Tackling the activity and selectivity challenges of electrocatalysts toward the CO2RR via biatom catalysts on the 2D extended phthalocyanines

The development of efficient CO2 electrocatalytic reduction catalysts has become increasingly important. However, addressing issues related to activity and selectivity remains challenging due to the lack of robust design criteria. Organometallic sheets, characterized by their high surface area and well-dispersed metal sites, offer a unique platform for catalysis. In this study, we employed large-scale density functional theory calculations to investigate the transition metal dimers doped two-dimensional extended phthalocyanines (TM2-Pcs) as the biatom catalysts for the electrocatalysis of the CO2 reduction reaction (CO2RR). After systematical studies, the four catalysts of Mo-2-Pc, W-2-Pc, Ti-2-Pc, and Re-2-Pc were determined from 26 different TM2-Pcs. Among them, Mo-2-Pc, Ti-2-Pc, and W-2-Pc have not only high faradaic efficiency (FE) but also small limiting potentials of reducing CO2 to CH4. Besides, the limiting potentials for the reduction of CO2 to CH2CH2 on Mo-2-Pc and Re-2-Pc fall within the range of -1.4 to -.8 V versus reversible hydrogen electrode. They demonstrate higher FE than the experimental results obtained on Cu(111). This work not only expands the possibilities for discovering more effective CO2 reduction catalysts but also provides a feasible strategy for the rational design of electrocatalysts CO2RR.