Theoretical study of decomposition of formic acid over Pd catalyst anchored on N‐doped graphene

Abstract

AbstractThe formic acid decomposition (FAD) reaction generates H2 or CO via two competing pathways. The development of high‐efficiency catalysts and clarification of the FAD reaction mechanism are therefore important. Single‐atom/single‐site catalysts (SACs/SSCs) are attracting considerable attention due to their maximum atomic utilization, considerable cost reductions, and superior potential catalytic activity and selectivity. In this work, we precisely designed PdN3‐G and Pd3N3‐G to elucidate the FAD reaction mechanism and used density functional theory (DFT) calculations to explain the effects of Pd atoms and Pd3 clusters. Calculations were performed for four possible FAD reaction pathways. The FAD reaction cannot be achieved completely on the PdN3‐G surface because of the high energy barriers. However, Pd3N3‐G is more favorable with a rate‐determining step energy barrier of 0.55 eV for the carboxyl pathway; the energy barrier for the formate pathway is 1.61 eV. The energy barriers of the two CO pathways are 1.31 and 3.01 eV, respectively. The results indicate that Pd3N3‐G is a promising catalyst for FAD reaction and provide a theoretical basis for the rational design of SACs/SSCs for FAD reaction.