1. Alkane C-H Bond Breaking at Catalytic Metal Surfaces: Theory
Alkane C-H Bond Breaking at Catalytic Metal Surfaces: Theory
Development Coupled with Effusive Molecular Beam Experiments
Ian Harrison, Department of Chemistry, University of Virginia
Microcanonical unimolecular rate theory (MURT) has been developed to treat activated dissociative chemisorption at surfaces – a reactive step that can rate-limit important petrochemical processes such as the steam reforming of alkanes over Ni catalysts. Nonequilibrium dissociative sticking coefficients S(Tg, Ts) for increasingly complex alkanes on single crystal metal surfaces are being measured using effusive molecular beams and modeled by MURT.
Over the last year, we:
demonstrated the ability of MURT to treat two benchmark systems for gas-surface reaction dynamics where detailed balance can be applied: (i) the dissociation and associative desorption of H2 on Cu(111), and (ii) the dissociation of CO2 and CO oxidation on Rh(111). For both systems, treating rotation as a spectator to the reaction dynamics was found to be a good approximation at thermally relevant energies.
developed an improved effusive molecular beam source.
began measurements of S(Tg, Ts) for higher alkanes, such as propane, on Pt(111).
Associative desorption dynamics for D2/Cu(111). MURT predictions
(lines & open points) compared to experimental data (filled points).