Structural and Energetic Trends of Ethylene Hydrogenation over Transition Metal Surfaces

Density functional theory calculations are used to investigate the catalytic hydrogenation of ethylene to ethane over a wide range of transition metal (TM) surfaces. Assuming the Horuiti–Polanyi mechanism, the enthalpies of adsorption, surface diffusion, and hydrogenation barriers are examined over close-packed surfaces of Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. Special attention is given to the effects of ethylene and hydrogen coverage on the reaction pathway and activation energies. The previously suggested importance of the balance between di-σ and π adsorption modes is reinvestigated, and most metals are found to exhibit a preference for the π state. Hydrogen coverage is found to control the reactant stability and promote a surface distortion which facilitates the hydrogen addition reaction. For all TMs, the calculated activation energies are low and span a narrow range.