DFT Study of Chemisorbed Atomic Oxygen Inducing Co Segregation in CoNi(111) Alloy

Chemisorbed atomic oxygen inducing Co segregation in CoNi (111) alloy is studied using periodic self-consistent density functional theory (DFT) calculations. In particular, the coverage dependence and possible adsorption-induced segregation phenomena are addressed by investigating segregation energies (the difference in calculated total free energy between surface sites and bulk-like sites) of isolated Co in CoNi (111) alloy. In agreement with previous experimental and theoretical investigations, segregation of Co is found to be oxygen-coverage dependent. While for ‘clean’ CoNi (111), Co prefers to be in the bulk. In the presence of more than 2/9 ML of oxygen, Co segregates to the surface. The analysis of oxygen adsorption trends and surface electronic structures explains the change in the local atomic arrangement which is expected to occur on the surface of alloys under reaction conditions. Our predictions for the high oxygen coverage cases are particularly relevant in underlining the importance of segregation phenomena to the hydrogen evolution performance of CoNi alloy hydrogen evolution electrode.