Theoretical investigation on the effect of doped Pd on the Cu(111) surface for formic acid oxidation: competing formation of CO2 and CO

Abstract DFT calculations are employed to study the formic acid oxidation mechanism on the Pd-Cu(111) surface and explore the effect of the doped-Pd atoms on the catalytic selectivity. Compared with that on Cu(111), it is indicated that the doped-Pd atoms alter the adsorption intensity of intermediates with the d-band center change of the bimetallic surface. About formic acid oxidation, the C-H bond cleavage in HCOOH is prior to the H-O and C-O bond cleavage. The competing formation of CO2 and CO is identified on the Pd-Cu(111) surface. The doped Pd atoms change the reaction pathways and enhance the selectivity of CO2.