{"title":"原位合成用于连续生产二氯甲烷的 NHC-CO2 异构催化剂","authors":"Zhentao Zhao, Yuxin Wang, Guangwen Xu, Lei Shi","doi":"10.1016/j.jcat.2024.115910","DOIUrl":null,"url":null,"abstract":"N-heterocyclic carbene CO<sub>2</sub> adducts (NHC–CO<sub>2</sub>) are typical zwitterionic ionic liquid compounds, known for their strong nucleophilicity and significant catalytic ability. However, NHC–CO<sub>2</sub> is sensitive to water, and its complex and polluting preparation process limits its widespread application. Furthermore, most reported NHC–CO<sub>2</sub> compounds function as homogeneous catalysts, posing considerable challenges for separation. In this study, an in-situ green synthesis method was employed to develop a heterogeneous NHC–CO<sub>2</sub> catalyst, PS–IMIL. This approach not only prevents direct contact between the catalyst and water but also simplifies the preparation process and mitigates environmental pollution. The synthesis conditions of PS–IMIL were optimized, and its structure and properties were analyzed. Furthermore, the synthesis mechanism of PS–IMIL was investigated, and its kinetics were also studied. The results indicate that the interaction between the material ethylene carbonate (EC) and the precursor is crucial for the in-situ synthesis of PS–IMIL. The prepared PS–IMIL not only preserves the catalytic ability of NHC–CO<sub>2</sub> but also exhibits characteristics of being metal- and halogen-free. Remarkably, the catalytic activity and structure of PS–IMIL remain unchanged after 300 h of continuous use in dimethyl carbonate (DMC) production. Compared to similar catalysts, PS–IMIL exhibits excellent catalytic activity and stability. This study provides a solid theoretical and practical reference for the development of heterogeneous NHC–CO<sub>2</sub> catalysts. The synthesized PS–IMIL demonstrates significant potential for the industrial production of DMC and other carbonate esters.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"201 1","pages":""},"PeriodicalIF":6.5000,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"In-situ synthesis of a heterogeneous NHC–CO2 catalyst for continuous DMC production\",\"authors\":\"Zhentao Zhao, Yuxin Wang, Guangwen Xu, Lei Shi\",\"doi\":\"10.1016/j.jcat.2024.115910\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"N-heterocyclic carbene CO<sub>2</sub> adducts (NHC–CO<sub>2</sub>) are typical zwitterionic ionic liquid compounds, known for their strong nucleophilicity and significant catalytic ability. However, NHC–CO<sub>2</sub> is sensitive to water, and its complex and polluting preparation process limits its widespread application. Furthermore, most reported NHC–CO<sub>2</sub> compounds function as homogeneous catalysts, posing considerable challenges for separation. In this study, an in-situ green synthesis method was employed to develop a heterogeneous NHC–CO<sub>2</sub> catalyst, PS–IMIL. This approach not only prevents direct contact between the catalyst and water but also simplifies the preparation process and mitigates environmental pollution. The synthesis conditions of PS–IMIL were optimized, and its structure and properties were analyzed. Furthermore, the synthesis mechanism of PS–IMIL was investigated, and its kinetics were also studied. The results indicate that the interaction between the material ethylene carbonate (EC) and the precursor is crucial for the in-situ synthesis of PS–IMIL. The prepared PS–IMIL not only preserves the catalytic ability of NHC–CO<sub>2</sub> but also exhibits characteristics of being metal- and halogen-free. Remarkably, the catalytic activity and structure of PS–IMIL remain unchanged after 300 h of continuous use in dimethyl carbonate (DMC) production. Compared to similar catalysts, PS–IMIL exhibits excellent catalytic activity and stability. This study provides a solid theoretical and practical reference for the development of heterogeneous NHC–CO<sub>2</sub> catalysts. The synthesized PS–IMIL demonstrates significant potential for the industrial production of DMC and other carbonate esters.\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"201 1\",\"pages\":\"\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-12-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1016/j.jcat.2024.115910\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.jcat.2024.115910","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
In-situ synthesis of a heterogeneous NHC–CO2 catalyst for continuous DMC production
N-heterocyclic carbene CO2 adducts (NHC–CO2) are typical zwitterionic ionic liquid compounds, known for their strong nucleophilicity and significant catalytic ability. However, NHC–CO2 is sensitive to water, and its complex and polluting preparation process limits its widespread application. Furthermore, most reported NHC–CO2 compounds function as homogeneous catalysts, posing considerable challenges for separation. In this study, an in-situ green synthesis method was employed to develop a heterogeneous NHC–CO2 catalyst, PS–IMIL. This approach not only prevents direct contact between the catalyst and water but also simplifies the preparation process and mitigates environmental pollution. The synthesis conditions of PS–IMIL were optimized, and its structure and properties were analyzed. Furthermore, the synthesis mechanism of PS–IMIL was investigated, and its kinetics were also studied. The results indicate that the interaction between the material ethylene carbonate (EC) and the precursor is crucial for the in-situ synthesis of PS–IMIL. The prepared PS–IMIL not only preserves the catalytic ability of NHC–CO2 but also exhibits characteristics of being metal- and halogen-free. Remarkably, the catalytic activity and structure of PS–IMIL remain unchanged after 300 h of continuous use in dimethyl carbonate (DMC) production. Compared to similar catalysts, PS–IMIL exhibits excellent catalytic activity and stability. This study provides a solid theoretical and practical reference for the development of heterogeneous NHC–CO2 catalysts. The synthesized PS–IMIL demonstrates significant potential for the industrial production of DMC and other carbonate esters.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.