▎ 摘　　要

The catalytic decomposition of formic acid (HCOOH) is a crucial process for hydrogen production technologies. Herein, periodic density functional theory (DFT) calculations were employed to explore the effect of N-doping on the decomposition of formic acid. We designed a series of single Pd-atoms deposited in the single vacancy of N-doped graphene sheets, namely Pd-DGr, Pd-N1Gr, Pd-N2Gr, and Pd-N3Gr, as the proposed catalysts. Our findings show that H2 production from HCOOH dehydrogenation on these surfaces pro-ceeds via the formate (HCOO) pathway (Path-I) rather than the carboxylate (COOH) pathway (Path-II). Furthermore, the Pd-N3Gr catalyst shows the greatest catalytic reac-tivity toward HCOOH dehydrogenation via Path-I, requiring an activation energy (Ea) of 0.38 eV.On the other hand, the undesirable dehydration of HCOOH to carbon monoxide (CO) through COOH (Path-IIIA) or formyl (HCO) (Path-IIIB) intermediates is unlikely to occur on Pd-N3Gr due to a large activation energy. We found that the active species on the catalyst surface increased with N-doping concentration. Additionally, microkinetic simulations of the HCOOH decomposition on these surfaces confirmed the high activity and selectivity of the Pd-N3Gr catalyst toward HCOOH dehydrogenation (Path-I). These calculated results highlight that the Pd-N3Gr catalyst is a promising candidate for the formic acid decom-position reaction to yield hydrogen.(c) 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.