Transition metal nitride catalysts for selective conversion of oxygen-containing molecules

Earth abundant transition metal nitrides (TMNs) are a promising group of catalysts for a wide range of thermocatalytic, electrocatalytic and photocatalytic reactions, with potential to achieve high activity and selectivity while reducing reliance on the use of Pt-group metals. However, current fundamental understanding of the active sites of these materials and the mechanisms by which selective transformations occur is somewhat lacking. Recent investigations of these materials from our group and others have utilized probe molecules, model surfaces, and in situ techniques to elucidate the origin of their activity, strong metal-support interactions, and unique d-band electronic structures. This Perspective discusses three classes of reactions for which TMNs have been used as case studies to highlight how these properties, along with synergistic interactions with metal overlayers, can be exploited to design active, selective and stable TMN catalysts. First, studies of the reactions of C₁ molecules will be discussed, specifically highlighting the ability of TMNs to activate CO₂. Second, the upgrading of biomass and biomass-derived oxygenates over TMN catalysts will be reviewed. Third, the use of TMNs for H₂ production via water electrolysis will be discussed. Finally, we will discuss the challenges and future directions in the study of TMN catalysts, in particular expanding on opportunities to enhance fundamental mechanistic understanding using model surfaces, the elucidation of active centers via in situ techniques, and the development of efficient synthesis methods and design principles.