Li Haobo, Wu Donghai, Wu Jiarui, Lv Wenjing, Duan Zhiyao, Ma Dongwei
Key Laboratory for Special Functional Materials of Ministry of Education, and School of Materials Science and Engineering, Henan University, Kaifeng 475004, China.
Henan Key Laboratory of Nanocomposites and Applications, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou 450006, China.
Nanoscale. 2024 Apr 4;16(14):7058-7067. doi: 10.1039/d4nr00028e.
The electrocatalytic NO reduction reaction (NORR) emerges as an intriguing strategy to convert harmful NO into valuable NH. Due to their unique intrinsic properties, graphene-based Fe single-atom catalysts (SACs) have gained considerable attention in electrocatalysis, while their potential for NORR and the underlying mechanism remain to be explored. Herein, using constant-potential density functional theory calculations, we systematically investigated the electrocatalytic NORR on the graphene-based Fe SACs. By changing the local coordination environment of Fe single atoms, 26 systems were constructed. Theoretical results show that, among these systems, the Fe SAC coordinated with four pyrrole N atoms and that co-coordinated with three pyridine N atoms and one O atom exhibit excellent NORR activity with low limiting potentials of -0.26 and -0.33 V, respectively, as well as have high selectivity toward NH by inhibiting the formation of byproducts, especially under applied potential. Furthermore, electronic structure analyses indicate that NO molecules can be effectively adsorbed and activated the electron "donation-backdonation" mechanism. In particular, the d-band center of the Fe SACs was identified as an efficient catalytic activity descriptor for NORR. Our work could stimulate and guide the experimental exploration of graphene-based Fe SACs for efficient NORR toward NH under ambient conditions.
电催化NO还原反应（NORR）作为一种将有害NO转化为有价值NH的有趣策略而出现。基于石墨烯的铁单原子催化剂（SACs）因其独特的内在性质，在电催化领域受到了广泛关注，但其NORR潜力及潜在机制仍有待探索。在此，我们使用恒电位密度泛函理论计算，系统地研究了基于石墨烯的铁SACs上的电催化NORR。通过改变铁单原子的局部配位环境，构建了26个体系。理论结果表明，在这些体系中，与四个吡咯N原子配位的铁SAC以及与三个吡啶N原子和一个O原子共配位的铁SAC表现出优异的NORR活性，其极限电位分别低至-0.26和-0.33 V，并且通过抑制副产物的形成对NH具有高选择性，尤其是在施加电位下。此外，电子结构分析表明，NO分子可通过电子“给予-反馈给予”机制被有效吸附和活化。特别是，铁SACs的d带中心被确定为NORR的有效催化活性描述符。我们的工作可以激发和指导基于石墨烯的铁SACs在环境条件下高效NORR生成NH的实验探索。
