With a half filled d-electron shell, molybdenum (Mo) plays an important role as catalysts in the petrochemical industry. However, Mo is generally regarded as not catalytically active for oxygen reduction reaction (ORR) compared with other transition metals such as Fe and Co. Inspired by molybdoenzymes, herein, we successfully endow Mo single-atom catalyst with highly ORR catalytic activity though engineering the coordination environment. This unique Mo single-atom catalyst consists of oxygen and nitrogen dual-component coordinated central Mo atom anchored on porous carbon (Mo-O/N-C), showing prominent ORR catalytic performance compared to the state-of-the-art Pt/C under alkaline condition. The extraordinary performance of Mo-O/N-C electrocatalyst is also demonstrated in Zn-air batteries as an air cathode. Density functional theory (DFT) calculations reveal the oxygen and nitrogen dual-component coordination could tailor the d-band center of Mo, subsequently optimizing its binding capability with reaction intermediates (O*, OH* and OOH*), hence accelerating overall ORR process. This work not only provides an efficient and commercially competitive ORR catalyst, but advancing further development of other electrocatalysts through engineering the coordination environment.

钼（Mo）具有半填充的d电子壳，在石化工业中起着重要的催化剂的作用。但是，与其他过渡金属（例如Fe和Co）相比，Mo通常被认为对氧还原反应（ORR）不具有催化活性。受钼酶的启发，本文通过工程改造成功地赋予Mo单原子催化剂以高ORR催化活性。协调环境。这种独特的Mo单原子催化剂由固定在多孔碳（Mo-O / NC）上的氧和氮双组分配位的中心Mo原子组成，与最先进的Pt / C相比，在高温下具有显着的ORR催化性能。碱性条件。Mo-O / NC电催化剂的非凡性能在作为空气阴极的Zn-空气电池中也得到了证明。密度泛函理论（DFT）计算显示，氧和氮的双组分配位可以定制Mo的d带中心，随后优化其与反应中间体（O *，OH *和OOH *）的结合能力，从而加快了整个ORR过程。这项工作不仅提供了一种高效且具有商业竞争力的ORR催化剂，还通过设计协调环境来促进其他电催化剂的进一步开发。