Small-Sized Fe n Clusters Supported on the Anatase TiO2(101) Surface as a Promising High-Performance Catalyst for the N2 Reduction Reaction

• Published in: Journal of physical chemistry. C 2024-06, Vol.128 (24), p.9993-10006
• Main Authors: Jin, Wenjing, Feng, Aohua, He, Taixin, Li, Dongdong, Qu, Bingyan, Zhou, Rulong
• Format: Article
• Language: English
• Subjects: C: Chemical and Catalytic Reactivity at Interfaces
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.4c02443

Based on an extensive structural search and first-principles calculations, the structural evolution, electronic properties, and catalytic properties for the nitrogen reduction reaction (NRR) of TiO2(101) surface supported Fe n clusters are systematically investigated. Much difference from those of Ni n /TiO2 and Cu n /TiO2 is observed. The growth pattern of Fe n /TiO2 is similar to that of Ni n /TiO2 for n ≤ 7 but different for n ≥ 8. The stronger Fe–Fe and Fe–TiO2 interactions lead to different size-dependent behaviors of thermodynamic stabilities of Fe n /TiO2 compared to Ni n /TiO2 and Cu n /TiO2. Fe3/TiO2, Fe5/TiO2, and Fe8/TiO2 are more stable compared to their neighbors. The strong orbital hybridization in Fe–O–Ti leads to a larger amount of charge transferring from Fe to the surface and different accumulation sites of the transferred charge compared to Ni n /TiO2 and Cu n /TiO2, different size-dependent behaviors of the average magnetic moments of Fe for the supported and isolated Fe n clusters, as well as the magnetization of surface Ti atoms. Fe5/TiO2 and Fe8/TiO2 exhibit excellent NRR catalytic performance, characterized by low energy barriers of the rate-determining steps and the desorption of the NH3 product. This work, combined with our previous work, presents a comprehensive understanding of the difference among Fe n /TiO2, Ni n /TiO2, and Cu n /TiO2, providing valuable insights for the design and development of efficient catalyst for nitrogen reduction.