Revealing the Role of d Orbitals of Transition-Metal-Doped Titanium Oxide on High-Efficient Oxygen Reduction
Fei Lu, Weiwei Xie, Yi Ding, Yan Wang, Fengchu Zhang, Yong Xu, Bo Zhou, Shoujie Liu, Xi Wang, Jiannian Yao
Abstract
Precise catalysis is critical for the high-quality catalysis industry. However, it remains challenging to fundamentally understand precise catalysis at the atomic orbital level. Herein, we propose a new strategy to unravel the role of specific d orbitals in catalysis. The oxygen reduction reaction (ORR) catalyzed by atomically dispersed Pt/Co-doped Ti$_{1−x}$O$_{2}$ nanosheets (Pt$_{1}$/Co$_{1}$–Ti$_{1−x}$O$_{2}$) is used as a model catalysis. The z-axis d orbitals of Pt/Co–Ti realms dominate the O$_{2}$ adsorption, thus triggering ORR. In light of orbital-resolved analysis, Pt$_{1}$/Co$_{1}$–Ti$_{1−x}$O$_{2}$ is experimentally fabricated, and the excellent ORR catalytic performance is further demonstrated. Further analysis reveals that the superior ORR performance of Pt$_{1}$–Ti$_{1−x}$O2 to Co$_{1}$–Ti$_{1−x}$O$_{2}$ is ascribed to stronger activation of Ti by Pt than Co via the d–d hybridization. Overall, this work provides a useful tool to understand the underlying catalytic mechanisms at the atomic orbital level and opens new opportunities for precise catalyst design.