Molybdenum Nitrides as Oxygen Reduction Reaction Catalysts: Structural and Electrochemical Studies

Monometallic (δ-MoN, Mo5N6, and Mo2N) and bimetallic molybdenum nitrides (Co0.6Mo1.4N2) were investigated as electrocatalysts for the oxygen reduction reaction (ORR), which is a key half-reaction in hydrogen fuel cells. Monometallic hexagonal molybdenum nitrides are found to exhibit improved activities over rock salt type molybdenum nitride (γ-Mo2N), suggesting that improvements are due to either the higher molybdenum valence or a more favorable coordination environment in the hexagonal structures. Further enhancements in activity were found for hexagonal bimetallic cobalt molybdenum nitride (Co0.6Mo1.4N2), resulting in a modest onset potential of 0.713 V versus reversible hydrogen electrode (RHE). Co0.6Mo1.4N2 exhibits good stability in acidic environments, and in the potential range lower than 0.5 V versus RHE, the ORR appears to proceed via a four-electron mechanism based on the analysis of rotating disc electrode results. A redetermination of the structures of the binary molybdenum nitrides was carried out using neutron diffraction data, which is far more sensitive to nitrogen site positions than X-ray diffraction data. The revised monometallic hexagonal nitride structures all share many common features with the Co0.6Mo1.4N2 structure, which has alternating layers of cations in octahedral and trigonal prismatic coordination, and are thus not limited to only trigonal prismatic Mo environments (as was originally postulated for δ-MoN).