Kinetic and Mechanistic Assessment of Alkanol/Alkanal Decarbonylation and Deoxygenation Pathways on Metal Catalysts.

This study combines theory and experiment to determine the kinetically relevant steps and site requirements for deoxygenation of alkanols and alkanals. These reactants deoxygenate predominantly via decarbonylation (C-C cleavage) instead of C-O hydrogenolysis on Ir, Pt, and Ru, leading to strong inhibition effects by chemisorbed CO (CO*). C-C cleavage occurs via unsaturated species formed in sequential quasi-equilibrated dehydrogenation steps, which replace C-H with C-metal bonds, resulting in strong inhibition by H2, also observed in alkane hydrogenolysis. C-C cleavage occurs in oxygenates only at locations vicinal to the C═O group in RCCO* intermediates, because such adjacency weakens C-C bonds, which also leads to much lower activation enthalpies for oxygenates than hydrocarbons. C-O hydrogenolysis rates are independent of H2 pressure and limited by H*-assisted C-O cleavage in RCHOH* intermediates on surfaces with significant coverages of CO* formed in decarbonylation events. The ratio of C-O hydrogenolysis to decarbonylation rates increased almost 100-fold as the Ir cluster size increased from 0.7 to 7 nm; these trends reflect C-O hydrogenolysis reactions favored on terrace sites, while C-C hydrogenolysis prefers sites with lower coordination, because of the relative size of their transition states and the crowded nature of CO*-covered surfaces. C-O hydrogenolysis becomes the preferred deoxygenation route on Cu-based catalysts, thus avoiding CO inhibition effects. The relative rates of C-O and C-C cleavage on these metals depend on their relative ability to bind C atoms, because C-C cleavage transitions states require an additional M-C attachment.