Similarities and differences for atomic and diatomic molecule adsorption on the B-5 type sites of the HCP(101̅6) surfaces of Co, Os, and Ru from DFT calculations

The differences in relative adsorption energies for mono-atomic and diatomic prototype species (C,N,O,S,H,CO,NO,SO,CH,NH,H(2),O(2)) relevant to catalytic processes such as Fischer-Tropsch and Ammonia Synthesis chemistry are investigated on the previously un-studied [Formula: see text] surface(s) of Co, Os, and Ru. Recent work in the literature has confirmed that catalytically relevant nanoparticles of HCP elements such as Co, Os, and Ru typically possess highly active ‘B5’ sites; unfortunately many early and extant theory and model-ing treatments of "stepped HCP surfaces" use ad-hoc created steps via manual deletion of atoms from an ideal HCP(0001) slab model. To date the differences in adsorption energies at various B5 step edge types, and any possible trends across the same type of B5 sites on various HCP catalyst species has not been thoroughly characterized. Our work in this manuscript uses the low energy [Formula: see text] Miller Index surface of Co, Os, and Ru which exposes 2 distinct and strongly adsorbing step edge sites, the B5B and B5A step edge which have been reported as relevant in the literature for Cobalt nanoparticle catalysis applications. Results from this study should be used to help further understand atomistic processes on the stepped surfaces of catalytically active HCP elements.