The catalytic decomposition of formic acid into carbon dioxide and hydrogen (HCO2H -> CO2 + H-2) on M(2 1 1) (M = Ni, Pd, Pt) was investigated by using spin-polarized plane-wave based density functional theory calculations. It is found that on M(2 1 1) formic acid prefers the O (O=C) atom atop adsorption and the H (H-O) atom bridging two neighboring metal atoms, and formate prefers the bidentate adsorption with O atoms atop on metal surface. For M = Ni, Pd, Pt, formic acid has close adsorption energies (-0.69, -0.58, -0.61 eV) and also close dissociation barriers (0.42, 0.53, 0.51 eV), and the dissociation step is exothermic (-0.95, -0.44, -0.81 eV). Formate dissociation into surface CO2 and H (HCOO -> CO2 + H) is the rate-determining step; and the effective barrier is higher on Ni(2 1 1) than on Pd(2 1 1) and Pt(2 1 1) (1.43 vs. 0.96 and 0.86 eV), and formate dissociation is endothermic (0.44 eV) on Ni(2 11), but exothermic on Pd(2 1 1) and Pt(2 1 1) (-0.09 vs. -0.19 eV). On M(2 11), CO2 has chemisorption (-0.32, -0.13, -0.27 eV for M = Ni, Pd, Pt, respectively). For formate dissociation, detailed comparisons between M(2 1 1) and M(1 1 1) show that Pd(1 1 1) and Pt(2 1 1) have the smallest effective barriers, while Pt(1 1 1) and Ni(2 1 1) have the largest effective barriers. (C) 2013 Elsevier B.V. All rights reserved.