Theoretical Investigations of (Oxidative) Dehydrogenation of Propane to Propylene over Palladium Surfaces

Herein we present density functional theory calculations of the (oxidative) dehydrogenation of propane on Pd(111) and Pd(211) surfaces. We find that, independently of the surfaces and the intermediate product (1-propyl or 2-propyl), O-assisted dehy-drogenation of propane is always less favorable than the direct or OH-assisted hydrogen abstraction. Additionally, we show that the transition state energies of the (oxidative) dehydro-genation of propane on Pd surfaces scale with the final state energies and are similar to trends observed for methane activa-tion. This work is a first and essential step to understand the role of surface oxygen species and mechanism of (O)DHP on Pd-based catalysts.