CN104672277A - Metal organic framework material based on bowl-shaped structure and application thereof - Google Patents
Metal organic framework material based on bowl-shaped structure and application thereof Download PDFInfo
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- CN104672277A CN104672277A CN201510111487.5A CN201510111487A CN104672277A CN 104672277 A CN104672277 A CN 104672277A CN 201510111487 A CN201510111487 A CN 201510111487A CN 104672277 A CN104672277 A CN 104672277A
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- WGQKYBSKWIADBV-UHFFFAOYSA-N NCc1ccccc1 Chemical compound NCc1ccccc1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a metal organic framework material based on a bowl-shaped structure and application thereof. According to the adopted technical scheme, the metal organic framework material comprises the following synthesis steps: adding Pb(NO3)2, organic ligands and N,N'-dimethyl formamide into a container, and stirring for 20-40 minutes at normal temperature; sealing the container, placing the container in an oven, and maintaining the temperature for 2-4 days at the temperature of 378K+/-50K; slowly cooling to the room temperature to obtain a colorless transparent rod crystal; washing, filtering and drying the colorless transparent rod crystal to obtain a target product. A preparation method of the prepared metal organic framework material based on the bowl-shaped structure is simple, the silylcyanation reaction can be efficiently catalyzed, the metal organic framework material can be recycled for over five times, the reaction time is 3h, and the catalysis efficiency can exceed 90 percent.
Description
Technical field
The present invention relates to a kind of metal-organic framework materials, specifically, relate to a kind of metal-organic framework materials based on bowl-type structure silicon cyanogenation to high catalytic activity.
Background technology
Because bowl-type molecule has the concern that charming structure and potential using value obtain more and more people.Not only organic synthesis field is devoted to develop new container molecule, and a lot of effort is also paid in supramolecule field.At this wherein, based on the molecule bowl system of precious metal by systematic research.In order to apply this quasi-molecule more widely, the avtive spot of molecule bowl needs to be utilized further.
Metal organic hybrid thing has the important component part that open metal active site is Lewis acid different-phase catalyst.But, obtain the metal organic hybrid thing of Heat stability is good and be not easy, because thermostability and unsaturated coordination are conflicting.Consider from catalysis angle, homogeneous catalyst catalytic efficiency is high but can not reclaim, and different-phase catalyst can reclaim but catalytic efficiency is low.Therefore, develop easily preparation, interest that reusable edible, different-phase catalyst that catalytic efficiency is high more and more evoke investigator.Active site and bowl shaped structure organically being combined design one efficient Lewis acid different-phase catalyst will be a strategy cleverly.
Summary of the invention
The object of the invention is to utilize Pb as metal node, utilize 5-tertiary butyl m-phthalic acid and homologue thereof as organic ligand, at a certain temperature, utilize solvent thermal process to synthesize the metal-organic framework materials with the bowl shaped structure of open metallic site.
The technical solution used in the present invention is as follows: the metal-organic framework materials based on bowl shaped structure with high catalytic activity of the present invention, comprises following synthesis step:
1) by Pb (NO
3)
2, organic ligand and N, N '-dimethyl formamide (DMF) joins in container, stirs 20-40 minute under normal temperature; Described organic ligand is 5-hydroxyisophthalic acid, oreinol diacid, 5-sulfydryl m-phthalic acid, 5-bromine m-phthalic acid, 5-chlorine m-phthalic acid, 5-fluorine m-phthalic acid, 5-tertiary butyl m-phthalic acid or 5-methoxyl group m-phthalic acid.
2) by after container sealing, baking oven is placed in, under 378K ± 50K, insulation 2-4 days;
3) progressively cool to room temperature, obtain water white transparency rhabdolith, washing, filtration are also dry, obtain target product.The described room temperature that progressively cools to is: rate of temperature fall is 4-8Kh
-1.
The structure of the bowl-type compound that the present invention synthesizes is: it belongs to tetragonal system, and spacer is P4nc, in its elementary cell, have four lead ions, four organic ligand parts, four DMF molecules and half lattice water molecule.The Pb of tetranuclear complex
iIo is taked by the carboxyl in adjacent organic ligand, O-chelating ligands, complex structure is special bowl-type structure, and four lead ions form the main body frame of bowl-type, the bottom of four DMF molecular composition bowls, four five tert-butyl isophthalic acid or its homologue part form the rim of a bowl part.Each Pb
iIion center is all seven coordinations, six carboxyl oxygen atoms are wherein had to come from four independently organic ligands, the coordination mode of carboxyl oxygen atom and metal center adopts monodentate chelating ligands and monodentate ligand two kinds of modes, and another one Sauerstoffatom is from the Sauerstoffatom of DMF solvent molecule.Each organic ligand is connected to three metal Pb
iIion center, forms a unlimited chain-like structure.The chain-like structure of unlimited extension constitutes the three-dimensional coordination polymer with pore space structure further by organic ligand.
As mentioned above, each structural unit of metal Pb and 5-tertiary butyl m-phthalic acid part and homologue and DMF molecule defines by complicated mode of connection the metal-organic framework materials that has special bowl structure unit.There is bowl-shape cavity in this structure, after removing guest molecule, cavity becomes large, has unsatuated metal avtive spot to be exposed in duct, can make Lewis acid catalyst.
Metal-organic framework materials based on bowl shaped structure of the present invention can be used for catalysis silicon cyanogenation as effective catalyst.Method is as follows: be dissolved in organic solvent by reaction substrate aromatic aldehyde and trimethylsilyl cyanide, add catalyzer, sealed reaction system, and under the protection of nitrogen, temperature of reaction is 30-50 DEG C, reaction 2-4 hour; Described catalyzer is the above-mentioned metal-organic framework materials based on bowl shaped structure.Reaction formula is as follows:
Wherein
Described aromatic aldehyde is phenyl aldehyde, 1-naphthaldehyde, 4-methoxybenzaldehyde or 4-benzoxybenzaldehyde.
The mol ratio of aromatic aldehyde and trimethylsilyl cyanide is 1:2.
Described organic solvent is methylene dichloride.
Preferably, catalyzer activates before use, at temperature 200 DEG C, and vacuum-drying 12 hours.
The invention has the beneficial effects as follows: the metal-organic framework materials preparation method based on bowl shaped structure prepared by the present invention is simple, can utilize by iterative cycles, use more than five times, catalytic efficiency still can reach more than 90%.Metal-organic framework materials based on bowl shaped structure prepared by the present invention, can efficient catalytic silicon cyanogenation as catalyzer, and catalyzed reaction is carried out under anhydrous and oxygen-free condition.
Accompanying drawing explanation
Fig. 1 is the structure iron 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
Embodiment 1 one kinds of metal-organic framework materials based on bowl shaped structure
(1) synthetic method
By Pb (NO
3)
2(0.015g, 0.045mmol), 5-tertiary butyl m-phthalic acid (H
2tbip) (0.010g, 0.045mmol) joining volume with DMF (3ml) is in the vial of 5ml, and stir 20 minutes under normal temperature condition, then by its good seal, put into baking oven, heating makes oven temperature reach 378K, and maintains the temperature at this condition lower 3 days, and (rate of temperature fall is 5Kh to be then slowly cooled to room temperature
-1), obtain water white transparency rhabdolith, washing, filtration are also dry, must based on the metal-organic framework materials of bowl shaped structure, and productive rate is 65%.
The metal-organic framework materials based on bowl shaped structure (obtain data through the test of X-ray single crystal diffraction instrument, the structure iron of acquisition as depicted in figs. 1 and 2) obtained.Fig. 1 is the basic structural unit figure of the metal-organic framework materials based on bowl shaped structure, this compound belongs to tetragonal system, spacer is P4nc, in its elementary cell, have four lead ions, four five tertiary butyl m-phthalic acid parts, four DMF molecules and half lattice water molecule.The Pb of this tetranuclear complex
iIo is taked by the carboxyl in five adjacent tertiary butyl m-phthalic acid negatively charged ion, O-chelating ligands, complex structure is special bowl-type structure, and four lead ions form the main body frame of bowl-type, the bottom of four DMF molecular composition bowls, four five tert-butyl isophthalic acid form the rim of a bowl part.Each Pb
iIion center is all seven coordinations (having two keys to be weak key action), six carboxyl oxygen atoms are wherein had to come from four independently five tertiary butyl m-phthalic acid parts, the coordination mode of carboxyl oxygen atom and metal center adopts monodentate chelating ligands and monodentate ligand two kinds of modes, and another one Sauerstoffatom is from the Sauerstoffatom of DMF solvent molecule.Each five tertiary butyl m-phthalic acid parts are connected to three metal Pb
iIion center, forms a unlimited chain-like structure.The chain-like structure of unlimited extension constitutes the three-dimensional coordination polymer Pb with pore space structure further by 5-tertiary butyl m-phthalic acid organic ligand
4(tbip)
4(DMF)
40.5H
2o (as shown in Figure 2).
Embodiment 2 one kinds of metal-organic framework materials based on bowl shaped structure
(1) synthetic method
By Pb (NO
3)
2(0.015g, 0.045mmol), 5-tertiary butyl m-phthalic acid (0.010g, 0.045mmol) joining volume with DMF (3ml) is in the vial of 5ml, and stirs 20 minutes under normal temperature condition, then by its good seal, put into baking oven, heating makes oven temperature reach 368K, and maintains the temperature at this condition lower 3 days, and (rate of temperature fall is 5Kh to be then slowly cooled to room temperature
-1), obtain water white transparency rhabdolith, washing, filtration are also dry, must based on the metal-organic framework materials of bowl shaped structure, and productive rate is 45%.
Embodiment 3 one kinds of metal-organic framework materials based on bowl shaped structure
(1) synthetic method
By Pb (NO
3)
2(0.015g, 0.045mmol), organic ligand (0.010g as shown in table 1,0.045mmol) joining volume with DMF (3ml) is in the vial of 5ml, and stirs 20 minutes under normal temperature condition, then by its good seal, put into baking oven, heating makes oven temperature reach 378K, and maintains the temperature at this condition lower 3 days, and (rate of temperature fall is 5Kh to be then slowly cooled to room temperature
-1), obtain water white transparency rhabdolith, washing, filtration are also dry, must based on the metal-organic framework materials of bowl shaped structure.
Table 1
The metal-organic framework materials structure based on bowl shaped structure of synthesis is: all belong to tetragonal system, spacer is P4nc, in its elementary cell, have four lead ions, four organic ligands, four DMF molecules and half lattice water molecule.The Pb of tetranuclear complex
iItake O by the carboxyl in adjacent organic ligand negatively charged ion, O-chelating ligands, complex structure is special bowl-type structure, and four lead ions form the main body frame of bowl-type, and the bottom of four DMF molecular composition bowls, four organic ligands form the rim of a bowl part.
Embodiment 4 is based on the metal-organic framework materials catalysis silicon cyanogenation of bowl shaped structure
The metal-organic framework materials based on bowl shaped structure embodiment 1 prepared activates before use, at temperature 200 DEG C, and vacuum-drying 12 hours.
Method: the phenyl aldehyde of 1mol and 2mol trimethylsilyl cyanide are dissolved in 5ml methylene dichloride.Add 40mg catalyzer (metal-organic framework materials based on bowl shaped structure prepared by embodiment 1), sealed reaction system, under the protection of nitrogen; temperature of reaction is 40 DEG C, and the reaction times is 3h, obtains product; by gas chromatographic analysis, the transformation efficiency of phenyl aldehyde is 99.5%.
Embodiment 5 is based on the metal-organic framework materials catalysis silicon cyanogenation of bowl shaped structure
The metal-organic framework materials based on bowl shaped structure embodiment 1 prepared activates before use, at temperature 200 DEG C, and vacuum-drying 12 hours.
Method: the 1-naphthaldehyde of 1mol and 2mol trimethylsilyl cyanide are dissolved in the methylene dichloride of 5ml.Add 40mg catalyzer (metal-organic framework materials based on bowl shaped structure prepared by embodiment 1), sealed reaction system, under the protection of nitrogen; temperature of reaction is 40 DEG C, and the reaction times is 3h, obtains product; by gas chromatographic analysis, the transformation efficiency of 1-naphthaldehyde is 99.0%.
Reaction formula is as follows:
Embodiment 6 is based on the metal-organic framework materials catalysis silicon cyanogenation of bowl shaped structure
Method: the aromatic aldehyde of 1mol and 2mol trimethylsilyl cyanide are dissolved in the methylene dichloride of 5ml.Add 40mg catalyzer (metal-organic framework materials based on bowl shaped structure prepared by embodiment 1), sealed reaction system, under the protection of nitrogen, temperature of reaction is 40 DEG C, and the reaction times is 3h, obtains target product, and the transformation efficiency of aromatic aldehyde is as table 2.
Table 2
| Aromatic aldehyde | 4-methoxybenzaldehyde | 4-benzoxybenzaldehyde |
| Transformation efficiency | 56.1％ | 33.0％ |
Claims (9)
1. based on a metal-organic framework materials for bowl shaped structure, it is characterized in that: comprise following synthesis step:
1) by Pb (NO
3)
2, organic ligand and N, N '-dimethyl formamide join in container, under normal temperature, stir 20-40 minute;
2) by after container sealing, baking oven is placed in, under 378K ± 50K, insulation 2-4 days;
3) progressively cool to room temperature, obtain water white transparency rhabdolith, washing, filtration are also dry, obtain target product.
2. the metal-organic framework materials based on bowl shaped structure according to claim 1, is characterized in that: described organic ligand is 5-hydroxyisophthalic acid, oreinol diacid, 5-sulfydryl m-phthalic acid, 5-bromine m-phthalic acid, 5-chlorine m-phthalic acid, 5-fluorine m-phthalic acid, 5-tertiary butyl m-phthalic acid or 5-methoxyl group m-phthalic acid.
3. the metal-organic framework materials based on bowl shaped structure according to claim 1, is characterized in that: the described room temperature that progressively cools to is: rate of temperature fall is 4-8Kh
-1.
4. the application of metal-organic framework materials in catalysis silicon cyanogenation based on bowl shaped structure described in claim 1,2 or 3.
5. application according to claim 4, is characterized in that method is as follows: be dissolved in organic solvent by reaction substrate aromatic aldehyde and trimethylsilyl cyanide, add catalyzer, sealed reaction system, under the protection of nitrogen, temperature of reaction is 30-50 DEG C, reaction 2-4 hour; Described catalyzer is the metal-organic framework materials based on bowl shaped structure described in claim 1,2 or 3.
6. application according to claim 5, is characterized in that: described aromatic aldehyde is phenyl aldehyde, 1-naphthaldehyde, 4-methoxybenzaldehyde or 4-benzoxybenzaldehyde.
7. application according to claim 5, is characterized in that: the mol ratio of aromatic aldehyde and trimethylsilyl cyanide is 1:2.
8. application according to claim 5, is characterized in that: described organic solvent is methylene dichloride.
9. application according to claim 5, is characterized in that: catalyzer before use at temperature 200 DEG C, vacuum activating 12 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237565A (en) * | 2015-11-19 | 2016-01-13 | 辽宁大学 | Metal organic framework material based on lead nitrate and application thereof |
| 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 |
| CN106732785A (en) * | 2017-01-23 | 2017-05-31 | 辽宁大学 | A kind of application of porous metal-organic framework compound based on rare earth in silicon cyanation |
| CN106831880A (en) * | 2017-02-06 | 2017-06-13 | 辽宁大学 | One kind is 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 |
| CN109456754A (en) * | 2018-12-07 | 2019-03-12 | 辽宁大学 | A kind of lead base metal-organic framework material and its preparation method and application |
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2015
- 2015-03-13 CN CN201510111487.5A patent/CN104672277B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| ANIRBAN KARMAKAR等: "Synthesis, structure and catalytic application of lead (Ⅱ) complexes in cyanosilylation reactions", 《DALTON TRANSACTIONS》 * |
| 付帅: "含二元羧酸配体配位聚合物的合成结构及性质研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237565A (en) * | 2015-11-19 | 2016-01-13 | 辽宁大学 | Metal organic framework material based on lead nitrate and application thereof |
| 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 |
| CN106732785A (en) * | 2017-01-23 | 2017-05-31 | 辽宁大学 | A kind of application of porous metal-organic framework compound based on rare earth in silicon cyanation |
| 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 |
| CN106831880A (en) * | 2017-02-06 | 2017-06-13 | 辽宁大学 | One kind is based on MnIIMetal-organic framework materials and its preparation method and application |
| 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 |
| CN109456754A (en) * | 2018-12-07 | 2019-03-12 | 辽宁大学 | A kind of lead base metal-organic framework material and its preparation method and application |
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