CN111790447A - For CO2Molecular crystalline catalyst for cycloaddition reaction with epoxy compound and preparation method thereof - Google Patents
For CO2Molecular crystalline catalyst for cycloaddition reaction with epoxy compound and preparation method thereof Download PDFInfo
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- CN111790447A CN111790447A CN202010677536.2A CN202010677536A CN111790447A CN 111790447 A CN111790447 A CN 111790447A CN 202010677536 A CN202010677536 A CN 202010677536A CN 111790447 A CN111790447 A CN 111790447A
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
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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
- C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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Abstract
The invention relates to the technical field of catalysts, and discloses a catalyst for CO2A molecular crystalline catalyst for cycloaddition reaction with epoxy compound, which has a chemical formula { [ Zn { [2(btca)2(ttz‑NH2)]·3solvents}nWherein btca2‑Is 5-carboxylic acid benzotriazole dianion, ttz-NH2Is 5-aminotetrazole, and 3solvents are 3solvent molecules. The molecular crystalline catalyst can be used as a catalyst for CO at normal temperature and normal pressure2The catalyst has the advantages of simple preparation process, high catalytic activity, good selectivity and good stability when being subjected to cycloaddition reaction with an epoxy compound, and can be used for preparing a catalyst for CO2With an epoxy compound ringAnd the method has great potential application value in the aspect of addition reaction.
Description
Technical Field
The invention relates to a molecular crystalline catalyst, in particular to a catalyst for CO2A molecular crystalline catalyst for cycloaddition reaction with an epoxy compound.
Background
In recent years, with the development of industry and the continuous progress of human society, on the one hand, CO is generated2The greenhouse effect caused by the method is increasingly serious, seriously threatens the human society and the ecological environment, and becomes an international problem to be solved urgently. On the other hand, due to CO2The method has the characteristics of wide distribution, rich content, low cost, no toxicity, reproducibility, safe use and non-flammability of C1 resource, and becomes a research hotspot of scientists. Therefore, how to capture CO2And the method is converted into chemical resources with high added value to relieve energy crisis and greenhouse effect, and simultaneously realizes resource utilization, thereby becoming a research hotspot of scientific researchers. There has been a constant effort to develop effective CO2Chemical immobilisation methods, e.g. CO2Cycloaddition reaction with an epoxy compound. However, due to CO2With high thermodynamic stability and kinetic inertness, the reaction process usually requires very severe conditions, such as highly active noble metal (Ag, Pd, Ru) catalysts, high temperature and pressure and long reaction time. Therefore, it is urgently required to develop a mild reaction system for reacting an epoxy compound with CO2A cycloaddition reaction is carried out.
Noble metal catalysts are valued for their excellent activity, selectivity, and stability. However, noble metal catalysts are prone to catalyst "poisoning", are prone to sintering at higher temperatures, and lose their activity due to sublimation. In addition, the precious metals are limited in resources and expensive, so that they cannot be used on a large scale. Compared with the noble metal (Ag, Pd, Ru) catalyst with high activity, the non-noble metal catalyst is more expensive than the noble metal, and although the catalytic activity is lower, the non-noble metal catalyst is paid attention to because of sufficient activity and excellent thermal stability. The molecular crystalline catalyst is used as a non-noble metal catalyst, has the characteristics of large surface area, modifiable pores, adjustable structure, more catalytic sites and the like, and is capable of effectively promoting CO2A material that undergoes a chemical transformation. Therefore, partial substitution is carried out on the premise of keeping good conversion effectOr all precious metals are replaced, and the search for other high-efficiency cheap non-precious metal catalysts to replace the traditional precious metal catalysts is a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a method for CO aiming at the technical analysis2The molecular crystalline catalyst for cycloaddition reaction with epoxy compound has simple preparation process, high catalytic activity, high selectivity, high stability and high CO content2Has great application value in the aspect of cycloaddition reaction with epoxy compounds.
The technical scheme of the invention is as follows2A molecular crystalline catalyst for cycloaddition reaction with epoxy compound, which has a chemical formula { [ Zn { [2(btca)2(ttz-NH2)]·3solvents}nWherein btca2-Is 5-carboxylic acid benzotriazole dianion, ttz-NH2Is 5-aminotetrazole, 3solvents are 3solvent molecules, and n is a natural number from 1 to infinity.
The molecular crystalline catalyst belongs to an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:
alpha is 90 deg., beta is 90 deg., gamma is 90 deg., crystal volume is
Z＝4。
1 Zn exists in the minimum asymmetric structural unit of the molecular crystalline catalyst2+Ion, 1 btca2-Ligand, 0.5 ttz-NH2In which Zn is2+The ions adopt a coordination mode of four-coordinate tetrahedron and are respectively linked with 3 btca2-1 oxygen atom, 2 nitrogen atoms and 1 ttz-NH in the ligand21 nitrogen atom of (2) to coordinate, adjacent Zn2+Ions first pass through btca2-The ligand forms a two-dimensional step-like structure, and thenBy ttz-NH2The ligands form a three-dimensional network structure; the molecular crystalline catalyst presents a regular hexagonal pore channel structure in the a direction, and the pore size of the molecular crystalline catalyst is about
For CO2A method for preparing a molecular crystalline catalyst for cycloaddition reaction with an epoxy compound, said method comprising the synthetic steps of:
(1) organic ligand H2btca、ttz-NH2And Zn (NO)3)2·6H2Dissolving O in a mixed solvent of N, N-dimethylformamide, deionized water and ethanol to obtain a mixed solution; the Hbtca and ttz-NH2、Zn(NO3)2·6H2O, N, the molar ratio of N-dimethylformamide to water to ethanol is 1:1:2:322.6:1667: 100;
(2) and (3) placing the mixed solution in a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 130 ℃, taking out a product, separating a solid, and washing the solid for multiple times by using N, N-dimethylformamide to obtain a yellow blocky crystal.
The molecular crystalline catalyst can be used as a catalyst for CO at normal temperature and normal pressure2Cycloaddition reaction with epoxy compound.
The invention also provides CO2Cycloaddition with epoxy Compound 20mmol of epoxy compound was added to a Schlenk reaction tube, followed by 5mg of molecular crystalline catalyst and 0.2mmol of tetrabutylammonium bromide, followed by introduction of 1atmCO2Reacting for 48 hours at room temperature by using gas to obtain the product.
The invention has the beneficial effects that (1) the molecular crystalline catalyst can be used as a catalyst for CO at normal temperature and normal pressure2Cycloaddition reaction with epoxy compound. (2) The molecular crystalline catalyst has the advantages of simple preparation process, high catalytic activity, good selectivity and good stability, and can be used for preparing CO2Has great potential application value in the aspect of cycloaddition reaction with epoxy compounds.
Drawings
FIG. 1 is a crystal diagram of a molecular crystalline catalyst of the present invention;
FIG. 2 is a three-dimensional structural view of the molecular crystalline catalyst of the present invention;
FIG. 3 is an x-ray powder diffraction pattern of the molecular crystalline catalyst of the present invention;
FIG. 4 is an infrared spectrum of a molecular crystalline catalyst of the present invention;
FIG. 5 is a thermal stability spectrum of the molecular crystalline catalyst of the present invention.
FIG. 6 shows CO2Cycloaddition with epoxy compounds.
Detailed Description
The present invention will be explained in further detail with reference to examples.
For CO2The preparation method of the molecular crystalline catalyst for cycloaddition reaction with the epoxy compound comprises the following synthetic steps:
zinc nitrate N, N-dimethylformamide solution with concentration of 0.1mol/L and H with concentration of 0.05mol/L2Mixing and performing ultrasonic treatment on a btca N, N-dimethylformamide solution for 10min, and adding ttz-NH with the concentration of 0.05mol/L into the mixed solution under the ultrasonic condition2Mixing the solution with ethanol and water, and continuing to perform ultrasonic treatment for 5 min; and (3) putting the mixed solution into a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 130 ℃, taking out a product, separating the solid, and washing for 3 times by using N, N-dimethylformamide to obtain blocky crystals.
The properties of the molecular crystalline catalyst prepared in this example are characterized as follows:
(1) the structure of the molecular crystalline catalyst of this example was determined:
the crystal structure is determined by Supernova X-ray single crystal diffractometer and Mo-Kalpha ray monochromatized by graphite
Collecting diffraction points in an omega-phi scanning mode for an incident radiation source, correcting by a least square method to obtain unit cell parameters, directly solving a difference Fourier electron density diagram by using SHELXL-97 to obtain a crystal structure, and correcting by Lorentz and a polarization effect. All H atoms are formed by the difference FourierSynthesized and determined by the ideal position calculation. The detailed crystal determination data are shown in table 1.
TABLE 1 crystallography data for molecular crystalline catalysts
FIG. 1 is a crystal diagram of a molecular crystalline catalyst, from which it can be seen that: presence of 1 Zn in the smallest asymmetric structural unit2+Ion, 1 btca2-Ligand, 0.5 ttz-NH2In which Zn is2+The ions adopt a coordination mode of four-coordinate tetrahedron and are respectively linked with 3 btca2-1 oxygen atom, 2 nitrogen atoms and 1 ttz-NH in the ligand21 nitrogen atom of (a) is coordinated.
FIG. 2 is a three-dimensional structure diagram of a molecular crystalline catalyst, from which it can be seen that: the molecular crystalline catalyst presents a regular hexagonal pore channel structure in the a direction, and the pore size of the molecular crystalline catalyst is about
(2) Phase purity testing of molecular crystalline catalysts:
the x-ray powder diffraction pattern of the molecular crystalline catalyst was tested in a room temperature environment. As can be seen from FIG. 3, the measured powder diffraction pattern is compared with its simulated pattern, except that the intensities of some peaks are slightly different, the positions and the peak shapes of the peaks can be well matched, which indicates that the molecular crystalline catalyst has higher phase purity.
(3) And (3) infrared spectrum characterization of the molecular crystalline catalyst:
FIG. 4 is an infrared spectrum of a molecular crystalline catalyst, which is seen at 3423cm-1cm-1A broad absorption band occurs, mainly due to O-H stretching vibration of water molecules in the molecular crystalline catalyst, and peaks are split and shifted to lower wave numbers due to association of hydrogen bonds. At 1635cm-1The strong absorption peaks in the vicinity are due to the antisymmetric stretching of the carboxyl groups. The absorption peak of the symmetric expansion and contraction of the carboxyl group appears at 1378cm-1Nearby.
Fig. 5 is a thermal stability spectrum of a molecular crystalline catalyst. As can be seen from the figure: when the temperature is increased to about 100 ℃, the weight loss is 6.82 percent, and when the temperature is continuously increased, the structure of the molecular crystalline catalyst collapses, which corresponds to 3 free guest molecules in the lost crystal lattice.
The molecular crystalline catalyst is used for CO2The cycloaddition reaction with epoxy compound includes the following steps:
20mmol of epoxide were introduced into a Schlenk reaction tube, followed by 5mg of molecular crystalline catalyst and 0.2mmol of tetrabutylammonium bromide, and then by introduction of 1atm CO2Reacting for 48 hours at room temperature by using gas to obtain the product. The blank control group was prepared by separately adding 5mg of molecular crystalline catalyst or 0.2mmol of tetrabutylammonium bromide, respectively, under otherwise unchanged conditions.
Table 2 shows the evaluation of the catalytic effect of the molecular crystalline catalyst of the present invention
TABLE 2 evaluation of catalytic Effect of molecular crystalline catalyst
As can be seen from Table 2, the molecular crystalline catalyst can be used as a catalyst for CO at normal temperature and pressure2The catalyst has the advantages of simple preparation process, high catalytic activity, good selectivity and good stability when being subjected to cycloaddition reaction with an epoxy compound, and can be used for preparing a catalyst for CO2Has great potential application value in the aspect of cycloaddition reaction with epoxy compounds. The molecular crystalline catalyst and tetrabutyl ammonium bromide are used as the catalyst together, and the effect is far better than that of a single catalyst.
Claims (6)
1. For CO2A molecular crystalline catalyst for cycloaddition reaction with epoxy compounds, characterized by: the chemical formula is { [ Zn ]2(btca)2(ttz-NH2)]·3solvents}nWherein b istca2-Is 5-carboxylic acid benzotriazole dianion, ttz-NH2Is 5-aminotetrazole, 3solvents are 3solvent molecules, and n is a natural number from 1 to infinity.
2. The method for CO of claim 12A molecular crystalline catalyst for cycloaddition reaction with epoxy compounds, characterized by: the molecular crystalline catalyst belongs to an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:
alpha is 90 deg., beta is 90 deg., gamma is 90 deg., crystal volume is
Z＝4。
3. Use for CO according to claim 22A molecular crystalline catalyst for cycloaddition reaction with epoxy compounds, characterized by: 1 Zn exists in the minimum asymmetric structural unit of the molecular crystalline catalyst2+Ion, 1 btca2-Ligand, 0.5 ttz-NH2In which Zn is2+The ions adopt a coordination mode of four-coordinate tetrahedron and are respectively linked with 3 btca2-1 oxygen atom, 2 nitrogen atoms and 1 ttz-NH in the ligand21 nitrogen atom of (2) to coordinate, adjacent Zn2+Ions first pass through btca2-The ligand forms a two-dimensional step-like structure and passes through ttz-NH2The ligands form a three-dimensional network structure; the molecular crystalline catalyst presents a regular hexagonal pore channel structure in the a direction, and the pore size of the molecular crystalline catalyst is
4. A process as claimed in claim 1 for CO2The preparation method of the molecular crystalline catalyst for cycloaddition reaction with the epoxy compound is characterized by comprising the following synthetic steps:
(1) will be organicLigand H2btca、ttz-NH2And Zn (NO)3)2 .6H2Dissolving O in a mixed solvent of N, N-dimethylformamide, deionized water and ethanol to obtain a mixed solution; said H2btca、ttz-NH2、Zn(NO3)2.6H2O, N, the molar ratio of N-dimethylformamide to water to ethanol is 1:1:2:322.6:1667: 100;
(2) and (3) placing the mixed solution in a closed hydrothermal reaction kettle, reacting for 72 hours at a constant temperature of 130 ℃, taking out a product, separating a solid, and washing the solid for multiple times by using N, N-dimethylformamide to obtain a yellow blocky crystal.
5. The method for CO of claim 12The application of the molecular crystalline catalyst for cycloaddition reaction with epoxy compound is characterized in that: the molecular crystalline catalyst can be used as a catalyst for CO at normal temperature and normal pressure2Cycloaddition reaction with epoxy compound.
6. CO (carbon monoxide)2The cycloaddition method with epoxy compound is characterized in that: 20mmol of epoxide were introduced into a Schlenk reaction tube, followed by 5mg of molecular crystalline catalyst and 0.2mmol of tetrabutylammonium bromide, and then by introduction of 1atm CO2Reacting for 48 hours at room temperature by using gas to obtain the product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110293496A1 (en) * | 2010-05-25 | 2011-12-01 | Valdez Carlos A | Synthesis of triazole-based and imidazole-based zinc catalysts |
| CN102336736A (en) * | 2011-07-18 | 2012-02-01 | 中国科学院过程工程研究所 | Method for catalyzing and preparing annular carbonic ester by supported ionic liquid |
| CN103936773A (en) * | 2014-04-08 | 2014-07-23 | 陕西师范大学 | 1, 4-terephthalic acid-regulated polyazole coordination polymer and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110293496A1 (en) * | 2010-05-25 | 2011-12-01 | Valdez Carlos A | Synthesis of triazole-based and imidazole-based zinc catalysts |
| CN102336736A (en) * | 2011-07-18 | 2012-02-01 | 中国科学院过程工程研究所 | Method for catalyzing and preparing annular carbonic ester by supported ionic liquid |
| CN103936773A (en) * | 2014-04-08 | 2014-07-23 | 陕西师范大学 | 1, 4-terephthalic acid-regulated polyazole coordination polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YIXING LI ET AL.: "Porous Zn(Bmic)(AT) MOF with Abundant Amino Groups and Open Metal Sites for Efficient Capture and Transformation of CO2", 《INORGANIC CHEMISTRY》 * |
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