{"title":"用于酸催化环氧化物烷氧基化的 1D 混合连接剂 Zn(II) 配位聚合物的后合成改性","authors":"Mahnaz Najafi, Jan Janczak","doi":"10.1002/cplu.202400400","DOIUrl":null,"url":null,"abstract":"Rational design of heterogeneous acid catalysts possessing uniform dispersion of active sites plays a significant role in the catalytic performance. In the present work, a coordination polymer, [Zn(4,4´‐bpy)(µ‐Hbtc)(H2O)]∙2H2O (Zn‐CP), was solvothermally synthesized using 4,4´‐bpy (= 4,4´‐bipyridine) and H3btc (= 1,3,5‐benzenetricarboxylic acid) mixed linkers. Single crystal X‐ray analysis of the polymer displayed that Zn‐CP chains were decorated with 4,4´‐bpy having unidentate coordination fashion. Then, the free N atom of the linker in Zn‐CP was functionalized by ‐SO3H groups to afford Zn‐CP‐SO3H with enhanced acidity. The structures were characterized by FT‐IR, thermogravimetric analysis, powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3‐TPD), and field emission scanning electron microscopy (FE‐SEM) analyses. The coordination polymer was employed as heterogeneous catalyst for alcoholysis of epoxides under room conditions. The Zn‐CP‐SO3H exhibited excellent catalytic activity and regioselectivity in the methanolysis of styrene oxide within short reaction time.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"249 1","pages":""},"PeriodicalIF":3.0000,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Post‐Synthetic Modification of a 1D Mixed‐Linker Zn(II) Coordination Polymer for Acid‐Catalyzed Alcoholysis of Epoxides\",\"authors\":\"Mahnaz Najafi, Jan Janczak\",\"doi\":\"10.1002/cplu.202400400\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Rational design of heterogeneous acid catalysts possessing uniform dispersion of active sites plays a significant role in the catalytic performance. In the present work, a coordination polymer, [Zn(4,4´‐bpy)(µ‐Hbtc)(H2O)]∙2H2O (Zn‐CP), was solvothermally synthesized using 4,4´‐bpy (= 4,4´‐bipyridine) and H3btc (= 1,3,5‐benzenetricarboxylic acid) mixed linkers. Single crystal X‐ray analysis of the polymer displayed that Zn‐CP chains were decorated with 4,4´‐bpy having unidentate coordination fashion. Then, the free N atom of the linker in Zn‐CP was functionalized by ‐SO3H groups to afford Zn‐CP‐SO3H with enhanced acidity. The structures were characterized by FT‐IR, thermogravimetric analysis, powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3‐TPD), and field emission scanning electron microscopy (FE‐SEM) analyses. The coordination polymer was employed as heterogeneous catalyst for alcoholysis of epoxides under room conditions. The Zn‐CP‐SO3H exhibited excellent catalytic activity and regioselectivity in the methanolysis of styrene oxide within short reaction time.\",\"PeriodicalId\":148,\"journal\":{\"name\":\"ChemPlusChem\",\"volume\":\"249 1\",\"pages\":\"\"},\"PeriodicalIF\":3.0000,\"publicationDate\":\"2024-09-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemPlusChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cplu.202400400\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemPlusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cplu.202400400","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
合理设计具有均匀分散活性位点的异质酸催化剂对催化性能起着重要作用。本研究利用 4,4´-bpy(= 4,4´-联吡啶)和 H3btc(= 1,3,5-苯三羧酸)混合连接体,通过溶解热合成了配位聚合物 [Zn(4,4´-bpy)(µ-Hbtc)(H2O)]∙2H2O(Zn-CP)。聚合物的单晶 X 射线分析表明,Zn-CP 链被 4,4´-bpy装饰,具有非同一配位方式。然后,Zn-CP 链节的自由 N 原子被 -SO3H 基团官能化,从而得到酸性增强的 Zn-CP-SO3H。通过傅立叶变换红外光谱、热重分析、粉末 X 射线衍射 (XRD)、X 射线光电子能谱 (XPS)、NH3 的温度编程解吸 (NH3-TPD) 以及场发射扫描电子显微镜 (FE-SEM) 分析对这些结构进行了表征。该配位聚合物被用作室温条件下醇解环氧化物的异相催化剂。Zn-CP-SO3H 在短反应时间内对氧化苯乙烯的甲醇分解具有优异的催化活性和区域选择性。
Post‐Synthetic Modification of a 1D Mixed‐Linker Zn(II) Coordination Polymer for Acid‐Catalyzed Alcoholysis of Epoxides
Rational design of heterogeneous acid catalysts possessing uniform dispersion of active sites plays a significant role in the catalytic performance. In the present work, a coordination polymer, [Zn(4,4´‐bpy)(µ‐Hbtc)(H2O)]∙2H2O (Zn‐CP), was solvothermally synthesized using 4,4´‐bpy (= 4,4´‐bipyridine) and H3btc (= 1,3,5‐benzenetricarboxylic acid) mixed linkers. Single crystal X‐ray analysis of the polymer displayed that Zn‐CP chains were decorated with 4,4´‐bpy having unidentate coordination fashion. Then, the free N atom of the linker in Zn‐CP was functionalized by ‐SO3H groups to afford Zn‐CP‐SO3H with enhanced acidity. The structures were characterized by FT‐IR, thermogravimetric analysis, powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3‐TPD), and field emission scanning electron microscopy (FE‐SEM) analyses. The coordination polymer was employed as heterogeneous catalyst for alcoholysis of epoxides under room conditions. The Zn‐CP‐SO3H exhibited excellent catalytic activity and regioselectivity in the methanolysis of styrene oxide within short reaction time.
期刊介绍:
ChemPlusChem is a peer-reviewed, general chemistry journal that brings readers the very best in multidisciplinary research centering on chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
Fully comprehensive in its scope, ChemPlusChem publishes articles covering new results from at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem). All suitable submissions undergo balanced peer review by experts in the field to ensure the highest quality, originality, relevance, significance, and validity.