{"title":"丙烷脱氢过程中 Rh/Al2O3 的表面动力学","authors":"Shuyi Li, Changle Mu, Nianqiu He, Jie Xu, Yanping Zheng, Mingshu Chen","doi":"10.1016/S1872-2067(24)60063-X","DOIUrl":null,"url":null,"abstract":"<div><p>The surface structures of heterogeneous catalysts significantly impact catalytic performance, especially for structure-sensitive reactions. In this study, we employed surface techniques such as low-energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy with CO as a probe (CO-FTIR) to investigate the surface dynamics of Rh/Al<sub>2</sub>O<sub>3</sub> catalysts for propane dehydrogenation (PDH). We observed a notable induction process for PDH on Rh/Al<sub>2</sub>O<sub>3</sub> catalysts, marked by significant variations in propane conversion, methane, and propylene selectivities. These changes were attributed to substantial coke formation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy) and CO-FTIR revealed the coexistence of Rh nanoparticles, clusters, and single atoms on the surface. Through various dynamic quasi <em>in-situ</em> characterizations, we found that coke preferentially covered Rh clusters, thereby inhibiting C–C bond breaking and methane formation. Meanwhile, Rh single atoms were less affected by coke coverage and remained exposed as active and selective sites for PDH, favoring propylene production. This work underscores the sensitivity of PDH to the sizes of Rh species, with isolated Rh single atoms promoting propylene formation.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"62 ","pages":"Pages 145-155"},"PeriodicalIF":15.7000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Surface dynamics of Rh/Al2O3 during propane dehydrogenation\",\"authors\":\"Shuyi Li, Changle Mu, Nianqiu He, Jie Xu, Yanping Zheng, Mingshu Chen\",\"doi\":\"10.1016/S1872-2067(24)60063-X\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The surface structures of heterogeneous catalysts significantly impact catalytic performance, especially for structure-sensitive reactions. In this study, we employed surface techniques such as low-energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy with CO as a probe (CO-FTIR) to investigate the surface dynamics of Rh/Al<sub>2</sub>O<sub>3</sub> catalysts for propane dehydrogenation (PDH). We observed a notable induction process for PDH on Rh/Al<sub>2</sub>O<sub>3</sub> catalysts, marked by significant variations in propane conversion, methane, and propylene selectivities. These changes were attributed to substantial coke formation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy) and CO-FTIR revealed the coexistence of Rh nanoparticles, clusters, and single atoms on the surface. Through various dynamic quasi <em>in-situ</em> characterizations, we found that coke preferentially covered Rh clusters, thereby inhibiting C–C bond breaking and methane formation. Meanwhile, Rh single atoms were less affected by coke coverage and remained exposed as active and selective sites for PDH, favoring propylene production. This work underscores the sensitivity of PDH to the sizes of Rh species, with isolated Rh single atoms promoting propylene formation.</p></div>\",\"PeriodicalId\":9832,\"journal\":{\"name\":\"Chinese Journal of Catalysis\",\"volume\":\"62 \",\"pages\":\"Pages 145-155\"},\"PeriodicalIF\":15.7000,\"publicationDate\":\"2024-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chinese Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S187220672460063X\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S187220672460063X","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Surface dynamics of Rh/Al2O3 during propane dehydrogenation
The surface structures of heterogeneous catalysts significantly impact catalytic performance, especially for structure-sensitive reactions. In this study, we employed surface techniques such as low-energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy with CO as a probe (CO-FTIR) to investigate the surface dynamics of Rh/Al2O3 catalysts for propane dehydrogenation (PDH). We observed a notable induction process for PDH on Rh/Al2O3 catalysts, marked by significant variations in propane conversion, methane, and propylene selectivities. These changes were attributed to substantial coke formation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy) and CO-FTIR revealed the coexistence of Rh nanoparticles, clusters, and single atoms on the surface. Through various dynamic quasi in-situ characterizations, we found that coke preferentially covered Rh clusters, thereby inhibiting C–C bond breaking and methane formation. Meanwhile, Rh single atoms were less affected by coke coverage and remained exposed as active and selective sites for PDH, favoring propylene production. This work underscores the sensitivity of PDH to the sizes of Rh species, with isolated Rh single atoms promoting propylene formation.
期刊介绍:
The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.