Coordination environment engineering of transition metal doped phthalocyanine single-atom catalysts for carbon dioxide reduction reaction: A DFT study

Developing of low cost and highly efficient electrocatalysts for carbon dioxide reduction (CRR) is becoming a research hotspot in both theoretical and experimental studies. In this work, we systematically investigated by first-principles calculations the electrocatalytic properties of transition-metal-anchored Phthalocyanine (Pc) monolayers with and without different heteroatom modifications, named TM-Pc and TM-X-Pc (TM = Sc similar to Zn, X = B, C, N, O, and S), respectively. The results show Cr-Pc, Mn-Pc, Sc-O-Pc, Cr-O-Pc, Mn-O-Pc, Fe-O-Pc, and Co-O-Pc exhibited excellent catalytic performance and high selectivity for CRR. The origin of catalytic activity analysis indicated the binding energy of intermediates E-b(*OH) and E-b(*CHO) serve as the descriptors for the catalytic performance of TM-X-Pc. Further comparative analyses showed that choosing appropriate coordination atoms is beneficial for adjusting the catalytic activity. The work suggests that the heteroatoms modified TM-X-Pc monolayer has high potential application as high-performance CRR catalyst and provides valuable theoretical guidance for designing efficient CRR catalysts.