{"title":"调节富铝框架沸石中的单核/双核铁物种以实现高效低温烷烃氧化","authors":"Qiang Zhang, Jialiang Li, Guangyuan He, Junyan Li, Ziyi Chen, Qing Zhang, Chunyu Wang, Guodong Qi, Qiang Wang, Peng Zhang, Jun Xu, Osamu Terasaki, Donghai Mei, Zhongmin Liu, Jihong Yu","doi":"10.31635/ccschem.024.202404123","DOIUrl":null,"url":null,"abstract":"Zeolite-encapsulated extra-framework mono/binuclear Fe<sup>3+</sup> species present higher catalytic activities compared to clusters and nanoparticles for direct low-temperature alkane oxidation. However, the fine control of mono/binuclear Fe<sup>3+</sup> in zeolites is challenging and the reaction mechanism of low-temperature alkane oxidation remains not clearly identified. Different from previous impregnation and ion-exchange methods generally generating clusters/nanoparticles, here we developed an efficient amino acid-assisted one-pot hydrothermal synthesis strategy for in situ incorporating mono/binuclear Fe<sup>3=</sup> species into framework Al-rich ZSM-5 zeolites. The high framework Al content (Si/Al=9) provided sufficient negatively-charged sites to anchor mono/binuclear Fe<sup>3+</sup> (Fe loading=0.44~0.90 wt%). The as-prepared 0.44Fe@Z-L<sub>0.3</sub>H<sub>6</sub>-9 catalyst exhibited superior catalytic properties for selective oxidation of both methane and ethane in the H<sub>2</sub>O<sub>2</sub> solution at 50 °C, presenting a top-level catalytic performance among various heterogeneous/homogeneous catalysts. Combining advanced characterizations and density functional theory calculations, the complex reaction networks for methane and ethane conversions into C1/C2 oxygenates over mononuclear and binuclear Fe<sup>3+</sup>, for the first time, were mapped out. The mononuclear Fe<sup>3+</sup> was found more active than binuclear Fe<sup>3+</sup> for both methane and ethane conversions. This work not only provides a whole picture on low-temperature alkane oxidation mechanisms but also guides the rational design of high-performance catalysts for C−H bond activation and beyond.\n<figure><img alt=\"\" data-lg-src=\"/cms/asset/5089ba4d-1638-4cd0-a1d2-d75a33f61caa/keyimage.jpg\" data-src=\"/cms/asset/39784551-9e90-43f1-91c7-78f75456622b/keyimage.jpg\" src=\"/specs/ux3/releasedAssets/images/loader-7e60691fbe777356dc81ff6d223a82a6.gif\"/><ul>\n<li>Download figure</li>\n<li>Download PowerPoint</li>\n</ul>\n</figure>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":null,"pages":null},"PeriodicalIF":9.4000,"publicationDate":"2024-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Regulating Mono/Binuclear Fe Species in Framework Al-Rich Zeolites for Efficient Low-Temperature Alkane Oxidation\",\"authors\":\"Qiang Zhang, Jialiang Li, Guangyuan He, Junyan Li, Ziyi Chen, Qing Zhang, Chunyu Wang, Guodong Qi, Qiang Wang, Peng Zhang, Jun Xu, Osamu Terasaki, Donghai Mei, Zhongmin Liu, Jihong Yu\",\"doi\":\"10.31635/ccschem.024.202404123\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Zeolite-encapsulated extra-framework mono/binuclear Fe<sup>3+</sup> species present higher catalytic activities compared to clusters and nanoparticles for direct low-temperature alkane oxidation. However, the fine control of mono/binuclear Fe<sup>3+</sup> in zeolites is challenging and the reaction mechanism of low-temperature alkane oxidation remains not clearly identified. Different from previous impregnation and ion-exchange methods generally generating clusters/nanoparticles, here we developed an efficient amino acid-assisted one-pot hydrothermal synthesis strategy for in situ incorporating mono/binuclear Fe<sup>3=</sup> species into framework Al-rich ZSM-5 zeolites. The high framework Al content (Si/Al=9) provided sufficient negatively-charged sites to anchor mono/binuclear Fe<sup>3+</sup> (Fe loading=0.44~0.90 wt%). The as-prepared 0.44Fe@Z-L<sub>0.3</sub>H<sub>6</sub>-9 catalyst exhibited superior catalytic properties for selective oxidation of both methane and ethane in the H<sub>2</sub>O<sub>2</sub> solution at 50 °C, presenting a top-level catalytic performance among various heterogeneous/homogeneous catalysts. Combining advanced characterizations and density functional theory calculations, the complex reaction networks for methane and ethane conversions into C1/C2 oxygenates over mononuclear and binuclear Fe<sup>3+</sup>, for the first time, were mapped out. The mononuclear Fe<sup>3+</sup> was found more active than binuclear Fe<sup>3+</sup> for both methane and ethane conversions. This work not only provides a whole picture on low-temperature alkane oxidation mechanisms but also guides the rational design of high-performance catalysts for C−H bond activation and beyond.\\n<figure><img alt=\\\"\\\" data-lg-src=\\\"/cms/asset/5089ba4d-1638-4cd0-a1d2-d75a33f61caa/keyimage.jpg\\\" data-src=\\\"/cms/asset/39784551-9e90-43f1-91c7-78f75456622b/keyimage.jpg\\\" src=\\\"/specs/ux3/releasedAssets/images/loader-7e60691fbe777356dc81ff6d223a82a6.gif\\\"/><ul>\\n<li>Download figure</li>\\n<li>Download PowerPoint</li>\\n</ul>\\n</figure>\",\"PeriodicalId\":9810,\"journal\":{\"name\":\"CCS Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.4000,\"publicationDate\":\"2024-04-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"CCS Chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.31635/ccschem.024.202404123\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"CCS Chemistry","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.31635/ccschem.024.202404123","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Regulating Mono/Binuclear Fe Species in Framework Al-Rich Zeolites for Efficient Low-Temperature Alkane Oxidation
Zeolite-encapsulated extra-framework mono/binuclear Fe3+ species present higher catalytic activities compared to clusters and nanoparticles for direct low-temperature alkane oxidation. However, the fine control of mono/binuclear Fe3+ in zeolites is challenging and the reaction mechanism of low-temperature alkane oxidation remains not clearly identified. Different from previous impregnation and ion-exchange methods generally generating clusters/nanoparticles, here we developed an efficient amino acid-assisted one-pot hydrothermal synthesis strategy for in situ incorporating mono/binuclear Fe3= species into framework Al-rich ZSM-5 zeolites. The high framework Al content (Si/Al=9) provided sufficient negatively-charged sites to anchor mono/binuclear Fe3+ (Fe loading=0.44~0.90 wt%). The as-prepared 0.44Fe@Z-L0.3H6-9 catalyst exhibited superior catalytic properties for selective oxidation of both methane and ethane in the H2O2 solution at 50 °C, presenting a top-level catalytic performance among various heterogeneous/homogeneous catalysts. Combining advanced characterizations and density functional theory calculations, the complex reaction networks for methane and ethane conversions into C1/C2 oxygenates over mononuclear and binuclear Fe3+, for the first time, were mapped out. The mononuclear Fe3+ was found more active than binuclear Fe3+ for both methane and ethane conversions. This work not only provides a whole picture on low-temperature alkane oxidation mechanisms but also guides the rational design of high-performance catalysts for C−H bond activation and beyond.
期刊介绍:
CCS Chemistry, the flagship publication of the Chinese Chemical Society, stands as a leading international chemistry journal based in China. With a commitment to global outreach in both contributions and readership, the journal operates on a fully Open Access model, eliminating subscription fees for contributing authors. Issued monthly, all articles are published online promptly upon reaching final publishable form. Additionally, authors have the option to expedite the posting process through Immediate Online Accepted Article posting, making a PDF of their accepted article available online upon journal acceptance.