal-organic framework material, by the Carboxylic acid ligand containing pyridine groups
Construct and form, its crystal belongs to tetragonal crystal system, space group is I41/amd。
Embodiment 2 is a kind of to be based on YbIIIFive core molecule construction units metal-organic framework material to the two of epoxides
The catalysis of carbonoxide cycloaddition reaction
Method：With the preparation of embodiment 1 based on YbIIIFive core molecule construction units metal-organic framework material conduct
Catalyst is catalyzed to the cycloaddition reaction of carbon dioxide and epoxides.
The activation process of catalyst：Take a certain amount of based on YbIIIFive core molecule construction units metal organic frame material
Material, vacuumizes under 323K heating conditions and dries 24 hours.
1) influence of differential responses time
Method：Take after the activation of 37.2mg (0.02mmol, 0.04mol%) based on YbIIIFive core molecule construction units
Metal-organic framework material, the expoxy propane of the TBAB and 50mmol of 0.075mmol is added in autoclave, is sealed,
It is passed through CO2Gas makes container inner pressure for 1.0Mpa, and temperature is 393K, and the reaction time is respectively 3h, 4h, 5h and 6h, is produced
Thing propene carbonate.Experimental result gas chromatographic detection.
Under the differential responses time, Yb should be based onIIIFive core molecule construction units metal-organic framework material to dioxy
Change the catalytic performance of the cycloaddition reaction of carbon and expoxy propane.Experimental result as shown in fig. 6, reaction is when carry out 5 hours,
The conversion ratio of expoxy propane has reached 87.2% (TOF:93.8h-1), even if reaction is carried out 6 hours, conversion ratio is also there is no bright
Aobvious increase, so the reaction time of 5 hours is the maximized optimal selection of products collection efficiency.
Product propene carbonate core：1H-NMR(400MHz,TMS,CDCl3):δ=4.84 (m, 1H, OCH), 4.53 (t, 1H,
=8.3Hz, OCH2), 3.98 (dd, 1H, J=7.8,7.9Hz, OCH2), 1.51 (d, 3H, J=6.3Hz, CH3)ppm.13C-NMR
(100MHz,CDCl3,TMS):δ=155.4 (- OC (O) O-), 74.6 (>CH–O–),70.6(–CH2–O–),19.1(–CH3)
ppm.
2) influence of catalyst amount
Method：By table 1, take after activation based on YbIIIFive core molecule construction units metal-organic framework material,
The expoxy propane of the TBAB and 50mmol of 0.075mmol is added in autoclave, sealing, is passed through CO2Gas makes in container
Pressure is 1.0Mpa, and temperature is 393K, reacts 5h；In molar ratio, the addition of catalyst is the 0.03mol% of expoxy propane,
0.04mol% and 0.05mol%.Experimental result gas chromatographic detection.Result such as table 1.
Table 1
| The amount of catalyst | 0.03mol% | 0.04mol% | 0.05mol% |
| The conversion ratio % of expoxy propane | 82.2 | 87.2 | 83.5 |
| TON | 548 | 436 | 334 |
| TOF(h-1) | 109.1 | 87.2 | 66.8 |
From table 1, when the amount of catalyst is 0.04mol%, the conversion ratio of epoxidation reaction is maximum, and is higher than
During 0.04mol%, conversion ratio is not improved and declined on the contrary, therefore the catalyst participation catalytic reaction of selection 0.04mol% is optimal
Selection.
3) influence of co-catalyst
Method：Take activation after based on YbIIIFive core molecule construction units metal-organic framework material, such as table 2 adds
Catalyst and co-catalyst, the expoxy propane of 50mmol are added in autoclave, sealing, are passed through CO2Gas makes in container
Pressure is 1.0Mpa, and temperature is 393K, reacts 5h.Experimental result gas chromatographic detection.Result such as table 2.
Table 2
| The amount of catalyst | 0 | 37.2mg (0.04mol%) | 37.2mg (0.04mol%) |
| The amount of co-catalyst | 0.075mmol | 0 | 0.075mmol |
| The conversion ratio % of expoxy propane | 17.2 | 9.9 | 87.2 |
| TON | — | 49.5 | 436 |
| TOF(h-1) | — | 9.9 | 87.2 |
From table 2, individually based on YbIIIFive core molecule construction units metal-organic framework material or TBAB pairs
The catalytic effect of the reaction is all very low, and two kinds of materials add while existing just show to carbon dioxide and epoxides ring
Into the good catalytic performance of reaction.
4) different epoxides
Method：Take after the activation of 37.2mg (0.04mol%) based on YbIIIThe metal of five core molecule construction units have
Machine frame frame material, the TBAB and 50mmol of 0.075mmol such as the epoxides of table 3, sealing is passed through CO2Gas makes in container
Pressure is 1.0Mpa, and temperature is 393K, reacts 5h.Experimental result gas chromatographic detection.Result such as table 3.
Table 3
As shown in table 3, based on YbIIIFive core molecule construction units metal-organic framework material to different epoxides
Cycloaddition reaction catalytic reaction, with the increase of epoxides size, conversion ratio is gradually reduced.This is due to of the invention
Based on YbIIIFive core molecule construction units metal-organic framework material structure in there is cage modle vestibule, can permit on vestibule
Perhaps reactant is limited into " window " size contacted with Lewis acid catalysis point, so being got over than the conversion ratio of larger reactant
It is low.Therefore, it is of the invention based on YbIIIFive core molecule construction units metal-organic framework material to carbon dioxide and epoxy
The cycloaddition reaction of compound shows size selectivity catalytic performance.
5) in cycloaddition reaction catalyst recyclable recycling property
The recovery of catalyst：After reaction terminates, filtering separates catalyst with reactant mixture, with methyl alcohol and dichloromethane
Alkane is washed, then is soaked six hours in methyl alcohol, is leached, and is dried.
The concrete operations of circulation experiment：Using the catalyst (0.04mol%) and co-catalyst TBAB that reclaim
(0.075mmol) is catalyzed the cycloaddition reaction of carbon dioxide and expoxy propane (50mmol), and 5h is reacted under 393K.
Experimental result as shown in fig. 7, circulation experiment proceed to the 5th wheel, catalyst activity still do not decline.Illustrate this
Based on YbIIIFive core molecule construction units metal-organic framework material as carbon dioxide and epoxides cycloaddition reaction
Catalyst reusable edible.
Claims (10)
1. it is a kind of to be based on YbIIIFive core molecule construction units metal-organic framework material, it is characterised in that preparation method bag
Include following steps：
1) by 5,5'- (substitutions of 4- carboxy-pyrid bases -2,5- two) -1,3- phthalic acids, Yb (NO3)3And N,N-dimethylformamide
It is added in container, in stirring and dissolving under normal temperature；
2) water is added, is stirred, be put into baking oven after container is sealed, in being heated under 373-383K, kept for 4-5 days；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal；Washed with DMF, filtered, dried, obtained
Target product.
2. according to claim 1 based on YbIIIFive core molecule construction units metal-organic framework material, its feature
It is：Step 1) in, in molar ratio, 5,5'- (4- carboxy-pyrids base -2, the substitutions of 5- bis-) -1,3- phthalic acids:Yb(NO3)3=1:
1.0-1.5。
3. according to claim 1 based on YbIIIFive core molecule construction units metal-organic framework material, its feature
It is：Step 2) in, it is put into baking oven after container is sealed, heating rate is 10Kmin-1。
4. according to claim 1 based on YbIIIFive core molecule construction units metal-organic framework material, its feature
It is：Step 3) in, the described rate of temperature fall being slowly cooled to room temperature is 10Kmin-1。
5. described in any one of claim 1-4 based on YbIIIThe metal-organic framework material of five core molecule construction units urging
Change CO2Application in gas and epoxides cycloaddition reaction.
6. application according to claim 5, it is characterised in that method is as follows：Epoxides and catalyst are taken in container,
Co-catalyst is added or be added without, under conditions of stirring, CO is passed through2Gas, reacts 3-6h under conditions of high pressure；Described
Catalyst is based on Yb described in claim any one of 1-4IIIFive core molecule construction units metal-organic framework material.
7. application according to claim 6, it is characterised in that：Described epoxides is expoxy propane, epoxy butane, alkene
Propyl glycidyl ether, n-butyl glycidyl ether or styrene oxide.
8. application according to claim 6, it is characterised in that：Described catalyst amount is in molar ratio epoxides
0.03-0.05%.
9. application according to claim 6, it is characterised in that：Described co-catalyst is TBAB.
10. application according to claim 6, it is characterised in that：It is passed through CO2Gas, makes pressure reach 1.0Mpa, and temperature is
3-6h is reacted under 363-413K.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710065864.5A CN106748994A (en) | 2017-02-06 | 2017-02-06 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
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| CN201710065864.5A CN106748994A (en) | 2017-02-06 | 2017-02-06 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
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| CN107501568A (en) * | 2017-09-06 | 2017-12-22 | 烟台智本知识产权运营管理有限公司 | The synthesis for the metal-organic framework material that tetrabasic carboxylic acid corproporphyrin part is constructed |
| CN107739444A (en) * | 2017-11-15 | 2018-02-27 | 辽宁大学 | Based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application |
| CN111393460A (en) * | 2020-04-20 | 2020-07-10 | 鲁东大学 | Zinc coordination compound of flavone derivative and preparation method and application thereof |
| CN114854036A (en) * | 2022-06-06 | 2022-08-05 | 安徽农业大学 | Metal organic framework material and preparation method thereof |
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| WO2004101575A2 (en) * | 2003-05-09 | 2004-11-25 | The Regents Of The University Of Michigan | Implementation of a strategy for achieving extraordinary levels of surface and porosity in crystals |
| WO2015030617A2 (en) * | 2013-09-02 | 2015-03-05 | Uniwersytet Jagielloński | New MOF-type layered coordination polymers of manganese, method of their preparation, modification and use thereof |
| CN105399602A (en) * | 2015-10-27 | 2016-03-16 | 辽宁大学 | V-shaped rigid bidentate carboxylic acid ligand, and preparation method and application thereof |
| CN105732487A (en) * | 2016-01-28 | 2016-07-06 | 辽宁大学 | Pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and preparation method and application thereof |
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| WO2004101575A2 (en) * | 2003-05-09 | 2004-11-25 | The Regents Of The University Of Michigan | Implementation of a strategy for achieving extraordinary levels of surface and porosity in crystals |
| WO2015030617A2 (en) * | 2013-09-02 | 2015-03-05 | Uniwersytet Jagielloński | New MOF-type layered coordination polymers of manganese, method of their preparation, modification and use thereof |
| CN105399602A (en) * | 2015-10-27 | 2016-03-16 | 辽宁大学 | V-shaped rigid bidentate carboxylic acid ligand, and preparation method and application thereof |
| CN105732487A (en) * | 2016-01-28 | 2016-07-06 | 辽宁大学 | Pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and preparation method and application thereof |
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| CN107501568A (en) * | 2017-09-06 | 2017-12-22 | 烟台智本知识产权运营管理有限公司 | The synthesis for the metal-organic framework material that tetrabasic carboxylic acid corproporphyrin part is constructed |
| CN107739444A (en) * | 2017-11-15 | 2018-02-27 | 辽宁大学 | Based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application |
| CN107739444B (en) * | 2017-11-15 | 2020-05-12 | 辽宁大学 | Based on amino functionalization of YbIIIMetal organic framework material with hexanuclear molecular structural unit and preparation method and application thereof |
| CN111393460A (en) * | 2020-04-20 | 2020-07-10 | 鲁东大学 | Zinc coordination compound of flavone derivative and preparation method and application thereof |
| CN111393460B (en) * | 2020-04-20 | 2023-01-17 | 鲁东大学 | Zinc coordination compound of flavone derivative and preparation method and application thereof |
| CN114854036A (en) * | 2022-06-06 | 2022-08-05 | 安徽农业大学 | Metal organic framework material and preparation method thereof |
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