Unlocking cathodic potential dependent Pd deactivation for energy efficient CO2 electroreduction to formate

Pd-based materials are among the best electrocatalysts with high CO2-to-formate selectivity at near-equilibrium potential. However, the efficiency of Pd is severely hindered by its deactivation at elevated overpotentials, resulting in limited formate production activity within a narrow potential window. Herein, by constructing a palladium/fullerene (PdC60) composite catalyst, we achieve improved activity towards formate production and enhanced resistance to deactivation at high overpotentials. As a result, the PdC60 composite achieves practically relevant current density of 250 mA cm−2 in 4 cm2 membrane electrode assembly reactor with a modest cell voltage of 1.71 V, along with the energy efficiency up to 72% towards formate, demonstrating its promise for future implementation. Mechanistically, we pinpoint the enhanced performance of PdC60 to the profound interfacial charge transfer from Pd to C60 substrate, which suppresses Pd-H phase transition and alleviates CO poisoning during catalysis. Overall, our discoveries shed light on the complex potential-dependent interplays between the phase evolution of Pd-based catalysts and CO2 electroreduction performance, highlighting its promise for energy-efficient CO2 conversion. The efficiency of palladium catalyzed CO2 electroreduction is severely hindered by catalyst deactivation. Here, the authors report that engineering a palladium-fullerene interface enhances resistance to deactivation, enabling energy-efficient CO2-to-formate conversion over a broad potential window.