Engineering the coordination environment enables molybdenum single-atom catalyst for efficient oxygen reduction reaction
Engineering the coordination environment enables molybdenum single-atom catalyst for efficient oxygen reduction reaction
复制标题
设计配位环境使钼单原子催化剂能够实现高效的氧还原反应
DOI：
10.1016/j.jcat.2020.05.034
复制
发表时间：
2020
影响因子：
7.3
通讯作者：
Chen Qianwang
中科院分区：
文献类型：
--
作者：
Wang Changlai;Wang Dongdong;Liu Shuai;Jiang Peng;Lin Zhiyu;Xu Pengping;Yang Kang;Lu Jian;Tong Huigang;Hu Lin;Zhang Wenjun;Chen Qianwang
钼 (Mo) 具有半填充的 d 电子层，在石化工业中作为催化剂发挥着重要作用。然而，与Fe和Co等其他过渡金属相比，Mo通常被认为对氧还原反应（ORR）没有催化活性。受钼酶的启发，我们通过设计配位环境，成功地赋予Mo单原子催化剂高ORR催化活性。这种独特的Mo单原子催化剂由锚定在多孔碳（Mo-O/N-C）上的氧和氮双组分配位中心Mo原子组成，与最先进的Pt/C相比，在碱性条件下表现出突出的ORR催化性能。 Mo-O/N-C电催化剂的非凡性能也在锌空气电池作为空气阴极中得到了体现。密度泛函理论（DFT）计算表明，氧和氮双组分配位可以调整Mo的d带中心，从而优化其与反应中间体（O*、OH*和OOH*）的结合能力，从而加速整个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，而且通过设计配位环境促进了其他电催化剂的进一步开发。
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.