Structure effects of benzene hydrogenation studied with sum frequency generation vibrational spectroscopy and kinetics on Pt(111) and Pt(100) single-crystal surfaces.

Sum frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have identified at least two reaction pathways for benzene hydrogenation on the Pt(100) and Pt(111) single-crystal surfaces at Torr pressures. Kinetic studies at low temperatures (310-370 K) show that benzene hydrogenation does not proceed through cyclohexene. A Langmuir-Hinshelwood-type rate law for the low-temperature reaction pathway is identified. The rate-determining step for this pathway is the addition of the first hydrogen atom to adsorbed benzene for both single-crystal surfaces, which is verified by the spectroscopic observation of adsorbed benzene at low temperatures on both the Pt(100) and Pt(111) crystal faces. Low-temperature SFG studies reveal chemisorbed and physisorbed benzene on both surfaces. At higher temperatures (370-440 K), hydrogenation of benzene to pi-allyl c-C(6)H(9) is observed only on the Pt(100) surface. Previous single-crystal studies have identified pi-allyl c-C(6)H(9) as the rate-determining step for cyclohexene hydrogenation to cyclohexane.