Revealing the Role of d Orbitals of Transition-Metal-Doped Titanium Oxide on High Efficient Oxygen Reduction

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 Ti1-xO2 nanosheets (Pt-1/Co-1-Ti1-xO2) 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-Ti1-xO2 is experimentally fabricated, and the excellent ORR catalytic performance is further demonstrated. Further analysis reveals that the superior ORR performance of Pt-1-Ti1-xO2 to Co-1-Ti1-xO2 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. [GRAPHICS] .

Automated summary

The study introduces a new strategy to understand the catalytic mechanisms at the atomic orbital level by focusing on the d orbitals of Pt/Co-Ti realms, using Pt-1/Co-1-Ti1-xO2 nanosheets as a model catalyst for the oxygen reduction reaction (ORR). It was found that Pt-1-Ti1-xO2 exhibits superior ORR performance compared to Co-1-Ti1-xO2 due to the stronger activation of Ti by Pt through d-d hybridization.