Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation
文献类型：期刊论文
| 作者 | Guo, Zhangtao1; Zhu, Qian1; Wang, Shaohua1; Jiang, Mengpei2; Fan, Xinxin1; Zhang, Wanyu1; Han, Mei1; Wu, Xiaotian1; Hou, Xiangyan1; Zhang, Yaowen1 |
| 刊名 | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
 |
| 出版日期 | 2024-08-12 |
| 页码 | 12 |
| 关键词 | Spin states Octahedral sites pi-pi type Orbital Coupling pi-donation e(g) Filling |
| ISSN号 | 1433-7851 |
| DOI | 10.1002/anie.202406711 |
| 通讯作者 | Wu, Xiaofeng(kkhuang@jlu.edu.cn) ; Huang, Keke(wuxf@jlu.edu.cn) |
| 英文摘要 | Spin state is often regarded as the crucial valve to release the reactivity of energy-related catalysts, yet it is also challenging to precisely manipulate, especially for the active center ions occupied at the specific geometric sites. Herein, a pi-pi type orbital coupling of 3d (Co)-2p (O)-4f (Ce) was employed to regulate the spin state of octahedral cobalt sites (Co-Oh) in the composite of Co3O4/CeO2. More specifically, the equivalent high-spin ratio of Co-Oh can reach to 54.7 % via tuning the CeO2 content, thereby triggering the average e(g) filling (1.094) close to the theoretical optimum value. The corresponding catalyst exhibits a superior water oxidation performance with an overpotential of 251 mV at 10 mA cm(-2), rivaling most cobalt-based oxides state-of-the-art. The pi-pi type coupling corroborated by the matched energy levels between Ce t(1u)/t(2u)-O and Co-Oh t(2g)-O pi type bond in the calculated crystal orbital Hamilton population and partial density of states profiles, stimulates a pi-donation between O 2p and pi-symmetric Ce 4f(yz)(2) orbital, consequently facilitating the electrons hopping from t(2g) to e(g) orbital of Co-Oh. This work offers an in-depth insight into understanding the 4f and 3d orbital coupling for spin state optimization in composite oxides. |
| 资助项目 | National Natural Science Foundation of China[22090044] ; National Natural Science Foundation of China[22171102] ; National Key R&D Program of China[2021YFF0500502] ; National Key R&D Program of China[2023YFA1506304] ; Jilin Province Science and Technology Development Plan[20230101024JC] ; Medicine+X cross-innovation team of Bethune Medical Department of Jilin University Leading the Charge with Open Competition construction project[2022JBGS04] ; Jilin University Graduate Training Office[2021JGZ08] ; Jilin University Graduate Training Office[2022YJSJIP20] ; Jilin University Graduate Training Office[2024JGY017] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:001289054900001 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 资助机构 | National Natural Science Foundation of China ; National Key R&D Program of China ; Jilin Province Science and Technology Development Plan ; Medicine+X cross-innovation team of Bethune Medical Department of Jilin University Leading the Charge with Open Competition construction project ; Jilin University Graduate Training Office |
| 源URL |  |
| 专题 | 金属研究所_中国科学院金属研究所 |
| 通讯作者 | Wu, Xiaofeng; Huang, Keke |
| 作者单位 | 1.Jilin Univ, Coll Chem, State Key Lab Inorgan Synth & Preparat Chem, Jilin Prov Int Cooperat Key Lab Adv Inorgan Solid, Changchun 130012, Peoples R China 2.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua RD, Shenyang 110016, Peoples R China |
| 推荐引用方式 GB/T 7714 | Guo, Zhangtao,Zhu, Qian,Wang, Shaohua,et al. Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2024:12. |
| APA | Guo, Zhangtao.,Zhu, Qian.,Wang, Shaohua.,Jiang, Mengpei.,Fan, Xinxin.,...&Feng, Shouhua.(2024).Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,12. |
| MLA | Guo, Zhangtao,et al."Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2024):12. |
入库方式： OAI收割
来源：金属研究所
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