CN109759137A - Heterogeneous catalysis and its synthetic method derived from a kind of metallo organic material - Google Patents
Heterogeneous catalysis and its synthetic method derived from a kind of metallo organic material Download PDFInfo
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- CN109759137A CN109759137A CN201910140497.XA CN201910140497A CN109759137A CN 109759137 A CN109759137 A CN 109759137A CN 201910140497 A CN201910140497 A CN 201910140497A CN 109759137 A CN109759137 A CN 109759137A
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Abstract
The invention discloses heterogeneous catalysis derived from a kind of metallo organic material and its synthetic methods.Use metallo organic material Co-BTC as the persursor material of synthetic catalyst, using methylimidazole 2MeIm as function dough reagent, the heterogeneous catalysis 2MeIm@Co-BTC of hexagonal prism structure derived from the Co-BTC of synthesis, the material has new crystal phase in 2 θ=12.22 °, and surface has mesoporous and micropore hierarchical porous structure with hexagonal prism structure and inside.First Co-BTC is dispersed in methanol solution, it is mixed again with 2MeIm methanol solution, 30min is stirred at room temperature, then fast sealing has catalyst (2MeIm@Co-BTC-x) derived from the Co-BTC of different quality ratio by solvent-thermal method preparation in the stainless steel autoclave of polytetrafluoroethyllining lining.The success of the method for preparing catalyst provides a kind of designed for catalysis CO2The method for being converted into synthesizing annular carbonate special material, to special appearance, the controlledly synthesis of catalytic performance and hierarchical porous structure has certain theory and directive significance.
Description
Technical field
The present invention relates to the controlledly synthesis of different-shape metallo organic material and CO2Epoxidation is fixed using field, more
It says to body, be related to heterogeneous catalysis and its synthetic method derived from a kind of metallo organic material, which can be used for urging
Change greenhouse gases CO2The catalytic fields such as chemical fixation, gas absorption, electrochemistry.
Background technique
In the past few decades, CO2 emissions sharply increase, this promotes weather that great variety has occurred.Cause
This, it is particularly important to sustainable development to develop catalysis transform of carbon dioxide approach.Carbon dioxide is nontoxic due to harmless, and price is honest and clean
Valence is preferably to can be used for chemically synthesized renewable C1 raw material.Importantly, being useful chemicals carbon dioxide conversion
Concern increasingly by industry and academia, wherein carbon dioxide, which is catalyzed and synthesized ring carbonic ether with epoxide, is
Carbon dioxide utilizes one of most promising reaction.This can be used as mainly due to cyclic carbonate has extensive commercial application
Polar solvent, the electrolyte in lithium battery produce the intermediate and polycarbonate synthesis and polyurethane drug of fine chemicals
Important compound and proparea body.
Up to the present, various compounds, such as ionic liquid, alkali halide, boron phosphate, functional polymer, quaternary ammonium
Salt or phosphonium salt have been widely used as the catalyst for promoting carbon dioxide epoxidation fixed.But difficulty is separated using such catalyst,
And the product treatment after reacting is complex.Therefore, the limitation of these technologies, to force researcher to be dedicated to developing in recent years
The catalyst system mild for synthesizing cyclic carbonate ester.It is interesting that some metallo organic materials exist in its crystal structure
Lewis Acid-Base active site, has been explored the catalyst as carbon dioxide cycloaddition.For example, utilizing MOF-5 and co-catalysis
Agent (n-Bu4NBr) it is catalyzed CO2With propylene oxide synthetizing propylene carbonate.In solvent-free system, ZIF-8 and Cu are utilized3
(BTC)2Catalyze and synthesize CO2Synthesis carbonic acid chloropropene ester (CPC).In addition, when being doped with Zn to ZIF-67 lattice, and
For carbon dioxide and epoxychloropropane catalyst system, compared with ZIF-67, the conversion ratio for aoxidizing chloropropane is remarkably reinforced.To sum up
It is described, the processing of function doughization is carried out to some MOFs, catalytic activity can be improved with it.Although [(CH3)2NH2][Co3(BTC)
(HCOO)4(H2O)]·H2O (Co-BTC) can be used for CO2Catalyzed conversion system, but required severe reaction conditions (120
DEG C, 9h).Although methylimidazole (2MeIm) is to CO2Catalytic activity with higher, but be difficult to recycle.In addition,
2MeIm can carry out coordination with Co ion and form ZIF-67 structure.
Therefore, it can be synthesized by unsaturation Co ion coordination in 2MeIm and Co-BTC, regulation a kind of for carbon dioxide
The fixed new material (2MeIm@Co-BTC) of epoxidation.The material is provided simultaneously with various active site, and catalytic activity is high, and prepares
It is fairly simple.The design that the success of the material is prepared as other catalysis materials provides a completely new thinking.
Summary of the invention
Technical problem: the catalytic activity in order to improve metallo organic material, the invention proposes a kind of metallo organic materials
The 2MeIm@Co-BTC catalyst of derivative heterogeneous catalysis and its synthetic method, synthesis has new crystal phase, microcosmic surface
There are hexagonal prism structure and relatively rich pore structure.Because the exposure of its surface has certain special crystal faces, catalytic activity is obviously mentioned
It is high.Thus, the success of the method for preparing catalyst provides a kind of designed for being catalyzed greenhouse gases synthesizing annular carbonate
The method of special material in terms of the controlledly synthesis of catalytic performance and cellular structure there is certain guidance to anticipate in material morphology
Justice.
Technical solution: the metallo organic material heterogeneous catalysis of hexagonal prism structure function dough of the invention, with gold
Belong to persursor material of the organic material Co-BTC as synthetic catalyst, using methylimidazole 2MeIm as function dough reagent, closes
At hexagonal prism structure function dough Co-BTC heterogeneous catalysis 2MeIm Co-BTC, which has in 2 θ=12.22 °
There is new crystal phase, surface has mesoporous and micropore hierarchical porous structure with hexagonal prism structure and inside.
The synthetic method of the metallo organic material heterogeneous catalysis of hexagonal prism structure function dough of the invention, specifically
Synthesis process is as follows:
A. by four water cobalt chloride CoCl2·4H2O, trimesic acid H3BTC is added sequentially to dimethylformamide DMF and goes
In the mixture of ionized water, after being vigorously stirred, mixed liquor is transferred to stainless steel autoclave and is sealed, then carry out crystallization；To crystalline substance
After change, crystal is washed with deionized for several times, and is dried in air to remove hydrone, Co-BTC is made；
B. Co-BTC compound is distributed in methanol solution, is then mixed with 2MeIm methanol solution, after stirring, will mixed
Solution fast sealing is closed in the stainless steel autoclave of polytetrafluoroethyllining lining, and carries out crystallization at a certain temperature；Crystallization
After, it filters and non-derived from metallo organic material of the dry sediment obtained to get hexagonal prism structure function dough
The heterogeneous catalysis 2MeIm@Co-BTC of hexagonal prism structure derived from homogeneous catalyst, that is, Co-BTC.
The CoCl2·4H2O and H3Molar fraction of the BTC in reaction solution is respectively 5~15 and 1.5~5mmol.
The volume of the DMF is 10~50ml.
The volume of the methanol is 30~80ml.
The mass ratio of the 2MeIm and Co-BTC is 0.1~3.0.
The temperature of the crystallization at a certain temperature is 100~160 DEG C.
The crystallization at a certain temperature, time are 12~96h.
Unsaturated Co ion is coordinated in 2MeIm and Co-BTC, is formd with special appearance hexagonal prism structure
Catalyst.Inside solvent thermal process, lattice material and surface forms hierarchical porous structure, is the exposure of more active sites
Provide advantageous condition.The heterogeneous catalysis of hexagonal prism structure derived from the Co-BTC of preparation has special nature, can
For being catalyzed greenhouse gases CO2The fields such as conversion, degradation of organic substances.
The utility model has the advantages that firstly, CoCl2·4H2O、H3BTC and DMF itself are common basic organic solvents, inexpensive easy
, and can simply prepare Co-BTC.Secondly, foring after 2MeIm is introduced with special appearance hexagonal prism and porous structure
New material, mainly since the unsaturated Co ion of 2MeIm and Co-BTC is coordinated.In addition, since Co-BTC is derivative
The heterogeneous catalysis of hexagonal prism structure there is cellular structure abundant, many active sites can be provided for it, to have
Improve the catalytic activity of catalyst itself in effect ground.
Detailed description of the invention
Fig. 1 is the XRD diagram of 2MeIm@Co-BTC sample in case study on implementation 1.
Fig. 2 is 2MeIm@Co-BTC catalyst SEM electron microscope in case study on implementation 1.
Fig. 3 is the nitrogen adsorption desorption curve figure of 2MeIm@Co-BTC sample in case study on implementation 1.
Specific embodiment
The heterogeneous catalysis catalysis carbon dioxide and epoxides of hexagonal prism structure derived from embodiment 1.Co-BTC
Coupling reaction
1. preparing presoma (Co-BTC)
By CoCl2·4H2O (15mmol) and H3BTC (5mmol) is added sequentially to DMF (30ml) and deionized water (30ml)
Mixture in, after being vigorously stirred 30 minutes, be transferred in the stainless steel autoclave of 100ml polytetrafluoroethyllining lining.Acutely stir
After mixing 30 minutes, autoclave is sealed, and is heated 96 hours at 120 DEG C.Acquired solution is cooled to room temperature, deionized water is used
Washing gained crystal for several times, is then dried in air to remove hydrone.
2. preparing the heterogeneous catalysis of hexagonal prism structure derived from Co-BTC
Prepare heterogeneous catalysis (mass ratio 2MeIm/Co-BTC) derived from Co-BTC.First by Co-BTC (1.0g)
Compound is distributed in 40ml methanol solution, is then mixed with 2MeIm (0.2g) methanol solution (30ml).After stirring 30 minutes,
By mixed solution fast sealing in the stainless steel autoclave of polytetrafluoroethyllining lining, and heated 24 hours at 120 DEG C.Filtering
The sediment of acquisition is in 60 DEG C of dry 12h to get the Co-BTC catalyst of function dough.By the 2MeIm with different quality ratio
Function dough Co-BTC is denoted as 2MeIm Co-BTC-0.2.
The heterogeneous catalysis catalysis carbon dioxide and epoxides of hexagonal prism structure derived from embodiment 2.Co-BTC
Coupling reaction
1. preparing presoma (Co-BTC)
By CoCl2·4H2O (15mmol) and H3BTC (5mmol) is added sequentially to DMF (30ml) and deionized water (30ml)
Mixture in, after being vigorously stirred 30 minutes, be transferred in the stainless steel autoclave of 100ml polytetrafluoroethyllining lining.By high pressure
Kettle sealing, and heated 96 hours at 120 DEG C.Acquired solution is cooled to room temperature, gained crystal is washed with deionized for several times,
Then it dries in air to remove hydrone.
2. preparing the heterogeneous catalysis of hexagonal prism structure derived from Co-BTC
Prepare heterogeneous catalysis (mass ratio 2MeIm/Co-BTC) derived from Co-BTC.First by Co-BTC (1.0g)
Compound is distributed in 40ml methanol solution, is then mixed with 2MeIm (1.0g) methanol solution (30ml).After stirring 30 minutes,
By mixed solution fast sealing in the stainless steel autoclave of polytetrafluoroethyllining lining, and heated 24 hours at 120 DEG C.Filtering
The sediment of acquisition is in 60 DEG C of dry 12h to get the Co-BTC catalyst of function dough.By the 2MeIm with different quality ratio
Function dough Co-BTC is denoted as 2MeIm Co-BTC-1.0.
The heterogeneous catalysis catalysis carbon dioxide and epoxides of hexagonal prism structure derived from embodiment 3.Co-BTC
Coupling reaction
1. preparing presoma (Co-BTC)
By CoCl2·4H2O (15mmol) and H3BTC (5mmol) is added sequentially to DMF (30ml) and deionized water (30ml)
Mixture in, after being vigorously stirred 30 minutes, be transferred in the stainless steel autoclave of 100ml polytetrafluoroethyllining lining.By high pressure
Kettle sealing, and heated 96 hours at 120 DEG C.Acquired solution is cooled to room temperature, gained crystal is washed with deionized for several times,
Then it dries in air to remove hydrone.
2. preparing the heterogeneous catalysis of hexagonal prism structure derived from Co-BTC
Prepare heterogeneous catalysis (mass ratio 2MeIm/Co-BTC) derived from Co-BTC.First by Co-BTC (1.0g)
Compound is distributed in 40ml methanol solution, is then mixed with 2MeIm (1.5g) methanol solution (30ml).After stirring 30 minutes,
By mixed solution fast sealing in the stainless steel autoclave of polytetrafluoroethyllining lining, and heated 24 hours at 120 DEG C.Filtering
The sediment of acquisition is in 60 DEG C of dry 12h to get the Co-BTC catalyst of function dough.By the 2MeIm with different quality ratio
Function dough Co-BTC is denoted as 2MeIm Co-BTC-1.5.
The experiment of the coupling reaction of catalyst carbon dioxide and epoxides derived from Co-BTC
The coupling reaction of carbon dioxide and epoxides carries out in stainless steel autoclave (100ml).Pass through electromagnetic agitation
Device promotes the mass transfer between reactant and catalyst, and passes through thermocouple measurement system temperature.In general, by reactant and urging first
Agent is added in stainless steel reactor, after sealing, is purified three times with carbon dioxide to system.Then, reactor is heated to setting
Determine temperature.When after reaction, system is rapidly cooled to room temperature.It collects without catalyst liquid and with equipped with SE-54 capillary
The gas chromatograph (Shandong Teng Hai, GC-6890) of the flame ionization detector of tubing string (30m × 0.32mm × 1 μm) is examined
It surveys.
The result shows that when using the catalyst of 0.75%ECH weight in catalyst system, in 2MeIm@Co-BTC-1.0
Highest catalytic activity is detected under (3.0MPa, 90 DEG C, 5h), i.e., ECH conversion ratio is 97.21% and CPC is selectively
98.79%.The heterogeneous catalysis can convert in 90 DEG C of promotion epoxychloropropane, and obtain higher yield.With conventional method
The catalyst of preparation is compared, and this method has apparent superiority.
Claims (8)
1. heterogeneous catalysis derived from a kind of metallo organic material, which is characterized in that use metallo organic material Co-BTC as
The persursor material of synthetic catalyst, using methylimidazole 2MeIm as function dough reagent, the surface of synthesis has hexagonal prism
The heterogeneous catalysis 2MeIm@Co-BTC of structure, the material have new crystal phase in 2 θ=12.22 °, and surface has six side's ribs
Rod structure and inside have mesoporous and micropore hierarchical porous structure.
2. a kind of synthetic method of heterogeneous catalysis derived from metallo organic material as described in claim 1, which is characterized in that
Specific synthesis process is as follows:
A. by four water cobalt chloride CoCl2·4H2O, trimesic acid H3BTC is added sequentially to dimethylformamide DMF and deionization
In the mixture of water, after being vigorously stirred, mixed liquor is transferred to stainless steel autoclave and is sealed, then carry out crystallization.To crystallization knot
Crystal is washed with deionized for several times in Shu Hou, and is dried in air to remove hydrone, and Co-BTC is made；
B. Co-BTC compound is distributed in methanol solution, is then mixed with 2MeIm methanol solution, after stirring, will mixed molten
Liquid fast sealing carries out crystallization in the stainless steel autoclave of polytetrafluoroethyllining lining at a certain temperature；Crystallization terminates
Afterwards, it filters and heterogeneous derived from metallo organic material of the dry sediment obtained to get hexagonal prism structure function dough
The heterogeneous catalysis 2MeIm@Co-BTC of hexagonal prism structure derived from catalyst, that is, Co-BTC.
3. the synthetic method of heterogeneous catalysis derived from metallo organic material according to claim 2, which is characterized in that
The CoCl2·4H2O and H3Molar fraction of the BTC in reaction solution is respectively 5~15 and 1.5~5mmol.
4. the synthetic method of heterogeneous catalysis derived from metallo organic material according to claim 2, which is characterized in that
The volume of the DMF is 10~50ml.
5. the synthetic method of heterogeneous catalysis derived from metallo organic material according to claim 2, which is characterized in that
The volume of the methanol is 30~80ml.
6. the synthetic method of heterogeneous catalysis derived from metallo organic material according to claim 2, which is characterized in that
The mass ratio of the 2MeIm and Co-BTC is 0.1~3.0.
7. the synthetic method of heterogeneous catalysis derived from metallo organic material according to claim 2, which is characterized in that
The temperature of the crystallization at a certain temperature is 100~160 DEG C.
8. the synthetic method of heterogeneous catalysis derived from metallo organic material according to claim 2, which is characterized in that
The crystallization at a certain temperature, time are 12~96h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833852A (en) * | 2016-05-26 | 2016-08-10 | 华南理工大学 | MOFs composite adsorption material IMI@Cu-BTC and preparation method thereof |
| US20160243525A1 (en) * | 2016-05-02 | 2016-08-25 | LiSo Plastics, L.L.C. | Multilayer Polymeric Membrane and Process |
| CN107096569A (en) * | 2017-04-28 | 2017-08-29 | 新疆大学 | A kind of efficient catalytic carbon dioxide and the catalyst of epoxides cycloaddition reaction |
| CN111187417A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Modification method and application of metal organic framework material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160243525A1 (en) * | 2016-05-02 | 2016-08-25 | LiSo Plastics, L.L.C. | Multilayer Polymeric Membrane and Process |
| CN105833852A (en) * | 2016-05-26 | 2016-08-10 | 华南理工大学 | MOFs composite adsorption material IMI@Cu-BTC and preparation method thereof |
| CN107096569A (en) * | 2017-04-28 | 2017-08-29 | 新疆大学 | A kind of efficient catalytic carbon dioxide and the catalyst of epoxides cycloaddition reaction |
| CN111187417A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Modification method and application of metal organic framework material |
Non-Patent Citations (2)
| Title |
|---|
| YUANFENG WU等: "2-Methylimidazole Modified Co-BTC MOF as an Efficient Catalyst for Chemical Fixation of Carbon Dioxide", 《CATALYSIS LETTERS 》 * |
| YUANFENG WU等: "Zn2(C9H3O6)(C4H5N2)(C4H6N2)3MOF as a highlyefficient catalyst for chemical fixation of CO2 intocyclic carbonates and kinetic studies", 《CHEMICAL ENGINEERING RESEARCH AND DESIGN》 * |
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