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Pivotal Role of Geometry Regulation on O-O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts.
Chen, Qi-Fa; Xian, Ke-Lin; Zhang, Hong-Tao; Su, Xiao-Jun; Liao, Rong-Zhen; Zhang, Ming-Tian.
Afiliación
  • Chen QF; Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, 100084, Beijing, China.
  • Xian KL; Key Laboratory for Large-Format Battery Materials and System, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 430074, Wuhan, China.
  • Zhang HT; Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, 100084, Beijing, China.
  • Su XJ; Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, 100084, Beijing, China.
  • Liao RZ; Key Laboratory for Large-Format Battery Materials and System, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 430074, Wuhan, China.
  • Zhang MT; Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, 100084, Beijing, China.
Angew Chem Int Ed Engl ; 63(9): e202317514, 2024 Feb 26.
Article en En | MEDLINE | ID: mdl-38179807
ABSTRACT
In this study, we highlight the impact of catalyst geometry on the formation of O-O bonds in Cu2 and Fe2 catalysts. A series of Cu2 complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, the catalytic performance of these Cu2 complexes is enhanced as their molecular skeletons become more rigid, which contrasts with the behavior observed in our previous investigation with Fe2 analogs. Moreover, mechanistic studies reveal that the reactivity of the bridging O atom results in distinct pathways for O-O bond formation in Cu2 and Fe2 catalysts. In Cu2 systems, the coupling takes place between a terminal CuIII -OH and a bridging µ-O⋅ radical. Whereas in Fe2 systems, it involves the coupling of two terminal Fe-oxo entities. Furthermore, an in-depth structure-activity analysis uncovers the spatial geometric prerequisites for the coupling of the terminal OH with the bridging µ-O⋅ radical, ultimately leading to the O-O bond formation. Overall, this study emphasizes the critical role of precisely adjusting the spatial geometry of catalysts to align with the O-O bonding pathway.
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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: 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