Quantifying π-electron delocalization as a universal descriptor for ORR activity in MN4 catalysts

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis Pub Date : 2025-03-24 DOI:10.1016/j.jcat.2025.116093

Miao-Ying Chen , Jiabo Le , Hao-Ran Wu , Wei-Dong Li , Jia-Nan Zhang , Bang-An Lu

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Abstract

The development of high-performance transition metal and nitrogen co-doped carbon (M−N−C) catalysts for the oxygen reduction reaction (ORR) hinges on identifying robust and quantitative descriptors for catalytic activity. In this study, we introduce the π-electron delocalization factor (Δπ) in the carbon basal plane as a universal and quantitative descriptor for ORR activity. By combining experimental data and density functional theory (DFT) calculations, we demonstrate that Δπ systematically tunes the d-orbital energy levels of MN₄ active sites, particularly the d_z² orbital, which governs the adsorption of oxygen intermediates and influences the rate-determining step of the ORR. A linear correlation between Δπ and ORR kinetics across different metal centers (Fe, Mn, Co, Ni) highlights the pivotal role of π-electron delocalization in optimizing the metal–oxygen interaction. This study provides a novel framework for quantifying catalytic performance and offers an efficient strategy for the rational design and screening of next-generation M−N−C catalysts with enhanced ORR activity.

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量化π-电子离域作为MN4催化剂中ORR活性的通用描述符

用于氧还原反应（ORR）的高性能过渡金属和氮共掺杂碳（M−N−C）催化剂的发展取决于确定催化活性的稳健和定量描述符。在本研究中，我们引入碳基面上π电子离域因子（Δπ）作为ORR活性的通用定量描述符。通过结合实验数据和密度功能理论（DFT）计算，我们证明Δπ系统地调节了MN4活性位点的d轨道能级，特别是dz2轨道，它控制着氧中间体的吸附并影响ORR的速率决定步骤。在不同金属中心（Fe, Mn, Co, Ni）上Δπ和ORR动力学之间的线性相关表明π-电子离域在优化金属-氧相互作用中的关键作用。该研究为量化催化性能提供了一个新的框架，并为合理设计和筛选下一代具有增强ORR活性的M - N - C催化剂提供了有效的策略。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.