Metal phthalocyanines (MPcs), as non-precious metal catalysts, have shown great promise in catalyzing the Oxygen Reduction Reaction (ORR). However, understanding their electronic structures during ORR and their impact on catalytic performance is still limited. In this work, we employed density functional theory (DFT) to investigate strategies to modulate the electronic structures of MPcs by altering central metals and introducing substituents. Our study revealed that changing central metals regulates the adsorption of key intermediate OOH* and promotes ORR activity. Subsequently, we introduced different substituents to optimize OOH* adsorption, achieving a low overpotential of only 0.37 V. Moreover, we proposed a novel bond order scheme to describe OOH* adsorption strength and the electronic origin of ORR activity. Our findings offer valuable insights into catalyst design for enhancing electrochemical reactions.

中文翻译：

---

促进金属酞菁的氧还原反应：改变中心金属和取代基


金属酞菁（MPcs）作为非贵金属催化剂，在催化氧还原反应（ORR）方面显示出巨大的前景。然而，了解它们在 ORR 过程中的电子结构及其对催化性能的影响仍然有限。在这项工作中，我们采用密度泛函理论（DFT）来研究通过改变中心金属和引入取代基来调节MPcs电子结构的策略。我们的研究表明，改变中心金属可以调节关键中间体 OOH* 的吸附并促进 ORR 活性。随后，我们引入不同的取代基来优化 OOH* 吸附，实现了仅 0.37 V 的低过电势。此外，我们提出了一种新颖的键序方案来描述 OOH* 吸附强度和 ORR 活性的电子起源。我们的研究结果为增强电化学反应的催化剂设计提供了宝贵的见解。