Single-atom tailored transition metal oxide enhances d-p hybridization in catalytic conversion for lithium-oxygen batteries

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2024-05, Vol.488, p.151064, Article 151064
• Main Authors: Guan, Shuyun, Li, Xudong, Zhao, Yang, Han, Guokang, Lou, Shuaifeng, Zhu, Yongming
• Format: Article
• Language: English
• Subjects: Catalytic conversion; D-p hybridization; Lithium-oxygen battery; single-atom Nb tailored Co3O4/h-PANI; Structure–function relationship
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2024.151064

•Nb-SA@Co3O4/h-PANI as electrocatalyst presents remarkable cycling performance.•Core-shell hollow polyaniline structure.•d-p orbital hybridization between TMOs and intermediate.•Growth kinetics of Li2O2 on Co sites in Nb-SA@Co3O4/h-PANI. Although the incorporation of d-block single atoms (d-SAs) into TMO is an effective strategy to regulate the intrinsic catalytic function, the comprehensive understanding of the electronic structure of the catalyst and the interaction mechanism with the reaction intermediates is still unclear, making it difficult to design the optimal active site. In this contribution, we establish a clear relationship between the active centers, electronic structure, and oxygen adsorption behavior of the active site. The Nb-SA induce an increase in the energy levels of dx2-y2 and effectively activate the redox activity of dx2-y2 at Co site, which dramatically optimized the adsorption behavior of key intermediate. Thereby the strong adsorption between the active cations and intermediates promotes uniform nucleation of discharge products, and significantly improve the energy storage performance of Nb-SA@Co3O4/h-PANI. The assembled Nb-SA@Co3O4-based LOB can operate with low overpotential and long-term cycle stability. Our findings provide insight into electronic structure regulation and activity promotion of efficient catalysts for LOBs.