1,3- and 1,4-cyclohexadiene reaction intermediates in cyclohexene hydrogenation and dehydrogenation on Pt(111) crystal surface: a combined reaction kinetics and surface vibrational spectroscopy study using sum frequency generation

The hydrogenation and dehydrogenation reactions of cyclohexene on Pt(lll) s urface were investigated by surface vibrational spectroscopy via sum freque ncy generation (SFG) both under ultrahigh vacuum (UHV) and high pressure co nditions with 10 Torr cyclohexene and various hydrogen pressures up to 590 Torr. Under UHV, cyclohexene on Pt(lll) undergoes a change from pi/sigma-bo nded, sigma-bonded, and c-C6H9 surface species to adsorbed benzene when the surface was heated. A site-blocking effect was observed at saturation cove rage of cyclohexene and caused the dehydrogenation to shift to higher surfa ce temperature, At high pressures, however, none of the species observed in UHV condition were seen. 1,4-cyclohexadiene (CHD) was found to be the majo r species on the surface at 295 K even in the presence of nearly 600 Torr o f hydrogen. Hydrogenation was the only detectable reaction at the temperatu re range between 300-400 K with I,3-CHD on the surface as revealed by SFG. Further increasing surface temperature results in a decrease in hydrogenati on reaction rate and an increase in dehydrogenation reaction rate with both 1,3-CHD and 1,4-CHD detectable on the surface simultaneously. Monitoring t he reaction kinetics and the chemical nature of surface species together al lows us to postulate a reaction mechanism: cyclohexene hydrogenates to cycl ohexane via a 1,3-CHD intermediate, and dehydrogenates to benzene through b oth 1,4-CHD and 1,3-CHD intermediates. Both 1,3- and 1,4-CHD dehydrogenate to benzene at sufficiently high temperature on Pt(111). (C) 1999 Elsevier S cience B.V. All rights reserved.