[20p-W631-1~8] New trends in computational materials science -Molecular electronics and bioelectronics

[20p-W631-4] Theoretical Study of Electron Transfer in Complex/Semiconductor system for photocatalytic CO₂ reduction

〇Ryoji Asahi¹, Ryosuke Jinnouchi¹, Soichi Shirai¹, Akimov A.V.², Prezhdo O.V.² (1.Toyota Central R&D Labs., Inc., 2.Univ. of Southern California)

Keywords:artificial photosynthesis,elecron transfer

Artificial photosynthesis is one of the promising routes toward sustainable and clean energy. Recently, there has been increasing interest in development of materials for efficient photocatalytic CO₂ reduction and its transformation to useful chemicals. To realize high selectivity for CO₂ reduction to H₂ production, Ta₂O₅/Ru-complex system was proposed. One of the rate limiting processes in the overall photocatalytic reduction is an interfacial electron transfer from N-doped Ta₂O₅ to Ru-complex. This process strongly depends on two factors: (A) the way the Ru-complex is attached to the semiconductor surface, including the length and the nature of linker, as well as the anchor binding mode, and (B) a band alignment between conduction band minimum of the semiconductor and LUMO of Ru-complex. Here we investigate the dynamical and electronic structure effects of anchoring groups, PO₃Hs, COOH, and OH, in Ta₂O₅/Ru-complex system, and discuss the role of anchor groups for the electron transfer. .