Your browser doesn't support javascript.
loading
Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation.
Guo, Zhangtao; Zhu, Qian; Wang, Shaohua; Jiang, Mengpei; Fan, Xinxin; Zhang, Wanyu; Han, Mei; Wu, Xiaotian; Hou, Xiangyan; Zhang, Yaowen; Shao, Zhiyu; Shi, Jingyu; Zhong, Xia; Li, Shuting; Wu, Xiaofeng; Huang, Keke; Feng, Shouhua.
Afiliación
  • Guo Z; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Zhu Q; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Wang S; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Jiang M; Shenyang National Laboratory for Materials Science Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua RD, Shenyang, 110016, China.
  • Fan X; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Zhang W; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Han M; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Wu X; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Hou X; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Zhang Y; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Shao Z; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Shi J; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Zhong X; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Li S; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Wu X; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Huang K; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
  • Feng S; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
Angew Chem Int Ed Engl ; : e202406711, 2024 Jun 24.
Article en En | MEDLINE | ID: mdl-38923764
ABSTRACT
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 π-π type orbital coupling of 3d (Co)-2p (O)-4f (Ce) was employed to regulate the spin state of octahedral cobalt sites (CoOh) in the composite of Co3O4/CeO2. More specifically, the equivalent high-spin ratio of CoOh can reach to 54.7 % via tuning the CeO2 content, thereby triggering the average eg 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 π-π type coupling corroborated by the matched energy levels between Ce t1u/t2u-O and CoOh t2g-O π type bond in the calculated crystal orbital Hamilton population and partial density of states profiles, stimulates a π-donation between O 2p and π-symmetric Ce 4fyz 2 orbital, consequently facilitating the electrons hopping from t2g to eg orbital of CoOh. This work offers an in-depth insight into understanding the 4f and 3d orbital coupling for spin state optimization in composite oxides.
Palabras clave
Texto completo
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2024 Tipo del documento: Article País de afiliación: China
Texto completo
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2024 Tipo del documento: Article País de afiliación: China