Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation

doi:10.1002/anie.202406711

IMR OpenIR

	Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation
	Guo, Zhangtao 1; Zhu, Qian 1; Wang, Shaohua 1; Jiang, Mengpei 2; Fan, Xinxin 1; Zhang, Wanyu 1; Han, Mei 1; Wu, Xiaotian 1; Hou, Xiangyan 1; Zhang, Yaowen 1; Shao, Zhiyu 1; Shi, Jingyu 1; Zhong, Xia 1; Li, Shuting 1; Wu, Xiaofeng 1; Huang, Keke 1; Feng, Shouhua 1
通讯作者	Wu, Xiaofeng(kkhuang@jlu.edu.cn) ; Huang, Keke(wuxf@jlu.edu.cn)
	2024-08-12
发表期刊	ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
ISSN	1433-7851
页码	12
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.
关键词	Spin states Octahedral sites pi-pi type Orbital Coupling pi-donation e(g) Filling
资助者	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
DOI	10.1002/anie.202406711
收录类别	SCI
语种	英语
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
WOS类目	Chemistry, Multidisciplinary
WOS记录号	WOS:001289054900001
出版者	WILEY-V C H VERLAG GMBH
引用统计
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/188881
专题	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.