Zijun Huang, Dedong He, Jichang Lu, Lanfang Han, Kongzhai Li, Dingkai Chen, Xiaohua Cao, Tan Li, Yongming Luo
{"title":"通过碳层调节改变四面体钴(II)中心的电荷密度,促进丙烷脱氢反应 (PDH) 中的 C-H 活化","authors":"Zijun Huang, Dedong He, Jichang Lu, Lanfang Han, Kongzhai Li, Dingkai Chen, Xiaohua Cao, Tan Li, Yongming Luo","doi":"10.1002/anie.202408391","DOIUrl":null,"url":null,"abstract":"<p>The electronic structure of active metal centers plays an indispensable role in regulating catalytic reactivity in heterogeneous catalysis, developing other metals as promoters to decorate electronic state is a common strategy, while non-metal component of carbon as electronic additives to regulate d-band center has rarely been studied in thermal-catalysis field. Herein, we report electron-deficient tetrahedral Co(II) (T<sub>d</sub>-cobalt(II)) centers through carbon-layer modulation for propane dehydrogenation (PDH). It is indicated that bifunctional sites of both T<sub>d</sub>-cobalt(II) and metallic-cobalt are designed, and the in situ generated carbon through the disproportionation of CO on metallic-cobalt can cover the inactive metallic-cobalt and tailor d-band of active T<sub>d</sub>-cobalt(II) simultaneously. More importantly, the pre-deposited carbon-layer is proposed to decrease electron density of T<sub>d</sub>-cobalt(II) and make d-band center closer to Fermi level, consequently promotes C−H activation in PDH reaction. This study provides new perspective for the utilization of inactive carbon as electronic promoters and unlocks new opportunity to fabricate efficient PDH and other heterogeneous catalysts.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Modifying the Charge-Density of Tetrahedral Cobalt(II) Centers through Carbon-Layer Modulation Promotes C-H Activation in the Propane Dehydrogenation Reaction (PDH)\",\"authors\":\"Zijun Huang, Dedong He, Jichang Lu, Lanfang Han, Kongzhai Li, Dingkai Chen, Xiaohua Cao, Tan Li, Yongming Luo\",\"doi\":\"10.1002/anie.202408391\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The electronic structure of active metal centers plays an indispensable role in regulating catalytic reactivity in heterogeneous catalysis, developing other metals as promoters to decorate electronic state is a common strategy, while non-metal component of carbon as electronic additives to regulate d-band center has rarely been studied in thermal-catalysis field. Herein, we report electron-deficient tetrahedral Co(II) (T<sub>d</sub>-cobalt(II)) centers through carbon-layer modulation for propane dehydrogenation (PDH). It is indicated that bifunctional sites of both T<sub>d</sub>-cobalt(II) and metallic-cobalt are designed, and the in situ generated carbon through the disproportionation of CO on metallic-cobalt can cover the inactive metallic-cobalt and tailor d-band of active T<sub>d</sub>-cobalt(II) simultaneously. More importantly, the pre-deposited carbon-layer is proposed to decrease electron density of T<sub>d</sub>-cobalt(II) and make d-band center closer to Fermi level, consequently promotes C−H activation in PDH reaction. This study provides new perspective for the utilization of inactive carbon as electronic promoters and unlocks new opportunity to fabricate efficient PDH and other heterogeneous catalysts.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2024-06-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie International Edition\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/anie.202408391\",\"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":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202408391","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
活性金属中心的电子结构在调节异相催化反应活性中起着不可或缺的作用,开发其他金属作为促进剂来装饰电子状态是一种常见的策略,而碳中的非金属成分作为电子添加剂来调节 d 波段中心在热催化领域还鲜有研究。在此,我们报告了通过碳层调节丙烷脱氢(PDH)的缺电子四面体钴(II)(Td-钴(II))中心。研究表明,Td-钴(II)和金属钴的双功能位点都是设计出来的,通过 CO 在金属钴上的歧化而原位生成的碳可以同时覆盖非活性金属钴和定制活性 Td-钴(II)的 d 带。更重要的是,预沉积碳层可降低镉钴(II)的电子密度,使 d 波段中心更接近费米级,从而促进 PDH 反应中 C-H 的活化。这项研究为利用非活性碳作为电子促进剂提供了新的视角,并为制造高效的 PDH 及其他异质催化剂提供了新的机遇。
Modifying the Charge-Density of Tetrahedral Cobalt(II) Centers through Carbon-Layer Modulation Promotes C-H Activation in the Propane Dehydrogenation Reaction (PDH)
The electronic structure of active metal centers plays an indispensable role in regulating catalytic reactivity in heterogeneous catalysis, developing other metals as promoters to decorate electronic state is a common strategy, while non-metal component of carbon as electronic additives to regulate d-band center has rarely been studied in thermal-catalysis field. Herein, we report electron-deficient tetrahedral Co(II) (Td-cobalt(II)) centers through carbon-layer modulation for propane dehydrogenation (PDH). It is indicated that bifunctional sites of both Td-cobalt(II) and metallic-cobalt are designed, and the in situ generated carbon through the disproportionation of CO on metallic-cobalt can cover the inactive metallic-cobalt and tailor d-band of active Td-cobalt(II) simultaneously. More importantly, the pre-deposited carbon-layer is proposed to decrease electron density of Td-cobalt(II) and make d-band center closer to Fermi level, consequently promotes C−H activation in PDH reaction. This study provides new perspective for the utilization of inactive carbon as electronic promoters and unlocks new opportunity to fabricate efficient PDH and other heterogeneous catalysts.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.