CN105732487B - A kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application - Google Patents
A kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application Download PDFInfo
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
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- 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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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- 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
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- 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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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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- 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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- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The present invention relates to a kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application.The technical solution of use is：By Yb (NO3)3, ligand 5,5'(pyridine radicals 2,5 two substitute) 1,3 phthalic acids, solvent N, N dimethylformamide, water add high temperature resistant spiral mouth vial in, stirred under room temperature；It is put into baking oven after container is sealed, is heated 4 days at 105 DEG C of temperature；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.The metal organic frame containing five core ytterbium cluster molecule construction units prepared by the present invention shows the carbon dioxide cycloaddition reaction of epoxides good size selectivity catalytic performance.
Description
Technical field
The present invention relates to a kind of metal organic frame containing five core ytterbium cluster molecule construction units and preparation method thereof and answer
With specifically, being related to the tool that a kind of carbon dioxide cycloaddition reaction to epoxides shows size selection catalytic activity
There are the preparation and its application of the metal-organic framework material of cage modle vestibule.
Background technology
In recent years, functional metal organic framework materials have been obtained for quite extensive as a field developed rapidly
Concern, a little it is critically important the reasons why be because they there are huge potentiality in practical application area.Metal cluster closes
Thing has become one of hot spot in current functional material research, not only due to they have the molecular structure of nano-scale, and
And also show interesting light, electricity, magnetic and catalytic property.But the current research overwhelming majority concentrates on the conjunction of multinuclear transition metal cluster
On thing, the research of multi-kernel rare-earth cluster compound is started late.In recent years, some four discrete cores, five cores, six cores, seven cores, eight cores,
Nine cores, ten cores, 12 cores, 15 cores etc. are synthesized in succession.The Long Lasheng of Xiamen University is taught in high core rare earth cluster compound
And do a lot of work in terms of rare earth-transition metal cluster compound.Using threonine ligand, four 60 chiral cores have been synthesized
Rare earth cluster compound, this is also the highest rare earth cluster compound of presently found check figure.In recent years, with terms of multi-kernel rare-earth cluster compound
The fast development of research, using rare earth cluster as molecular structure unit complex functionality rare earth cluster metal organic frame, since its is other
The structure of cause, abundant hole and offunctional site, causes the attention of chemist and material scholar.
Due to reasons such as the warm industrial developments of confession, the content of the carbon dioxide in air increasingly increases, and becoming causes the whole world
The principal element to warm.As chemistry and the accessory substance of energy industry, carbon dioxide has non-toxic and being readily available property, therefore
Carbon source can be used as to participate in commercial synthesis, such as the disubstituted urease of N, N ', cyclic carbonate, the conjunction for circulating polyurethane and formic acid
Into etc..Since cyclic carbonate can be used as aprotic, polar type solvent, the electrolysis element of battery, or as fine chemicals,
Many applications such as the intermediate or presoma of medicine and Polymer Synthesizing, so synthesizing ring using carbon dioxide and epoxides
Shape carbonic ester is constantly subjected to extensive concern.
The content of the invention
The purpose of the present invention is utilize 5,5'- (pyridine radicals -2,5- two substitutes) -1,3- phthalic acids containing pyridine radicals
(H4PDDI organic ligand) is used as, by adjusting synthesis condition, is constructed out using the method for solvent heat a kind of novel containing five
The metal-organic framework material of core ytterbium cluster, and it is studied as catalysis of the Lewis acid catalysts to carbon dioxide cycloaddition reaction
Performance.
The technical solution adopted by the present invention is：A kind of metal organic frame containing five core ytterbium cluster molecule construction units, system
Preparation Method includes the following steps：
1) by 5,5'- (pyridine radicals -2,5- two substitutes) -1,3- phthalic acids (H4PDDI)、Yb(NO3)3And N, N- dimethyl methyl
Acid amides is added in container, stirs lower dissolving；
2) deionized water is added, stirs evenly, is put into after container is sealed in baking oven, 4-5 is heated at 100-110 DEG C
My god；
3) it is slowly cooled to room temperature, whether there is the generation of color bulk crystals；
4) washed, filtered with n,N-Dimethylformamide, it is dry, obtain target product.
The above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units, in molar ratio, 5,5'- (pyridine radicals -2,
5- bis- substitutes) -1,3- phthalic acids (H4PDDI)：Yb(NO3)3=1:1.0-1.5.
The above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units, in step 2), puts after container is sealed
Enter in baking oven, heating rate is 5 DEG C of min-1。
The above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units, the drop being slowly cooled to room temperature
Warm speed is 5 DEG C of h-1。
The metal organic frame containing five core ytterbium cluster molecule construction units of the present invention, abundant unsaturation is contained in structure
Yb (III) center, can be used as Lewis acid catalysts to carry out catalytic applications to carbon dioxide cycloaddition reaction.Method is as follows：Take ring
Oxide and catalyst add in container or do not add co-catalyst, under stirring, be passed through CO2, 3-6h is reacted under high pressure；
The catalyst is the above-mentioned metal organic frame containing five core ytterbium cluster molecule construction units.Reaction equation is as follows：
The epoxides be propylene oxide, epoxy butane, allyl glycidyl ether, n-butyl glycidyl ether or
Styrene oxide.
In molar ratio, the dosage of the catalyst is the 0.03-0.05% of epoxides
The co-catalyst is tetrabutylammonium bromide (TBAB).
Described is passed through CO2, reacting under high pressure is：It is passed through CO2It is 1.0MPa, temperature 90-130 to make container inner pressure
℃。
The beneficial effects of the invention are as follows：The metal containing five core ytterbium cluster molecule construction units prepared by the present invention has machine frame
Frame is the first metal-organic framework material constructed by five core cluster molecule construction units.And the Yb in five core ytterbium clusters
(III) ion is seven coordinations or eight-coordinate, so containing abundant undersaturated Yb (III) center in structure, can conduct
Lewis acid site, makes the complex of invention can be used as a kind of Lewis acid catalysts, and the titanium dioxide carbocyclic ring of epoxide is added
Good catalytic performance is shown into reaction.And the because metal containing five core ytterbium cluster molecule construction units prepared by the present invention
Vestibule containing cage modle in the structure of organic frame, when carrying out catalytic reaction, " window " on the vestibule of cage modle is larger to size
Reactant have an interception effect, therefore the complex of the present invention is shown to the carbon dioxide cycloaddition reaction of epoxide
Size selectivity catalytic performance.Synthetic method is simple, has application prospect.
Brief description of the drawings
Fig. 1 a are the five core Yb cluster molecule construction units of trigonal biyramid type in metal-organic framework of the present invention.
Fig. 1 b are the coordination environments of Yb (III) ion in metal-organic framework of the present invention.
H in Fig. 2 a metal-organic frameworks of the present invention4A kind of coordination mode of PPDI ligands.
H in Fig. 2 b metal-organic frameworks of the present invention4Another coordination mode of PPDI ligands.
Each molecular structure unit [Yb in Fig. 3 metal-organic frameworks of the present invention5(μ3-OH)6(O2C-)8] be simplified to
Double cap triangular prism cylinder building blocks.
Fig. 4 is the three-dimensional apertures cavity configuration simplification figure of metal organic frame of the present invention.
Fig. 5 is the structure diagram of cage modle vestibule configuration in metal-organic framework of the present invention.
Fig. 6 a are the first windows of cage modle vestibule in metal organic frame of the present invention.
Fig. 6 b are second of windows of cage modle vestibule in metal organic frame of the present invention.
Fig. 6 c are the third windows of cage modle vestibule in metal organic frame of the present invention.
Fig. 7 is that the carbon dioxide that is catalyzed to metal organic frame of the present invention the differential responses time and propylene oxide cycloaddition are anti-
The influence answered.
Fig. 8 is the catalytic activity that metal organic frame of the present invention carries out five wheel circulation catalytic reactions.
Embodiment
Metal organic frame of the embodiment 1 containing five core ytterbium cluster molecule construction units
By H4PDDI (0.01g, 0.025mmol) and Yb (NO3)3·5H2O (0.015g, 0.03mmol) is added to volume and is
In the high temperature resistant spiral mouth vial of 5mL, 1.5mL DMF are added, magnetic stirrer is dissolved, and adds 1.5ml
H2O, up to metal salt, all dissolving is uniformly mixed with ligand within 15 minutes for stirring, is put into after vial is sealed in 105 DEG C of baking ovens,
Heat 4 days at such a temperature, with 5 DEG C of h-1Rate of temperature fall be slowly cooled to room temperature, whether there is color bulk crystals generation, with N, N-
Dimethylformamide washs, and filters, dry, obtains target product, i.e., the metal containing five core ytterbium cluster molecule construction units has machine frame
Frame, yield 50%.
The metal organic complex that the present invention synthesizes is one by the tetrabasic carboxylic acid ligand H containing pyridine groups4PDDI and three
The three-dimensional porous metals organic frame that five core Yb cluster molecule construction units (Fig. 1 a) of angle bicone are built into.Five in structure
Core Yb clusters [Yb5(μ3-OH)6(O2C-)8], it is to have a kind of molecular structure unit of eight connections as shown in Figure 1 b.Each five core Yb oxygen
Three kinds of different Yb are all included in cluster3+Center, one of Yb1 and two Yb3 ion are located on the equatorial plane of trigonal biyramid,
Also two Yb2 ions occupy the axial vertex position of trigonal biyramid.Yb1 and Yb3 is eight-coordinate, and Yb1 is and four μ3-
OH groups and four oxygen atom ligands, wherein four oxygen atoms are respectively from the carboxyl of four independent L1 ligands；Yb3 and four
A μ3- OH groups and four oxygen atom ligands, two of which oxygen atom come from the hydrone of two coordinations, two oxygen atoms
Come from the carboxyl of two independent L1 ligands.A kind of anti-cubic prism geometric configuration is presented in the coordination mode of Yb1 and Yb3, its
In anti-cubic prism a plane by four carboxyl oxygen atoms (Yb1) from four independent L1 ligands, or by two solely
The oxygen atom of two oxygen atoms and two hydrones on vertical L1 ligands forms (Yb3)；Another plane is then by four μ3-
The oxygen atom composition of OH.Yb2 and three μ3- OH oxygen atoms, the carboxyl oxygen atom and a water of coordination of three independent L1 ligands
Oxygen atom formed seven coordination, show single cap octahedral coordination geometric configuration.In the structure of metal organic frame, PDDI matches somebody with somebody
Two kinds of connection modes are showed respectively between body and Yb (III) ion, such as Fig. 2 a and 2b.
The carbon atom on carboxyl that will be coordinated with Yb centers regards the five abducent tie points of core Yb clusters as, will can each divide
Minor structure unit [Yb5(μ3-OH)6(O2C-)8] a double cap triangular prism cylinder (Fig. 3) is simplified to, the node of one eight connection, leads to
The bridging with PDDI ligands is crossed, expansion surrounds and forms a kind of frame structure (Fig. 4) with cage modle vestibule.As shown in figure 5, this contains
There is the cage modle vestibule in the metal organic frame of five core ytterbium cluster molecule construction units that a kind of octoploids structure, this octahedron is presented
Each vertex in occupation of a five core Yb clusters.There are three kinds " windows ", size in each cage modle vestibule structure to be respectively(Fig. 6 a),(Fig. 6 b) and(Fig. 6 c).
This contains the metal organic frame of five core ytterbium cluster molecule construction units, constructed by the Carboxylic acid ligand containing pyridine groups and
Into its crystal belongs to tetragonal crystal system, space group I41/amd。
Metal organic frame of the embodiment 2 containing five core ytterbium cluster molecule construction units adds the titanium dioxide carbocyclic ring of epoxides
Into the catalysis of reaction
The metal organic frame for containing five core ytterbium cluster molecule construction units prepared using embodiment 1 is as catalyst to dioxy
The cycloaddition reaction for changing carbon and epoxides is catalyzed.
The activation process of catalyst：A certain amount of metal organic frame containing five core ytterbium cluster molecule construction units is taken,
Vacuumized under 50 DEG C of heating conditions dry 24 it is small when.
1) influence of differential responses time
Method：Take after the activation of 37.2mg (0.02mmol, 0.04mol%) containing five core ytterbium cluster molecule construction units
Metal organic frame, the propylene oxide of the TBAB and 50mmol of 0.075mmol are added in autoclave, and sealing, is passed through CO2
It is 1.0MPa to make container inner pressure, and temperature is 120 DEG C, and the reaction time is respectively 3h, 4h, 5h and 6h, obtains product propylene carbonate
Ester.Experimental result gas chromatographic detection.
Under the differential responses time, should metal organic frame containing five core ytterbium cluster molecule construction units to carbon dioxide and
The catalytic performance of the cycloaddition reaction of propylene oxide.Experimental result as shown in fig. 7, reaction carry out 5 hours when, epoxy third
The conversion ratio of alkane has reached 87.2% (TOF:93.8h-1), even if reaction progress 6 is small, conversion ratio also increases there is no obvious
Greatly, so reaction time when 5 is small is the maximized optimal selection of products collection efficiency.
Product propene carbonate nuclear-magnetism：1H-NMR(400MHz,TMS,CDCl3):δ=4.84 (m, 1H, OCH), 4.53 (t,
1H, J=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, the metal organic frame containing five core ytterbium cluster molecule construction units after activation, 0.075mmol are taken
TBAB and the propylene oxide of 50mmol be added in autoclave, seal, be passed through CO2It is 1.0MPa to make container inner pressure,
Temperature is 120 DEG C, reacts 5h；In molar ratio, the addition of catalyst be propylene oxide 0.03mol%, 0.04mol% and
0.05mol%.Experimental result gas chromatographic detection.As a result such as table 1.
Table 1
| The amount of catalyst | 0.03mol% | 0.04mol% | 0.05mol% |
| The conversion ratio % of propylene oxide | 82.2 | 87.2 | 83.5 |
| TON | 548 | 436 | 334 |
| TOF(h-1) | 109.1 | 87.2 | 66.8 |
By table 1 as it can be seen that 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 does not improve to be declined on the contrary, therefore it is optimal that the catalyst of selection 0.04mol%, which participates in catalytic reaction,
Selection.
3) influence of co-catalyst
Method：The metal organic frame containing five core ytterbium cluster molecule construction units after activation is taken, as table 2 adds catalyst
And co-catalyst, the propylene oxide of 50mmol are added in autoclave, sealing, is passed through CO2The container inner pressure is set to be
1.0MPa, temperature are 120 DEG C, react 5h.Experimental result gas chromatographic detection.As a 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 propylene oxide | 17.2 | 9.9 | 87.2 |
| TON | — | 49.5 | 436 |
| TOF(h-1) | — | 9.9 | 87.2 |
By table 2 as it can be seen that the metal organic frame or TBAB individually containing five core ytterbium cluster molecule construction units are to the reaction
Catalytic effect it is all very low, and two kinds of materials exist can just show to carbon dioxide and epoxides cycloaddition reaction at the same time
Good catalytic performance.
4) different epoxides
Method：Take the metal containing five core ytterbium cluster molecule construction units after the activation of 37.2mg (0.04mol%) organic
Frame, the TBAB and 50mmol of 0.075mmol such as the epoxides of table 3, sealing, is passed through CO2The container inner pressure is set to be
1.0MPa, temperature are 120 DEG C, react 5h.Experimental result gas chromatographic detection.As a result such as table 3.
Table 3
As shown in table 3, the metal organic frame containing five core ytterbium cluster molecule construction units adds the ring of different epoxides
Into the catalytic reaction of reaction, with the increase of epoxides size, conversion ratio gradually reduces.This is because the present invention's contains five
There are cage modle vestibule in the structure of the metal organic frame of core ytterbium cluster molecule construction unit, reactant can allow for enter on vestibule
It is limited with " window " size of Lewis acid catalysis point contacts, so the conversion ratio of bigger reactant is lower.Therefore, this hair
Cycloaddition reaction exhibition of the bright metal organic frame containing five core ytterbium cluster molecule construction units to carbon dioxide and epoxides
Size selectivity catalytic performance is shown.
5) in cycloaddition reaction catalyst recyclable recycling property
The recycling of catalyst：After reaction, filter, catalyst is separated with reaction mixture, with methanol and dichloromethane
Alkane washs, then soaks six hours in methyl alcohol, filters out, and dries.
The concrete operations of circulation experiment：Utilize the catalyst (0.04mol%) and co-catalyst TBAB of recycling
(0.075mmol) is catalyzed carbon dioxideWith the cycloaddition reaction of propylene oxide (50mmol), at 120 DEG C
React 5 it is small when.
As shown in figure 8, circulation experiment proceeds to the 5th wheel, the activity of catalyst does not still decline experimental result.Illustrate this
Contain the metal organic frame of five core ytterbium cluster molecule construction units as carbon dioxide and epoxides cycloaddition reaction catalyst
Reusable edible.
Claims (9)
- A kind of 1. metal organic frame containing five core ytterbium cluster molecule construction units, it is characterised in that：Preparation method includes as follows Step：1）By 5,5'- (pyridine radicals -2,5- two substitutes) -1,3- phthalic acids, Yb (NO3)3Appearance is added to N,N-dimethylformamide In device, lower dissolving is stirred；In molar ratio, 5,5'- (pyridine radicals -2,5- bis- substitutes) -1,3- phthalic acids: Yb(NO3)3=1: 1.0-1.5；2）Water is added, stirs evenly, is put into after container is sealed in baking oven, heated 4-5 days at 100-110 DEG C；3）It is slowly cooled to room temperature, generates crystal；4）Washed, filtered with n,N-Dimethylformamide, it is dry, obtain target product.
- 2. the metal organic frame according to claim 1 containing five core ytterbium cluster molecule construction units, it is characterised in that：Step Rapid 2）In, it is put into after container is sealed in baking oven, heating rate is 5 DEG C of min-1。
- 3. the metal organic frame according to claim 1 containing five core ytterbium cluster molecule construction units, it is characterised in that：Step Rapid 3）In, the rate of temperature fall being slowly cooled to room temperature is 5 DEG C of h-1。
- 4. any metal organic frames containing five core ytterbium cluster molecule construction units of claim 1-3 are in catalysis CO2And ring Application in oxide cycloaddition reaction.
- 5. application according to claim 4, it is characterised in that method is as follows：Epoxides and catalyst are taken in container, Whether addition co-catalyst or not, under stirring, is passed through CO2, 3-6h is reacted under high pressure；The catalyst is claim 1- 3 any metal organic frames containing five core ytterbium cluster molecule construction units.
- 6. application according to claim 5, it is characterised in that：The epoxides is propylene oxide, epoxy butane, alkene Propyl glycidyl ether, n-butyl glycidyl ether or styrene oxide.
- 7. application according to claim 5, it is characterised in that：In molar ratio, the dosage of the catalyst is epoxidation The 0.03-0.05% of thing.
- 8. application according to claim 5, it is characterised in that：The co-catalyst is tetrabutylammonium bromide.
- 9. application according to claim 5, it is characterised in that：Described is passed through CO2, reacting under high pressure is：It is passed through CO2 It is 1.0MPa to make container inner pressure, and temperature is 90-130 DEG C.
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|---|---|---|---|---|
| US20150065737A1 (en) * | 2013-09-05 | 2015-03-05 | King Abdullah University Of Science And Technology | Tunable rare-earth fcu-metal-organic frameworks |
| CN104785209A (en) * | 2015-04-09 | 2015-07-22 | 厦门大学 | Metal organic framework material as well as preparation method and application thereof |
| CN104788309A (en) * | 2014-01-20 | 2015-07-22 | 任燕萍 | Metal organic framework, preparation method and use thereof, and carbon dioxide conversion method |
| WO2015149072A1 (en) * | 2014-03-28 | 2015-10-01 | The University Of Chicago | Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations |
-
2016
- 2016-01-28 CN CN201610065621.7A patent/CN105732487B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150065737A1 (en) * | 2013-09-05 | 2015-03-05 | King Abdullah University Of Science And Technology | Tunable rare-earth fcu-metal-organic frameworks |
| CN104788309A (en) * | 2014-01-20 | 2015-07-22 | 任燕萍 | Metal organic framework, preparation method and use thereof, and carbon dioxide conversion method |
| WO2015149072A1 (en) * | 2014-03-28 | 2015-10-01 | The University Of Chicago | Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations |
| CN104785209A (en) * | 2015-04-09 | 2015-07-22 | 厦门大学 | Metal organic framework material as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| A combined experimental and computational study of novel nanocage-based metal–organic frameworks for drug delivery;Jian-Qiang Liu,等;《Dalton Transactions》;20151009(第44期);第19370-19382页 * |
| 胺基桥联多芳氧基稀土金属化合物催化二氧化碳和环氧烷反应;秦杰;《苏州大学硕士学位论文》;20151231;全文 * |
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