Single-atom catalysts: Effects of end-group regulation on catalytic activity

The role of 14 metal elements as porphyrin-like monatomic catalysts in carbon dioxide reduction reaction (CO 2 RR) was studied using density functional theory (DFT) and computational hydrogen electrode (CHE) model. It highlights the ability of the catalyst to convert carbon from the + 4 valence state to the + 2 valence state, indicating that the end -tone node significantly improves metal properties and catalytic efficiency. Notably, the modification of the end group improved the structure of the Bi, Sb, and Sn-based catalysts and reduced the free energy barrier, although their initial configuration deviated from the expected configuration. In contrast, Fe, Ti, and V based catalysts showed good initial activity, but performance decreased after the terminal node. In addition, the free energy barrier of Co, Ni, Pd and Ir-based catalysts was significantly reduced by end -group regulation. Detailed analysis of the electron structure, especially Co and Ni, shows that the arrangement of electrons and the localization of d -band electrons through the terminal node are critical for regulating catalyst activity. This study not only highlights the importance of end -tone system in optimizing catalyst performance, but also provides a theoretical basis for designing efficient CO 2 RR catalysts, which is of great significance for the development of sustainable technologies.