{"title":"用于 1-己烯加氢甲酰化的高效中空 Rh@H-S-1 催化剂","authors":"Gongcheng Sun, Subing Fan, Junmin Lv, Tiansheng Zhao","doi":"10.1016/j.jcat.2024.115770","DOIUrl":null,"url":null,"abstract":"<div><div>A hollow zeolite encapsulated Rh catalyst Rh@H-S-1 with an “eggshell” structure was prepared using the method of organic alkali treatment and recrystallization. Compared with catalysts with directly encapsulated Rh@S-1 and surface impregnated Rh/S-1, this catalyst exhibited both superior activity and a higher TOF value in hydroformylation of 1-hexene due to the high dispersion of Rh and high diffusion. The Rh element did not need to be reduced in the preparation, and it was <em>in situ</em> reduced by the syngas. The content of lower valence Rh<sup>δ+</sup> gradually increased with the reaction procedure and played as an active center. The low oxidized state Rh<sup>+</sup> or Rh<sup>δ+</sup> in the form of Rh(CO)<sub>2</sub> are proposed as active sites in hydroformylation, which were generated under the synergistic effect between CO and H<sub>2</sub>. Importantly, the hollow encapsulated catalyst effectively decreased Rh leaching to 0.1 ppm and showed better stability compared with the impregnated Rh/S-1 catalyst.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"439 ","pages":"Article 115770"},"PeriodicalIF":6.5000,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effective hollow Rh@H-S-1 catalyst for hydroformylation of 1-hexene\",\"authors\":\"Gongcheng Sun, Subing Fan, Junmin Lv, Tiansheng Zhao\",\"doi\":\"10.1016/j.jcat.2024.115770\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>A hollow zeolite encapsulated Rh catalyst Rh@H-S-1 with an “eggshell” structure was prepared using the method of organic alkali treatment and recrystallization. Compared with catalysts with directly encapsulated Rh@S-1 and surface impregnated Rh/S-1, this catalyst exhibited both superior activity and a higher TOF value in hydroformylation of 1-hexene due to the high dispersion of Rh and high diffusion. The Rh element did not need to be reduced in the preparation, and it was <em>in situ</em> reduced by the syngas. The content of lower valence Rh<sup>δ+</sup> gradually increased with the reaction procedure and played as an active center. The low oxidized state Rh<sup>+</sup> or Rh<sup>δ+</sup> in the form of Rh(CO)<sub>2</sub> are proposed as active sites in hydroformylation, which were generated under the synergistic effect between CO and H<sub>2</sub>. Importantly, the hollow encapsulated catalyst effectively decreased Rh leaching to 0.1 ppm and showed better stability compared with the impregnated Rh/S-1 catalyst.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"439 \",\"pages\":\"Article 115770\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724004834\",\"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://www.sciencedirect.com/science/article/pii/S0021951724004834","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Effective hollow Rh@H-S-1 catalyst for hydroformylation of 1-hexene
A hollow zeolite encapsulated Rh catalyst Rh@H-S-1 with an “eggshell” structure was prepared using the method of organic alkali treatment and recrystallization. Compared with catalysts with directly encapsulated Rh@S-1 and surface impregnated Rh/S-1, this catalyst exhibited both superior activity and a higher TOF value in hydroformylation of 1-hexene due to the high dispersion of Rh and high diffusion. The Rh element did not need to be reduced in the preparation, and it was in situ reduced by the syngas. The content of lower valence Rhδ+ gradually increased with the reaction procedure and played as an active center. The low oxidized state Rh+ or Rhδ+ in the form of Rh(CO)2 are proposed as active sites in hydroformylation, which were generated under the synergistic effect between CO and H2. Importantly, the hollow encapsulated catalyst effectively decreased Rh leaching to 0.1 ppm and showed better stability compared with the impregnated Rh/S-1 catalyst.
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.