C-O bond scission of methoxide on Pd nanoparticles: a density functional study

C-O bond scission of methoxide species adsorbed at the surface of Pd nanoparticle was studied by DF calculations for the example of cuboctahedral Pd(79). To investigate different locations of adsorbed intermediates as well as the transition state of C-O bond scission, a substrate model was used, which allows one to consider adsorbates without any local geometry restrictions. In contrast to reaction sites on the flat Pd(111) surface and on extended facets, scission of the C-O bond of methoxide at cluster edges is exothermic by approximately 40 kJ mol(-1) and the decomposition product CH(3) is found to be stabilized there. However, the high calculated activation barrier, approximately 140 mol(-1), implies only a very slow reaction compared to dehydrogenation of CH(3)O.