{"title":"双功能固定化催化剂与N, N-二甲基甲酰胺协同作用,由CO2和环氧丙烷合成碳酸丙烯","authors":"Yue Fu, Hui Lv, Gui-Ping Cao, Shuang Ji, Peng Gao","doi":"10.1007/s11144-024-02723-w","DOIUrl":null,"url":null,"abstract":"<div><p>In the present work, bifunctional immobilized catalysts, incorporating Lewis acid and nucleophilic reagent, were prepared by supporting Zn–Br with ZSM-5 for the synthesis of propylene carbonate from CO<sub>2</sub> and propylene oxide. When the total loading of Zn–Br, <i>ω</i>, is 7.5wt%, and the molar ratio, <i>n</i>(Br)/<i>n</i>(Zn), is 3.0, ZnO-KBr-7.5-3.0@ZSM-5 exhibits the highest activity with the solvent N, N-dimethylformamide (DMF). The conversion of propylene oxide and the selectivity of propylene carbonate are up to 97.73% and 98.83%, respectively. Gas chromatography results reveal the presence of by-products, specifically acetone and propylene glycol, in addition to propylene carbonate. Characterizations identify the active components in ZnO-KBr-7.5-3.0@ZSM-5 as ZnO and KBr. Meanwhile, the experimental results prove that DMF serves as a co-catalyst. The catalytic mechanism of DMF and ZnO-KBr-7.5-3.0@ZSM-5 on the cycloaddition is proposed, and the reaction process is simulated. DMF contains a tertiary nitrogen structure, able to function as a Lewis base, thereby activating CO<sub>2</sub>. ZnO and KBr in ZnO-KBr-7.5–3.0@ZSM-5 work synergistically to boost epoxide ring opening. Subsequently, the activated CO<sub>2</sub> integrates into the ring-opened epoxide, resulting in the formation of propylene carbonate. Additionally, four cycles of replicate experiments show that the catalyst ZnO-KBr-7.5-3.0@ZSM-5 possessed good stability.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 1","pages":"189 - 205"},"PeriodicalIF":1.7000,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Bifunctional immobilized catalyst and N, N-dimethylformamide synergistically synthesize propylene carbonate from CO2 and propylene oxide\",\"authors\":\"Yue Fu, Hui Lv, Gui-Ping Cao, Shuang Ji, Peng Gao\",\"doi\":\"10.1007/s11144-024-02723-w\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In the present work, bifunctional immobilized catalysts, incorporating Lewis acid and nucleophilic reagent, were prepared by supporting Zn–Br with ZSM-5 for the synthesis of propylene carbonate from CO<sub>2</sub> and propylene oxide. When the total loading of Zn–Br, <i>ω</i>, is 7.5wt%, and the molar ratio, <i>n</i>(Br)/<i>n</i>(Zn), is 3.0, ZnO-KBr-7.5-3.0@ZSM-5 exhibits the highest activity with the solvent N, N-dimethylformamide (DMF). The conversion of propylene oxide and the selectivity of propylene carbonate are up to 97.73% and 98.83%, respectively. Gas chromatography results reveal the presence of by-products, specifically acetone and propylene glycol, in addition to propylene carbonate. Characterizations identify the active components in ZnO-KBr-7.5-3.0@ZSM-5 as ZnO and KBr. Meanwhile, the experimental results prove that DMF serves as a co-catalyst. The catalytic mechanism of DMF and ZnO-KBr-7.5-3.0@ZSM-5 on the cycloaddition is proposed, and the reaction process is simulated. DMF contains a tertiary nitrogen structure, able to function as a Lewis base, thereby activating CO<sub>2</sub>. ZnO and KBr in ZnO-KBr-7.5–3.0@ZSM-5 work synergistically to boost epoxide ring opening. Subsequently, the activated CO<sub>2</sub> integrates into the ring-opened epoxide, resulting in the formation of propylene carbonate. Additionally, four cycles of replicate experiments show that the catalyst ZnO-KBr-7.5-3.0@ZSM-5 possessed good stability.</p></div>\",\"PeriodicalId\":750,\"journal\":{\"name\":\"Reaction Kinetics, Mechanisms and Catalysis\",\"volume\":\"138 1\",\"pages\":\"189 - 205\"},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2024-09-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reaction Kinetics, Mechanisms and Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11144-024-02723-w\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reaction Kinetics, Mechanisms and Catalysis","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11144-024-02723-w","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
采用ZSM-5负载Zn-Br,制备了Lewis酸和亲核试剂的双功能固定化催化剂,用于CO2和环氧丙烷合成碳酸丙烯。当Zn - Br的总负荷量ω为7.5wt%, n(Br)/n(Zn)的摩尔比为3.0时,ZnO-KBr-7.5-3.0@ZSM-5对溶剂n, n -二甲基甲酰胺(DMF)的活性最高。环氧丙烷的转化率和碳酸丙烯酯的选择性分别达到97.73%和98.83%。气相色谱结果显示,除了碳酸丙烯酯外,还存在副产物,特别是丙酮和丙二醇。表征表明ZnO-KBr-7.5-3.0@ZSM-5中的活性组分为ZnO和KBr。同时,实验结果证明DMF具有助催化剂的作用。提出了DMF和ZnO-KBr-7.5-3.0@ZSM-5对环加成的催化机理,并对反应过程进行了模拟。DMF含有叔氮结构,能够发挥路易斯碱的作用,从而激活CO2。ZnO-KBr-7.5 - 3.0@ZSM-5中ZnO和KBr协同作用促进环氧化物环开度。随后,活性CO2与开环环氧化物结合,形成碳酸丙烯酯。另外,4个循环的重复实验表明,该催化剂ZnO-KBr-7.5-3.0@ZSM-5具有良好的稳定性。
Bifunctional immobilized catalyst and N, N-dimethylformamide synergistically synthesize propylene carbonate from CO2 and propylene oxide
In the present work, bifunctional immobilized catalysts, incorporating Lewis acid and nucleophilic reagent, were prepared by supporting Zn–Br with ZSM-5 for the synthesis of propylene carbonate from CO2 and propylene oxide. When the total loading of Zn–Br, ω, is 7.5wt%, and the molar ratio, n(Br)/n(Zn), is 3.0, ZnO-KBr-7.5-3.0@ZSM-5 exhibits the highest activity with the solvent N, N-dimethylformamide (DMF). The conversion of propylene oxide and the selectivity of propylene carbonate are up to 97.73% and 98.83%, respectively. Gas chromatography results reveal the presence of by-products, specifically acetone and propylene glycol, in addition to propylene carbonate. Characterizations identify the active components in ZnO-KBr-7.5-3.0@ZSM-5 as ZnO and KBr. Meanwhile, the experimental results prove that DMF serves as a co-catalyst. The catalytic mechanism of DMF and ZnO-KBr-7.5-3.0@ZSM-5 on the cycloaddition is proposed, and the reaction process is simulated. DMF contains a tertiary nitrogen structure, able to function as a Lewis base, thereby activating CO2. ZnO and KBr in ZnO-KBr-7.5–3.0@ZSM-5 work synergistically to boost epoxide ring opening. Subsequently, the activated CO2 integrates into the ring-opened epoxide, resulting in the formation of propylene carbonate. Additionally, four cycles of replicate experiments show that the catalyst ZnO-KBr-7.5-3.0@ZSM-5 possessed good stability.
期刊介绍:
Reaction Kinetics, Mechanisms and Catalysis is a medium for original contributions in the following fields:
-kinetics of homogeneous reactions in gas, liquid and solid phase;
-Homogeneous catalysis;
-Heterogeneous catalysis;
-Adsorption in heterogeneous catalysis;
-Transport processes related to reaction kinetics and catalysis;
-Preparation and study of catalysts;
-Reactors and apparatus.
Reaction Kinetics, Mechanisms and Catalysis was formerly published under the title Reaction Kinetics and Catalysis Letters.