{"title":"磁性 NPs 上固定的 (TEMPO)-co-(Chlorophyll b)/Co(III) 聚合物作为一种双功能、自氧化磁性可回收纳米催化剂高效环氧化烯烃:与聚(苯甲酸)的智能分离","authors":"Milad Kazemnejadi, Mohsen Esmaeilpour","doi":"10.1007/s11164-024-05394-3","DOIUrl":null,"url":null,"abstract":"<div><p>A selective and efficient olefin epoxidation has been developed by Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>/(TEMPO)-copolymer-(Chlorophyll <i>b</i>)-Co<sup>(III)</sup> NPs as a heterogeneous magnetically recyclable nanocatalyst. The nanocatalyst was synthesized through several steps including chlorophyll <i>b</i> de-metallation, imine functionalization with ally amine, co-polymerization with acrylated TEMPO, re-metalation with cobalt, and immobilization on magnetite NPs. Selective catalytic epoxidation of olefins was accomplished under mild conditions and in an O<sub>2</sub> atmosphere. High selectivity and conversion were achieved for a variety of substrates. The results indicated a synergistic effect between TEMPO moieties and the coordinated Co<sup>(III)</sup> centers as two active sites. The epoxide products could be separated by the heterogeneous poly(benzoic acid) with the highest possible isolated yields. Also, the heterogeneous nanocatalyst could be recycled for at least 7 consecutive cycles with a negligible reactivity loss.</p><h3>Graphical abstract</h3><p>A selective and efficient olefin epoxidation with smart isolation has been developed by Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>/(TEMPO)-copolymer-(Chlorophyll <i>b</i>)-Co<sup>(III)</sup> NPs under mild conditions.</p>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":753,"journal":{"name":"Research on Chemical Intermediates","volume":"50 10","pages":"4775 - 4794"},"PeriodicalIF":2.8000,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Efficient epoxidation of olefins by immobilized (TEMPO)-co-(Chlorophyll b)/Co(III) polymer on magnetic NPs as a bi-functional, self-co-oxidant magnetically recyclable nanocatalyst: smart isolation with poly(benzoic acid)\",\"authors\":\"Milad Kazemnejadi, Mohsen Esmaeilpour\",\"doi\":\"10.1007/s11164-024-05394-3\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A selective and efficient olefin epoxidation has been developed by Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>/(TEMPO)-copolymer-(Chlorophyll <i>b</i>)-Co<sup>(III)</sup> NPs as a heterogeneous magnetically recyclable nanocatalyst. The nanocatalyst was synthesized through several steps including chlorophyll <i>b</i> de-metallation, imine functionalization with ally amine, co-polymerization with acrylated TEMPO, re-metalation with cobalt, and immobilization on magnetite NPs. Selective catalytic epoxidation of olefins was accomplished under mild conditions and in an O<sub>2</sub> atmosphere. High selectivity and conversion were achieved for a variety of substrates. The results indicated a synergistic effect between TEMPO moieties and the coordinated Co<sup>(III)</sup> centers as two active sites. The epoxide products could be separated by the heterogeneous poly(benzoic acid) with the highest possible isolated yields. Also, the heterogeneous nanocatalyst could be recycled for at least 7 consecutive cycles with a negligible reactivity loss.</p><h3>Graphical abstract</h3><p>A selective and efficient olefin epoxidation with smart isolation has been developed by Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>/(TEMPO)-copolymer-(Chlorophyll <i>b</i>)-Co<sup>(III)</sup> NPs under mild conditions.</p>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":753,\"journal\":{\"name\":\"Research on Chemical Intermediates\",\"volume\":\"50 10\",\"pages\":\"4775 - 4794\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2024-09-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Research on Chemical Intermediates\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11164-024-05394-3\",\"RegionNum\":3,\"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":"Research on Chemical Intermediates","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11164-024-05394-3","RegionNum":3,"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
采用 Fe3O4@SiO2/(TEMPO)-共聚物-(叶绿素 b)-Co(III) NPs 作为异相磁性可回收纳米催化剂,开发了一种选择性高效烯烃环氧化反应。该纳米催化剂的合成经历了多个步骤,包括叶绿素 b 脱金属、与烯丙基胺进行亚胺官能化、与丙烯酸化 TEMPO 进行共聚合、与钴进行再金属化以及固定在磁铁矿 NPs 上。在温和的条件下和氧气环境中完成了烯烃的选择性催化环氧化反应。对多种底物都实现了高选择性和高转化率。研究结果表明,作为两个活性位点的 TEMPO 分子和配位 Co(III)中心之间存在协同效应。环氧化物产物可以通过异相聚(苯甲酸)分离出来,并获得最高的分离产率。图解摘要 在温和的条件下,Fe3O4@SiO2/(TEMPO)-聚合物-(叶绿素 b)-Co(III) NPs 开发了一种选择性的高效烯烃环氧化反应。
Efficient epoxidation of olefins by immobilized (TEMPO)-co-(Chlorophyll b)/Co(III) polymer on magnetic NPs as a bi-functional, self-co-oxidant magnetically recyclable nanocatalyst: smart isolation with poly(benzoic acid)
A selective and efficient olefin epoxidation has been developed by Fe3O4@SiO2/(TEMPO)-copolymer-(Chlorophyll b)-Co(III) NPs as a heterogeneous magnetically recyclable nanocatalyst. The nanocatalyst was synthesized through several steps including chlorophyll b de-metallation, imine functionalization with ally amine, co-polymerization with acrylated TEMPO, re-metalation with cobalt, and immobilization on magnetite NPs. Selective catalytic epoxidation of olefins was accomplished under mild conditions and in an O2 atmosphere. High selectivity and conversion were achieved for a variety of substrates. The results indicated a synergistic effect between TEMPO moieties and the coordinated Co(III) centers as two active sites. The epoxide products could be separated by the heterogeneous poly(benzoic acid) with the highest possible isolated yields. Also, the heterogeneous nanocatalyst could be recycled for at least 7 consecutive cycles with a negligible reactivity loss.
Graphical abstract
A selective and efficient olefin epoxidation with smart isolation has been developed by Fe3O4@SiO2/(TEMPO)-copolymer-(Chlorophyll b)-Co(III) NPs under mild conditions.
期刊介绍:
Research on Chemical Intermediates publishes current research articles and concise dynamic reviews on the properties, structures and reactivities of intermediate species in all the various domains of chemistry.
The journal also contains articles in related disciplines such as spectroscopy, molecular biology and biochemistry, atmospheric and environmental sciences, catalysis, photochemistry and photophysics. In addition, special issues dedicated to specific topics in the field are regularly published.