STRUCTURE-SENSITIVITY AND ENSEMBLE EFFECTS IN REACTIONS OF STRONGLY ADSORBED INTERMEDIATES - CATALYTIC DEHYDROGENATION AND DEHYDRATION OF FORMIC-ACID ON NICKEL

Formic acid (HCOOH) dehydrogenates and dehydrates catalytically on Ni surfaces by unimolecular decomposition of strongly adsorbed formate intermediates. The rate of these reactions and the identity and decomposition selectivity of surface formate are not affected by Ni dispersion or by changes in Ni ensemble size resulting from Cu alloying or from coadsorption of CO and oxygen. Dehydrogenation and dehydration occur via identical intermediates that require small Ni ensembles (1-2 surface atoms) and that decompose with similar activation energy, a surprising result because the required molecular rearrangements differ markedly in the two decomposition modes. We suggest that reaction trajectories bifurcate after the formation of the activated complex in the rate-determining formate-decomposition step, leading to two kinetically indistinguishable decomposition paths. The decomposition selectivity on metal catalysts is controlled by entropy differences between the two reaction paths and by the binding energy of adsorbed oxygen atoms on these metal surfaces.