Towards understanding the catalytic bond-breaking sequences of polyol oxidation on PD(111) single crystal model catalysts

Understanding the bond-breaking sequences of catalytic polyol oxidation on transition metal catalysts is critical for the chemical transformation of biomass derived chemical feedstock into value-added products which may also offer new alternatives to fossil fuel-based commodity chemicals. In the current work, oxidation of ethylene glycol on an atomically well-defined Pd(111) single crystal planar model catalysts was investigated via temperature programmed desorption (TPD) technique under ultra-high vacuum (UHV) conditions. Presence of surface oxygen atoms was found to promote the formation of formaldehyde (H2CO) and carbon dioxide as the most prominent catalytic oxidation products. Enhancement in formaldehyde generation was observed upon increasing the ethylene glycol-to-oxygen ratio. Our results indicate that the activation of C-C bonds was primarily facilitated by atomic oxygen, preceding the complete dehydrogenation of the C2HxOz surface species. The formation of H2CO was mainly attributed to the most unstable surface species in terms of C-C bond scission, namely -OCH2CO- and -OCH2CHO-. Other surface species such as -OCHCHO- and -OCHCO- led to additional decomposition products such as CO rather than formaldehyde.