CN104672277B - A kind of metal-organic framework materials and its application based on bowl shaped structure - Google Patents
A kind of metal-organic framework materials and its application based on bowl shaped structure Download PDFInfo
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- CN104672277B CN104672277B CN201510111487.5A CN201510111487A CN104672277B CN 104672277 B CN104672277 B CN 104672277B CN 201510111487 A CN201510111487 A CN 201510111487A CN 104672277 B CN104672277 B CN 104672277B
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Abstract
The present invention relates to a kind of metal-organic framework materials based on bowl shaped structure and its application.The technical solution of use is：Including following synthesis step：By Pb (NO3)2, organic ligand and N, N ' dimethylformamide are added in container, are stirred 20 40 minutes under room temperature；After container is sealed, it is placed in baking oven, under 378K ± 50K, keeps the temperature 24 days；It is slowly cooled to room temperature, obtains water white transparency rhabdolith, washing, filtering and drying, obtain target product.Metal-organic framework materials preparation method based on bowl shaped structure prepared by the present invention is simple, can efficient catalytic silicon cyanogenation, and can iterative cycles utilize, using more than five times, reaction 3 it is small when, catalytic efficiency remains to reach more than 90%.
Description
Technical field
The present invention relates to a kind of metal-organic framework materials, specifically, it is related to and a kind of silicon cyanogenation is urged with height
Change the metal-organic framework materials based on bowl-type structure of activity.
Background technology
Since there is bowl-type molecule charming structure and potential application value to obtain the concern of more and more people.Not only have
Machine synthesis field is directed to developing new container molecule, and oversubscription subdomains also pay many effort.Among these, based on expensive
The molecule bowl body system of metal is by systematic research.In order to more be widely applied this quasi-molecule, the avtive spot of molecule bowl
Need further to be utilized.
Metal organic hybrid thing has the important composition portion that open metal active site is Lewis acid different-phase catalysts
Point.It is not easy to however, obtaining the good metal organic hybrid thing of heat endurance, because heat endurance and unsaturated coordination are mutual
Conflict.Consider that homogeneous catalyst high catalytic efficiency but cannot recycle, different-phase catalyst can be recycled but is catalyzed from catalysis angle
Efficiency is low.Therefore, easily preparation, reusable edible, the different-phase catalyst of high catalytic efficiency increasingly evoke researcher's for exploitation
Interest.Active site is organically combined the efficient Lewis acid different-phase catalyst of design one with bowl shaped structure will
It is one cleverly tactful.
The content of the invention
The purpose of the present invention is by the use of Pb as metal node, by the use of 5- tert-butyl groups isophthalic acid and its homologue as having
Machine ligand, at a certain temperature, the metal using bowl shaped structure of the solvent thermal process synthesis with open metallic site are organic
Framework material.
The technical solution adopted by the present invention is as follows：The metal based on bowl shaped structure with high catalytic activity of the present invention has
Machine framework material, including following synthesis step：
1) by Pb (NO3)2, organic ligand and N, N '-dimethylformamide (DMF) are added in container, are stirred under room temperature
20-40 minutes；The organic ligand is between 5- hydroxyisophthalic acids, oreinol diacid, 5- sulfydryls isophthalic acid, 5- bromines
Phthalic acid, 5- chlorine isophthalic acid, 5- fluorine isophthalic acid, 5- tert-butyl groups isophthalic acid or 5- methoxyl group isophthalic acids.
2) after container is sealed, it is placed in baking oven, under 378K ± 50K, keeps the temperature 2-4 days；
3) it is slowly cooled to room temperature, obtains water white transparency rhabdolith, washing, filtering and drying, obtain target product.It is described
Be slowly cooled to room temperature and be：Rate of temperature fall is 4-8Kh-1。
The structure for the bowl-type compound that the present invention synthesizes is：It belongs to tetragonal crystal system, space group P4nc, its one
There are four lead ions, four organic ligand ligands, four DMF molecules and half of lattice hydrone in a elementary cell.Four cores
The Pb of complexIIO, O- chelating ligands are taken by the carboxyl in adjacent organic ligand, complex structure is special bowl-type
Structure, four lead ions form the main body frame of bowl-type, and four DMF molecules form the bottom of bowl, four five tert-butyl group isophthalic two
Formic acid or its homologue ligand form the rim of a bowl part.Each PbIIIon center is all seven coordinations, wherein there is six carboxyl oxygen originals
Son comes from four independent organic ligands, and the coordination mode of carboxyl oxygen atom and metal center uses monodentate chelating ligands and list
Tooth is coordinated two ways, oxygen atom of another oxygen atom from DMF solvent molecule.Each organic ligand is connected to three
Metal PbIIIon center, forms a unlimited chain structure.The chain structure infinitely extended is further connected by organic ligand
Connect and form the three-dimensional coordination polymer with pore space structure.
As described above, metal Pb and 5- tert-butyl group isophthalic acid ligands and its each structure of homologue and DMF molecules
Unit forms a metal-organic framework materials with special bowl structure unit by complicated connection mode.This structure
In there are bowl-shape cavity, after removing guest molecule, cavity becomes larger, and has unsatuated metal avtive spot to be exposed in duct, can be with
Make Lewis acid catalysts.
The metal-organic framework materials based on bowl shaped structure of the present invention can be used as effective catalyst to be used to be catalyzed silicon cyanogen
Change reaction.Method is as follows：Reaction substrate aromatic aldehyde and trimethylsilyl cyanide are dissolved in organic solvent, add catalyst, sealing
Reaction system, under the protection of nitrogen, reaction temperature is 30-50 DEG C, when reaction 2-4 is small；The catalyst is above-mentioned base
In the metal-organic framework materials of bowl shaped structure.Reaction equation is as follows：
Wherein
The aromatic aldehyde is benzaldehyde, 1- naphthaldehydes, 4-methoxybenzaldehyde or 4- benzoxybenzaldehydes.
The molar ratio of aromatic aldehyde and trimethylsilyl cyanide is 1:2.
The organic solvent is dichloromethane.
Preferably, catalyst is activated before use, at 200 DEG C of temperature, when vacuum drying 12 is small.
The beneficial effects of the invention are as follows：Metal-organic framework materials preparation method based on bowl shaped structure prepared by the present invention
Simply, can iterative cycles utilize, using more than five times, catalytic efficiency remains to reach more than 90%.The present invention prepare based on bowl
The metal-organic framework materials of shape structure as catalyst, can efficient catalytic silicon cyanogenation, catalytic reaction is in anhydrous and oxygen-free bar
Carried out under part.
Brief description of the drawings
Fig. 1 is the structure chart based on bowl-type metal-organic framework materials basic structural unit prepared by embodiment 1.
Fig. 2 is the tomograph based on bowl-type metal-organic framework materials prepared by embodiment 1.
Embodiment
A kind of metal-organic framework materials based on bowl shaped structure of embodiment 1
(1) synthetic method
By Pb (NO3)2(0.015g, 0.045mmol), 5- tert-butyl group isophthalic acids (H2Tbip) (0.010g,
0.045mmol) it is added in the vial that volume is 5ml, and is stirred under normal temperature condition 20 minutes with DMF (3ml), then will
Its good seal, is put into baking oven, and heating makes oven temperature reach 378K, and maintains the temperature under the conditions of this 3 days, then slowly cold
But room temperature (rate of temperature fall 5Kh is arrived-1), water white transparency rhabdolith is obtained, washing, filtering and drying, obtain based on bowl-type knot
The metal-organic framework materials of structure, yield 65%.
Obtain based on bowl shaped structure metal-organic framework materials (test to obtain data through X-ray single crystal diffractometer,
The structure chart of acquisition is as depicted in figs. 1 and 2).Fig. 1 is the basic structural unit of the metal-organic framework materials based on bowl shaped structure
Figure, the compound belong to tetragonal crystal system, space group P4nc, there is four lead ions in its elementary cell, four five
Tert-butyl group isophthalic acid ligand, four DMF molecules and half of lattice hydrone.The Pb of the tetranuclear complexIIBy adjacent
Carboxyl in five tert-butyl group isophthalic acid anion takes O, O- chelating ligands, and complex structure is special bowl-type structure, and four
A lead ion forms the main body frame of bowl-type, and four DMF molecules form the bottom of bowl, and four five tert-butyl isophthalic acids are formed
The rim of a bowl part.Each PbIIIon center is all seven coordinations (it is weak key action to have two keys), wherein there is six carboxyl oxygen atoms
Come from four five independent tert-butyl group isophthalic acid ligands, the coordination mode of carboxyl oxygen atom and metal center uses monodentate chela
Close coordination and monodentate ligand two ways, oxygen atom of another oxygen atom from DMF solvent molecule.Between each five tert-butyl group
Phthalic acid ligand is all connected to three metal PbIIIon center, forms a unlimited chain structure.The chain knot infinitely extended
Structure further constitutes the three-dimensional coordination polymer Pb with pore space structure by 5- tert-butyl group isophthalic acid organic ligands4
(tbip)4(DMF)4·0.5H2O (as shown in Figure 2).
A kind of metal-organic framework materials based on bowl shaped structure of embodiment 2
(1) synthetic method
By Pb (NO3)2(0.015g, 0.045mmol), 5- tert-butyl groups isophthalic acid (0.010g, 0.045mmol) and DMF
(3ml) is added in the vial that volume is 5ml, and is stirred 20 minutes under normal temperature condition, is then sealed against, is put into baking
In case, heating makes oven temperature reach 368K, and maintains the temperature under the conditions of this 3 days, is then slowly cooled to room temperature (cooling speed
Rate is 5Kh-1), water white transparency rhabdolith is obtained, washing, filtering and drying, obtain the metal organic framework based on bowl shaped structure
Material, yield 45%.
A kind of metal-organic framework materials based on bowl shaped structure of embodiment 3
(1) synthetic method
By Pb (NO3)2(0.015g, 0.045mmol), organic ligand (0.010g, 0.045mmol) as shown in Table 1 and
DMF (3ml) is added in the vial that volume is 5ml, and is stirred 20 minutes under normal temperature condition, is then sealed against, is put
Enter in baking oven, heating makes oven temperature reach 378K, and maintains the temperature under the conditions of this 3 days, is then slowly cooled to room temperature (drop
Warm speed is 5Kh-1), water white transparency rhabdolith is obtained, washing, filtering and drying, it is organic to obtain the metal based on bowl shaped structure
Framework material.
Table 1
Synthesis the metal-organic framework materials structure based on bowl shaped structure be：Tetragonal crystal system is belonged to, space group is
P4nc, there is four lead ions, four organic ligands, four DMF molecules and half of lattice watter in its elementary cell
Molecule.The Pb of tetranuclear complexIIO, O- chelating ligands, complex knot are taken by the carboxyl in adjacent organic ligand anion
Structure is special bowl-type structure, and four lead ions form the main body frame of bowl-type, and four DMF molecules form the bottom of bowl, four
Organic ligand forms the rim of a bowl part.
Metal-organic framework materials catalysis silicon cyanogenation of the embodiment 4 based on bowl shaped structure
Metal-organic framework materials based on bowl shaped structure prepared by embodiment 1 are activated before use, in temperature
At 200 DEG C, when vacuum drying 12 is small.
Method：The benzaldehyde of 1mol and 2mol trimethylsilyl cyanides are dissolved in 5ml dichloromethane.Add 40mg catalyst
(metal-organic framework materials based on bowl shaped structure prepared by embodiment 1), seal reaction system, under the protection of nitrogen, instead
It is 40 DEG C to answer temperature, and reaction time 3h, obtains product, and by gas chromatographic analysis, the conversion ratio of benzaldehyde is 99.5%.
Metal-organic framework materials catalysis silicon cyanogenation of the embodiment 5 based on bowl shaped structure
Metal-organic framework materials based on bowl shaped structure prepared by embodiment 1 are activated before use, in temperature
At 200 DEG C, when vacuum drying 12 is small.
Method：The 1- naphthaldehydes of 1mol and 2mol trimethylsilyl cyanides are dissolved in the dichloromethane of 5ml.40mg is added to urge
Agent (metal-organic framework materials based on bowl shaped structure prepared by embodiment 1), seals reaction system, in the protection of nitrogen
Under, reaction temperature is 40 DEG C, and reaction time 3h, obtains product, and by gas chromatographic analysis, the conversion ratio of 1- naphthaldehydes is
99.0%.
Reaction equation is as follows：
Metal-organic framework materials catalysis silicon cyanogenation of the embodiment 6 based on bowl shaped structure
Method：The aromatic aldehyde of 1mol and 2mol trimethylsilyl cyanides are dissolved in the dichloromethane of 5ml.Add 40mg catalysis
Agent (metal-organic framework materials based on bowl shaped structure prepared by embodiment 1), seals reaction system, under the protection of nitrogen,
Reaction temperature is 40 DEG C, reaction time 3h, obtains target product, the conversion ratio such as table 2 of aromatic aldehyde.
Table 2
| Aromatic aldehyde | 4-methoxybenzaldehyde | 4- benzoxybenzaldehydes |
| Conversion ratio | 56.1% | 33.0% |
Claims (5)
- A kind of 1. application based on the metal-organic framework materials of bowl shaped structure in silicon cyanogenation is catalyzed, it is characterised in that side Method is as follows：Reaction substrate aromatic aldehyde and trimethylsilyl cyanide are dissolved in organic solvent, add catalyst, seals reaction system, Under the protection of nitrogen, reaction temperature is 30-50 DEG C, when reaction 2-4 is small；The catalyst is the metal-organic framework materials Pb based on bowl shaped structure4(tbip)4(DMF)4·0.5H2O；Described Metal-organic framework materials Pb based on bowl shaped structure4(tbip)4(DMF)4·0.5H2The structure of O is：Belong to tetragonal crystal system, it is empty Between group beP4nc, there is four lead ions, four 5- tert-butyl group isophthalic acids H in its elementary cell2Tbip ligands, four A DMF molecules and half of lattice hydrone, the Pb of tetranuclear complexIIPass through adjacent 5- tert-butyl group isophthalic acids H2Tbip is cloudy Carboxyl in ion takes O, O- chelating ligands, and complex structure is special bowl shaped structure, and four lead ions form bowl-type Main body frame, four DMF molecules form the bottom of bowl, four 5- tert-butyl group isophthalic acids H2Tbip forms the rim of a bowl part；The aromatic aldehyde is benzaldehyde or 1- naphthaldehydes.
- 2. application according to claim 1, it is characterised in that：The metal-organic framework materials based on bowl shaped structure Pb4(tbip)4(DMF)4·0.5H2The preparation method of O, including following synthesis step：By 0.015 g Pb (NO3)2, 0.010 g H2Tbip and 3 ml DMF is added in the vial that volume is 5ml, and is stirred 20 minutes under normal temperature condition, then that its is close Seal, be put into baking oven, heating makes oven temperature reach 378 K, and maintains the temperature under the conditions of this 3 days, then Slow cooling To room temperature, rate of temperature fall is 5 Kh-1, water white transparency rhabdolith is obtained, washing, filtering and drying, obtain target product.
- 3. application according to claim 1, it is characterised in that：The molar ratio of aromatic aldehyde and trimethylsilyl cyanide is 1:2.
- 4. application according to claim 1, it is characterised in that：The organic solvent is dichloromethane.
- 5. application according to claim 1, it is characterised in that：Catalyst is before use at 200 DEG C of temperature, vacuum activating 12 it is small when.
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| CN105237565B (en) * | 2015-11-19 | 2018-09-21 | 辽宁大学 | A kind of metal-organic framework materials and its application based on plumbi nitras |
| CN105906818A (en) * | 2016-06-16 | 2016-08-31 | 桂林理工大学 | Isophthalic acid-5-copper sulfonate coordination polymer and preparation method thereof |
| CN106083914A (en) * | 2016-06-16 | 2016-11-09 | 桂林理工大学 | M-phthalic acid 5 sulfonic acid lead coordination polymer and preparation method thereof |
| CN106732785B (en) * | 2017-01-23 | 2019-07-02 | 辽宁大学 | A kind of application of the porous metal-organic framework compound in silicon cyanation based on rare earth |
| CN106831880B (en) * | 2017-02-06 | 2019-03-15 | 辽宁大学 | One kind being based on MnIIMetal-organic framework materials and its preparation method and application |
| CN109233816A (en) * | 2018-10-25 | 2019-01-18 | 陕西科技大学 | A kind of lead coordination polymer ion fluorescence probe material and its preparation method and application |
| CN109456754B (en) * | 2018-12-07 | 2021-06-18 | 辽宁大学 | Lead-based metal organic framework material and preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
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| Synthesis, structure and catalytic application of lead (Ⅱ) complexes in cyanosilylation reactions;Anirban Karmakar等;《Dalton Transactions》;20141020(第44期);第268-280页，参见第268页左栏第1段、左栏第3段1-8行，第269页左栏倒数第1段1-7行，第273页左栏第1段，第275页表1，第276页表2，第276页图8，第278页左栏第2段1-5行 * |
| 含二元羧酸配体配位聚合物的合成结构及性质研究;付帅;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20130315;B014-232，参见第1章第10页图1-10，第2章第13页倒数第1段、第18页倒数第1段3-4行 * |
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