In this study, we employed first-principles computations to design two-dimensional (2D) metal organic framework (MOF) electrocatalysts with metal-porphyrin nanosheets (TM-TCPP-MOF), for CO₂ electroreduction. We investigated 3d-transition metal doping on the porphyrin units to screen for efficient catalysts. Structural stability, including thermodynamic and electrochemical stability, was evaluated through binding energy, cohesive energy, formation energy, and dissolution potential analyses. Our results show that TM-TCPP-MOF catalysts are both thermodynamically and electrochemically stable, and the predicted Gibbs free energy profiles indicate HCOOH and CO as the most likely products. The stability of *COOH on Fe-, Co-, Ni-, and Cu-TCPP-MOF leads to CO formation, while *OCHO stabilization on Sc-, Ti-, V-, Cr-, and Mn-TCPP-MOF favors HCOOH production. The competitive hydrogen evolution reaction (HER) was evaluated to study the selectivity. Cr-TCPP-MOF and Co-TCPP-MOF exhibit superior selectivity and activity for CO₂ electroreduction.

中文翻译：

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通过包含金属配位卟啉的 2D 金属有机框架的非均相催化剂进行电化学 CO2 还原


在这项研究中，我们采用第一性原理计算设计了带有金属卟啉纳米片 （TM-TCPP-MOF） 的二维 （2D） 金属有机框架 （MOF） 电催化剂，用于 CO₂ 电还原。我们研究了卟啉单元上的 3D 过渡金属掺杂，以筛选有效的催化剂。通过结合能、内聚能、形成能和溶解势分析来评估结构稳定性，包括热力学和电化学稳定性。我们的结果表明，TM-TCPP-MOF 催化剂在热力学和电化学上都具有稳定性，预测的吉布斯自由能分布表明 HCOOH 和 CO 是最可能的产物。*COOH 对 Fe-、Co-、Ni- 和 Cu-TCPP-MOF 的稳定性导致 CO 形成，而 *OCHO 对 Sc-、Ti-、V-、Cr- 和 Mn-TCPP-MOF 的稳定性有利于 HCOOH 的产生。评估竞争性析氢反应 （HER） 以研究选择性。Cr-TCPP-MOF 和 Co-TCPP-MOF 对 CO₂ 电还原表现出优异的选择性和活性。