CN109759137B - Heterogeneous catalyst derived from metal organic material and synthetic method thereof - Google Patents
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- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明公开了一种金属有机材料衍生的非均相催化剂及其合成方法。用金属有机材料Co‑BTC作为合成催化剂的前驱体材料，以二甲基咪唑2MeIm为官能团化试剂，合成的Co‑BTC衍生的六方棱柱结构的非均相催化剂2MeIm@Co‑BTC，该材料在2θ＝12.22°具有新的晶相，表面具有六方棱柱结构以及内部具有介孔和微孔的多级孔结构。先将Co‑BTC分散在甲醇溶液中，再与2MeIm甲醇溶液混合，室温搅拌30min，然后快速密封在聚四氟乙烯内衬的不锈钢高压釜中，通过溶剂热法制备具有不同质量比的Co‑BTC衍生的催化剂(2MeIm@Co‑BTC‑x)。该催化剂制备方法的成功，提供了一种设计用于催化CO2转化为合成环状碳酸酯特殊材料的方法，对特殊形貌，催化性能以及多级孔结构的可控合成具有一定的理论和指导意义。
The invention discloses a heterogeneous catalyst derived from a metal organic material and a synthesis method thereof. The metal-organic material Co-BTC is used as the precursor material for the synthesis catalyst, and the dimethylimidazole 2MeIm is used as the functionalization reagent to synthesize the Co-BTC-derived hexagonal prism-structured heterogeneous catalyst 2MeIm@Co-BTC. The material is in 2θ=12.22° has a new crystal phase, with a hexagonal prism structure on the surface and a hierarchical pore structure with mesopores and micropores inside. Co-BTC was first dispersed in methanol solution, then mixed with 2MeIm methanol solution, stirred at room temperature for 30 min, and then quickly sealed in a PTFE-lined stainless steel autoclave to prepare Co-BTC with different mass ratios by solvothermal method BTC-derived catalyst (2MeIm@Co‑BTC‑x). The success of this catalyst preparation method provides a method designed to catalyze the conversion of CO2 into special materials for the synthesis of cyclic carbonates, with certain theoretical and Guiding significance.
Description
Technical Field
The invention relates to controllable synthesis of metal organic materials with different morphologies and CO2The field of epoxidation fixed utilization, in particular to a heterogeneous catalyst derived from a metal organic material and a synthesis method thereof, wherein the catalyst can be used for catalyzing greenhouse gas CO2Chemical fixation, gas adsorption, electrochemistry and other catalysis fields.
Background
Over the past few decades, there has been a dramatic increase in carbon dioxide emissions, which has prompted dramatic changes in climate. Therefore, the development of a catalytic carbon dioxide conversion pathway is particularly important for sustainable development. Carbon dioxide is an ideal renewable C1 raw material for chemical synthesis because it is harmless, non-toxic, and cheap. Importantly, the conversion of carbon dioxide to useful chemicals is of increasing interest to the industrial and academic community, where the catalytic synthesis of cyclic carbonates from carbon dioxide with epoxy compounds is one of the most promising reactions for carbon dioxide utilization. This is mainly due to the wide commercial use of cyclic carbonates as polar solvents, electrolytes in lithium batteries, intermediates for the production of fine chemicals and important compounds and precursors for the synthesis of polycarbonates and polyurethane pharmaceuticals.
Up to now, various compounds such as ionic liquids, alkali metal halides, boron phosphates, functional polymers, quaternary ammonium salts or phosphonium salts have been widely used as catalysts for promoting fixation of epoxidation of carbon dioxide. However, the use of such catalysts is difficult to separate and the treatment of the products after the reaction is complicated. Therefore, limitations of these techniques have forced researchers to work in recent years to develop mild catalytic systems for the synthesis of cyclic carbonates. Interestingly, some metal organic materials have Lewis acid-base active sites within their crystal structure and have been explored for use as catalysts for carbon dioxide cycloaddition. For example, using MOF-5 and a cocatalyst (n-Bu)4NBr) catalysis of CO2And propylene oxide to synthesize propylene carbonate. In a solvent-free system, using ZIF-8 and Cu3(BTC)2Catalytic synthesis of CO2And (3) converting to synthesize the propylene carbonate (CPC). In addition, when the ZIF-67 lattice is doped with Zn and used in a carbon dioxide and epichlorohydrin catalytic system, the conversion of epichlorohydrin is significantly enhanced compared to ZIF-67. In summary, some MOFs can be functionalized to improve catalytic activity. Albeit [ (CH)3)2NH2][Co3(BTC)(HCOO)4(H2O)]·H2O (Co-BTC) can be used for CO2But the reaction conditions required are severe (120 ℃, 9 h). Although, 2-methylimidazole (2MeIm) on CO2Has high catalytic activity, but is difficult to recycle. In addition, 2MeIm can coordinate with Co ions to form a ZIF-67 structure.
Therefore, a new material (2MeIm @ Co-BTC) for carbon dioxide epoxidation fixation can be regulated and synthesized through coordination of 2MeIm and unsaturated Co ions in Co-BTC. The material has multiple active sites, high catalytic activity and simple preparation. The successful preparation of the material provides a brand new idea for the design of other catalytic materials.
Disclosure of Invention
The technical problem is as follows: in order to improve the catalytic activity of the metal organic material, the invention provides a heterogeneous catalyst derived from the metal organic material and a synthesis method thereof, and the synthesized 2MeIm @ Co-BTC catalyst has a new crystal phase and a hexagonal prism structure and a rich porous structure on the microscopic surface. Because some special crystal faces are exposed on the surface of the catalyst, the catalytic activity is obviously improved. Therefore, the success of the preparation method of the catalyst provides a method for designing a special material for catalyzing greenhouse gases to synthesize cyclic carbonate, and has certain guiding significance in the aspects of material morphology, catalytic performance and controllable synthesis of pore channel structures.
The technical scheme is as follows: the invention relates to a metal organic material heterogeneous catalyst with a functionalized hexagonal prism structure, which is characterized in that a metal organic material Co-BTC is used as a precursor material for synthesizing the catalyst, 2-methylimidazole 2MeIm is used as a functionalizing reagent, and the synthesized Co-BTC heterogeneous catalyst 2MeIm @ Co-BTC with the functionalized hexagonal prism structure has a new crystal phase at 2 theta of 12.22 degrees, and the surface of the material has a hexagonal prism structure and a hierarchical pore structure with mesopores and micropores inside.
The invention relates to a synthesis method of a metal organic material heterogeneous catalyst with a functionalized hexagonal prism structure, which comprises the following specific synthesis processes:
a. cobalt chloride tetrahydrate CoCl2·4H2O, trimesic acid H3BTC is sequentially added into a mixture of dimethyl formamide DMF and deionized water, after vigorous stirring, the mixed solution is transferred into a stainless steel autoclave and sealed, and then crystallization is carried out; after the crystallization is finished, useWashing the crystal with deionized water for several times, and drying in air to remove water molecules to obtain Co-BTC;
b. dispersing a Co-BTC compound into a methanol solution, then mixing the Co-BTC compound with a 2MeIm methanol solution, stirring, quickly sealing the mixed solution in a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, and crystallizing at a certain temperature; and after crystallization is finished, filtering and drying the obtained precipitate to obtain the heterogeneous catalyst derived from the metal organic material with the functionalized hexagonal prism structure, namely the heterogeneous catalyst 2MeIm @ Co-BTC with the hexagonal prism structure derived from Co-BTC.
The CoCl2·4H2O and H3The molar weight of BTC in the reaction solution is 5-15 mmol and 1.5-5 mmol respectively.
The volume of the DMF is 10-50 ml.
The volume of the methanol is 30-80 ml.
The mass ratio of the 2MeIm to the Co-BTC is 0.1-3.0.
The crystallization temperature at a certain temperature is 100-160 ℃.
And crystallizing at a certain temperature for 12-96 hours.
The 2MeIm is coordinated with unsaturated Co ions in Co-BTC to form the catalyst with a hexagonal prism structure with special appearance. In the solvothermal process, a hierarchical pore structure is formed inside and on the surface of the crystal lattice material, and favorable conditions are provided for exposing more active sites. The prepared heterogeneous catalyst with the Co-BTC derived hexagonal prism structure has special properties and can be used for catalyzing greenhouse gas CO2Converting and degrading organic matters.
Has the advantages that: first, CoCl2·4H2O、H3BTC and DMF are common basic organic solvents, are cheap and easily available, and can be used for simply preparing Co-BTC. And secondly, after the 2MeIm is introduced, a new material with a hexagonal prism and a porous structure with special shapes is formed, and the 2MeIm is mainly coordinated with unsaturated Co ions of Co-BTC. In addition, the heterogeneous catalyst with the hexagonal prism structure derived from Co-BTC has rich pore channel structure, so that much activity can be provided for the heterogeneous catalystThereby effectively improving the catalytic activity of the catalyst.
Drawings
FIG. 1 is an XRD pattern of the 2MeIm @ Co-BTC sample in example 1.
FIG. 2 is an SEM image of the 2MeIm @ Co-BTC catalyst in example 1.
FIG. 3 is a graph showing the nitrogen adsorption and desorption of the 2MeIm @ Co-BTC sample in example 1.
Detailed Description
Example 1 heterogeneous Co-BTC derived hexagonal prism Structure catalyst for coupling reaction of carbon dioxide with epoxide
1. Preparation of precursor (Co-BTC)
Adding CoCl2·4H2O (15mmol) and H3BTC (5mmol) was added sequentially to a mixture of DMF (30ml) and deionised water (30ml) and after vigorous stirring for 30 minutes was transferred to a 100ml stainless steel autoclave lined with Teflon. After stirring vigorously for 30 minutes, the autoclave was sealed and heated at 120 ℃ for 96 hours. The resulting solution was cooled to room temperature, and the resulting crystals were washed several times with deionized water, and then dried in air to remove water molecules.
2. Preparation of heterogeneous Co-BTC-derived hexagonal prism structured catalyst
A Co-BTC derived heterogeneous catalyst (mass ratio 2MeIm/Co-BTC) was prepared. The Co-BTC (1.0g) compound was first dispersed in 40ml of methanol solution and then mixed with 2MeIm (0.2g) of methanol solution (30 ml). After stirring for 30 minutes, the mixed solution was quickly sealed in a polytetrafluoroethylene-lined stainless steel autoclave and heated at 120 ℃ for 24 hours. And drying the precipitate obtained by filtering at 60 ℃ for 12h to obtain the functionalized Co-BTC catalyst. 2MeIm functionalized Co-BTC with different mass ratios was designated as 2MeIm @ Co-BTC-0.2.
Example 2 heterogeneous Co-BTC derived hexagonal prism Structure catalyst for coupling reaction of carbon dioxide with epoxide
1. Preparation of precursor (Co-BTC)
Adding CoCl2·4H2O (15mmol) and H3BTC (5mmol) was added successivelyInto a mixture of DMF (30ml) and deionized water (30ml) and after vigorous stirring for 30 minutes was transferred to a 100ml stainless steel autoclave lined with Teflon. The autoclave was sealed and heated at 120 ℃ for 96 hours. The resulting solution was cooled to room temperature, and the resulting crystals were washed several times with deionized water, and then dried in air to remove water molecules.
2. Preparation of heterogeneous Co-BTC-derived hexagonal prism structured catalyst
A Co-BTC derived heterogeneous catalyst (mass ratio 2MeIm/Co-BTC) was prepared. The Co-BTC (1.0g) compound was first dispersed in 40ml of methanol solution and then mixed with 2MeIm (1.0g) of methanol solution (30 ml). After stirring for 30 minutes, the mixed solution was quickly sealed in a polytetrafluoroethylene-lined stainless steel autoclave and heated at 120 ℃ for 24 hours. And drying the precipitate obtained by filtering at 60 ℃ for 12h to obtain the functionalized Co-BTC catalyst. 2MeIm functionalized Co-BTC with different mass ratios was designated as 2MeIm @ Co-BTC-1.0.
Example 3 heterogeneous Co-BTC derived hexagonal prism Structure catalyst for coupling reaction of carbon dioxide with epoxide
1. Preparation of precursor (Co-BTC)
Adding CoCl2·4H2O (15mmol) and H3BTC (5mmol) was added sequentially to a mixture of DMF (30ml) and deionised water (30ml) and after vigorous stirring for 30 minutes was transferred to a 100ml stainless steel autoclave lined with Teflon. The autoclave was sealed and heated at 120 ℃ for 96 hours. The resulting solution was cooled to room temperature, and the resulting crystals were washed several times with deionized water, and then dried in air to remove water molecules.
2. Preparation of heterogeneous Co-BTC-derived hexagonal prism structured catalyst
A Co-BTC derived heterogeneous catalyst (mass ratio 2MeIm/Co-BTC) was prepared. The Co-BTC (1.0g) compound was first dispersed in 40ml of methanol solution and then mixed with 2MeIm (1.5g) of methanol solution (30 ml). After stirring for 30 minutes, the mixed solution was quickly sealed in a polytetrafluoroethylene-lined stainless steel autoclave and heated at 120 ℃ for 24 hours. And drying the precipitate obtained by filtering at 60 ℃ for 12h to obtain the functionalized Co-BTC catalyst. 2MeIm functionalized Co-BTC with different mass ratios was designated as 2MeIm @ Co-BTC-1.5.
Co-BTC derived catalyst for catalyzing coupling reaction experiment of carbon dioxide and epoxide
The coupling reaction of carbon dioxide with epoxide was carried out in a stainless steel autoclave (100 ml). Mass transfer between the reactants and catalyst was facilitated by an electromagnetic stirrer and the system temperature was measured by a thermocouple. Typically, the reactants and catalyst are first charged to a stainless steel reactor, which is sealed and the system is purified three times with carbon dioxide. Subsequently, the reactor was heated to the set temperature. When the reaction was complete, the system was rapidly cooled to room temperature. The catalyst-free liquid was collected and detected with a gas chromatograph (Shandong Tenghai, GC-6890) equipped with a flame ionization detector of SE-54 capillary column (30 m.times.0.32 mm.times.1 μm).
The results show that the highest catalytic activity, namely an ECH conversion of 97.21% and a CPC selectivity of 98.79%, was detected at 2MeIm @ Co-BTC-1.0(3.0MPa, 90 ℃, 5h) when 0.75% ECH weight of catalyst was used in the catalytic system. The heterogeneous catalyst can promote the conversion of epoxy chloropropane at 90 ℃, and obtains higher yield. Compared with the catalyst prepared by the traditional method, the method has obvious superiority.
Claims (8)
1. The heterogeneous catalyst derived from the metal organic material is characterized in that the metal organic material Co-BTC is used as a precursor material for synthesizing the catalyst, 2-methylimidazole 2MeIm is used as a functional group reagent, and the synthesized heterogeneous catalyst 2MeIm @ Co-BTC with the surface having a hexagonal prism structure is prepared by the method that the material is subjected to reaction at the temperature of 2 theta =12.22oHas a new crystal phase, a hexagonal prism structure on the surface and a hierarchical pore structure with mesopores and micropores inside.
2. A method for synthesizing the organometallic material derived heterogeneous catalyst according to claim 1, wherein the specific synthesis process is as follows:
a. cobalt chloride tetrahydrate CoCl2·4H2O, trimesic trimethyl benzeneAcid H3Sequentially adding BTC into a mixture of dimethyl formamide DMF and deionized water, stirring vigorously, transferring the mixed solution into a stainless steel autoclave, sealing, crystallizing, washing the crystal for several times by using deionized water after crystallization is finished, and drying in air to remove water molecules to obtain Co-BTC;
b. dispersing a Co-BTC compound into a methanol solution, then mixing the Co-BTC compound with a 2MeIm methanol solution, stirring, quickly sealing the mixed solution in a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, and crystallizing at a certain temperature; and after crystallization is finished, filtering and drying the obtained precipitate to obtain the heterogeneous catalyst derived from the metal organic material with the functionalized hexagonal prism structure, namely the heterogeneous catalyst 2MeIm @ Co-BTC with the hexagonal prism structure derived from Co-BTC.
3. The method of claim 2, wherein the CoCl is present in the heterogeneous catalyst2·4H2O and H3The molar weight of BTC in the reaction solution is 5-15 mmol and 1.5-5 mmol respectively.
4. The method of claim 2, wherein the volume of the DMF is 10-50 ml.
5. The method for synthesizing the organometallic material derived heterogeneous catalyst according to claim 2, wherein the volume of the methanol is 30 to 80 ml.
6. The method for synthesizing the organometallic material derived heterogeneous catalyst according to claim 2, wherein the mass ratio of the 2MeIm to the Co-BTC is 0.1 to 3.0.
7. The method for synthesizing the organometallic material derived heterogeneous catalyst according to claim 2, wherein the crystallization temperature at a certain temperature is 100 to 160 ℃.
8. The method for synthesizing the organometallic material derived heterogeneous catalyst according to claim 2, wherein the crystallization is performed at a certain temperature for 12 to 96 hours.
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| Zn2(C9H3O6)(C4H5N2)(C4H6N2)3MOF as a highlyefficient catalyst for chemical fixation of CO2 intocyclic carbonates and kinetic studies;Yuanfeng Wu等;《Chemical Engineering Research and Design》;20181026;第140卷;第273-282页 * |
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