Orbital Dependence in Single-Atom Electrocatalytic Reactions,The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Orbital Dependence in Single-Atom Electrocatalytic Reactions
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2022-06-23 , DOI: 10.1021/acs.jpclett.2c01381
Yanan Wang _{1,

2} , Yingzong Liang _{1,

2} , Tao Bo _{1,

2} , Sheng Meng _{1,

2} , Miao Liu _{1,

2,

3}

Affiliation

Transition metal single-atom catalysts supported on N-doped graphene (TM–N–C) could serve as an ideal model for studying orbital dependence in electrocatalytic reactions because the atom on the catalytic active site has discrete single-atom-like orbitals. In this work, the catalytic efficiency of Fe–N–C for the oxygen evolution reaction (OER) under a small structural perturbation has been comprehensively investigated with density functional theory calculations. The results suggest that the subtle local environment of a single atom can significantly modulate the catalytic reactivity. Further analysis demonstrates that the energy level of the TM d_z² orbital center, rather than the d-band center, is responsible for the OER catalytic efficiency as the d_z² orbital participates mainly in the reactions. Essentially, the d-band theory can be extended to the sub-d orbital level, and a small perturbation of the crystal field, induced by lattice strain or z-direction displacement of the TM atom, can prominently change the sub-d orbital associated with the reaction and in turn affect the catalytic activity.

中文翻译：

单原子电催化反应中的轨道依赖性

负载在 N 掺杂石墨烯 (TM-N-C) 上的过渡金属单原子催化剂可以作为研究电催化反应中轨道依赖性的理想模型，因为催化活性位点上的原子具有离散的类单原子轨道。在这项工作中，通过密度泛函理论计算，全面研究了 Fe-N-C 在小结构扰动下对析氧反应 (OER) 的催化效率。结果表明，单个原子的微妙局部环境可以显着调节催化反应性。_{进一步分析表明，与 d z}_{^{2一样，TM d}}_{z ²}轨道中心的能级而不是 d 带中心是 OER 催化效率的原因轨道主要参与反应。本质上，d 带理论可以扩展到亚 d 轨道水平，由晶格应变或TM 原子的z方向位移引起的晶体场的小扰动可以显着改变亚 d 轨道相关反应，进而影响催化活性。

更新日期：2022-06-23

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11