Thermal activation and reaction of allyl alcohol on Ni(100)

The thermal chemistry of allyl alcohol (CH2CHCH2OH) on a Ni(100) single-crystal surface was studied by the temperature programmed desorption (TPD) and the X-ray photoelectron spectroscopy (XPS). The allyl alcohol adsorbs molecularly on the metal surface at 100 K. Intact molecular desorption from the surface occurs at temperatures around 180 K, but some molecules exhibit chemical reactivity on the surface: activation of the OH, CC, and CO bonds produces η1(O)-allyloxy CH2CHCH2O(a), η2(C, C) allyl alcohol (C(a)H2C(a)HCH2OH), and η3(C, C, O)-alkoxide (C(a)H2C(a)CH2 O(a)) intermediates. Further thermal activation of allyl alcohol on the surface yields propylene (CH2CHCH3), 1-propanol (CH3CH2CH2OH), propanal (CH3CH2CHO), and combustion and dehydrogenation products (H2O, H2, and CO). Propylene desorbs from the surface at temperatures of around 270 K. Hydrogenation to the η3(C, C, O)-alkoxide intermediate leads to the production of propanal which desorbs from the surface around 320 K, while hydrogenation of the η2(C, C) allyl alcohol intermediate produces 1-propanol, which desorbs at around 310 K. The co-adsorption of hydrogen atoms on the surface enhances the formation of the saturated alcohol, while co-adsorption of oxygen enhances the formation of both the saturated alcohol and the saturated aldehydes.