Metalloporphyrin-based covalent organic frameworks (Por-COFs) are emerging as electrocatalysts; however, so far experiments have primarily focused on M–N₄-coordinated Por-COFs. A wealth of coordination modified systems with potential catalytic capability remains to be explored. Herein, we report a proof-of-concept computational study on the coordination engineering of Por-COFs as electrocatalysts for reducing CO₂ and O₂. Systematic density functional theory calculations were performed on 15 types of heteroatomic Por-COFs, featuring M–N_xO_yS_z (M = Fe, Co, and Ni; x + y + z = 4) centers. Calculations predicted that the Co–N₂O₂-Por-COF is an optimal CO₂-to-CO catalyst candidate (limiting potential ) and the Ni–N₂S₂-Por-COF is an optimal O₂-to-H₂O catalyst candidate (overpotential η^ORR = 0.46 V); both heteroatomic-Por-COFs display better catalytic activity and selectivity than their corresponding parent M–N₄-Por-COFs. Electronic structure analysis attributes the enhanced catalytic performance to the additional stabilization, endowed by the heteroatoms, of critical reaction intermediates. Furthermore, feature importance analysis based on machine learning models confirmed that the interplay between the central metal and the coordinated atoms is crucial for catalytic performance. This work predicts new Por-COFs as electrocatalysts for CO₂ and O₂ reduction and showcases the great potential of coordination regulation strategies in designing high-performance COF-based electrocatalysts.

中文翻译：

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通过配位工程提高金属卟啉基共价有机框架的 CO2 和 O2 还原催化性能

基于金属卟啉的共价有机骨架（Por-COF）正在成为电催化剂；然而，到目前为止，实验主要集中在 M-N ₄配位的 Por-COFs 上。大量具有潜在催化能力的配位修饰系统仍有待探索。_{在此，我们报告了关于 Por-COF 的配位工程作为还原 CO 2}和 O ₂的电催化剂的概念验证计算研究。_{对 15 种具有 M–N x} O _y S _z（M = Fe、Co 和 Ni；x + y + z = 4）中心的杂原子 Por-COF 进行了系统密度泛函理论计算。计算预测Co–N ₂ O ₂ -Por-COF是最佳的CO ₂制CO催化剂候选物（极限潜力），而Ni–N ₂ S ₂ -Por-COF是最佳的O ₂制H催化剂。 ₂ O候选催化剂（过电势η ^ORR = 0.46 V）；_{与相应的母体 M–N 4} -Por-COF相比，两种杂原子-Por-COF 均表现出更好的催化活性和选择性。电子结构分析将催化性能的增强归因于杂原子赋予关键反应中间体的额外稳定性。此外，基于机器学习模型的特征重要性分析证实，中心金属和配位原子之间的相互作用对于催化性能至关重要。这项工作预测了新型Por-COF作为CO ₂和O ₂还原的电催化剂，并展示了配位调控策略在设计高性能COF基电催化剂中的巨大潜力。