Nitride or Oxynitride? Elucidating the Composition–Activity Relationships in Molybdenum Nitride Electrocatalysts for the Oxygen Reduction Reaction

Molybdenum nitride (Mo−N) catalysts have shown promising activity and stability for the oxygen reduction reaction (ORR) in acid. However, the effect of oxygen (O) incorporation (from synthesis, catalysis, or exposure to air) on their activity remains elusive. Here, we use reactive sputtering to synthesize three compositions of thin-film catalysts and use extensive materials characterization to investigate the depth-dependent structure and incorporated O. We show that the as-deposited Mo−N films are highly oxidized both at the surface (>30% O) and in the bulk (3− 21% O) and that the ORR performance is strongly correlated with the bulk structure and composition. Activity for 4e− ORR is highest for compositions with the highest N/O and N/Mo ratio. Furthermore, H2O2 production for the films with moderate O content is comparable to or higher than the most H2O2-selective nonprecious metal catalysts in acidic electrolyte, on a moles per mass or surface area of catalyst basis. Density functional theory provides insight into the energetics of O incorporation and vacancy formation, and we hypothesize that activity trends with O/N ratios can be traced to the varying crystallite phases and their interactions with ORR adsorbates. This work demonstrates the prevalence and significance of O in metal nitride electrocatalysts and motivates further investigation into the role of O in other nonprecious metal materials

Identifying and Tuning the In Situ Oxygen-Rich Surface of Molybdenum Nitride Electrocatalysts for Oxygen Reduction

Rigorous in situ studies of electrocatalysts are required to enable the design of higher performing materials. Nonplatinum group metals for oxygen reduction reaction (ORR) catalysis containing light elements such as O, N, and C are known to be susceptible to both ex situ and in situ oxidation, leading to challenges associated with ex situ characterization methods. We have previously shown that the bulk O content plays an important role in the activity and selectivity of Mo–N catalysts, but further understanding of the role of composition and morphological changes at the surface is needed. Here, we report the measurement of in situ surface changes to a molybdenum nitride (MoN) thin film under ORR conditions using grazing incidence X-ray absorption and reflectivity. We show that the half-wave potential of MoN can be improved by ∼90 mV by potential conditioning up to 0.8 V versus RHE. Utilizing electrochemical analysis, dissolution monitoring, and surface-sensitive X-ray techniques, we show that under moderate polarization (0.3–0.7 V vs RHE) there is local ligand distortion, O incorporation, and amorphization of the MoN surface, without changes in roughness. Furthermore, with a controlled potential hold procedure, we show that the surface changes concurrent with potential conditioning are stable under ORR relevant potentials. Conversely, at higher potentials (≥0.8 V vs RHE), the film incorporates O, dissolves, and roughens, suggesting that in this higher potential regime, the performance enhancements are due to increased access to active sites. Density functional theory calculations and Pourbaix analysis provide insights into film stability and O incorporation as a function of potential. These findings coupled with in situ electrochemical surface-sensitive X-ray techniques demonstrate an approach to studying nontraditional surfaces in which we can leverage our understanding of surface dynamics to improve performance with the rational, in situ tuning of active sites