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−xO₂ nanosheets (Pt₁/Co₁–Ti_1−xO₂) is used as a model catalysis. The z-axis d orbitals of Pt/Co–Ti realms dominate the O₂ adsorption, thus triggering ORR. In light of orbital-resolved analysis, Pt₁/Co₁–Ti_1−xO₂ is experimentally fabricated, and the excellent ORR catalytic performance is further demonstrated. Further analysis reveals that the superior ORR performance of Pt₁–Ti_1−xO₂ to Co₁–Ti_1−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.

精确催化对于高质量催化行业至关重要。然而，从根本上理解原子轨道水平上的精确催化作用仍然具有挑战性。在这里，我们提出了一种新的策略来揭示特定d轨道在催化中的作用。通过原子分散的Pt / Co掺杂的Ti ₁ - _x O ₂纳米片（Pt ₁ / Co ₁ -Ti _{1- x} O ₂）催化的氧还原反应（ORR ）被用作模型催化。Pt / Co-Ti区域的z轴d轨道主导O ₂吸附，从而触发ORR。根据轨道分辨分析，Pt ₁ / Co ₁ -Ti通过实验制备了_{1- x} O ₂，并进一步证明了其优异的ORR催化性能。进一步的分析表明，Pt ₁ -Ti _{1- x} O ₂优于Co ₁ -Ti _{1- x} O _2的ORR性能归因于Pd通过d-d杂交对Co的Ti活化作用强于Co。总体而言，这项工作提供了一个有用的工具，可用于了解原子轨道水平上的潜在催化机制，并为精确催化剂设计提供了新机会。