(176h) The Role of Competitive Water Adsorption in Controlling Anodic Dinitrogen Activation

Activation of dinitrogen in heterogeneous catalysis is a problem more than a century old. Following the discovery of the Haber-Bosch process, which occurrs at only a handful of centralized facilities and at extreme temperature and pressure, recent efforts have focused on identifying alternative processes that could be achieved in a less centralized fashion. Given the selectivity challenges associated with cathodic activation of dinitrogen, more recent efforts are investigating anodic dinitrogen activation, which would compete with the comparatively sluggish oxygen evolution reaction. In this work, we utilize density functional theory calculations to probe the role of water, and in particular its competitive binding with dinitrogen on transition metals and transition metal oxides, in controlling the rate of anodic dinitrogen activation. Using the simple computational hydrogen electrode model of the double layer, we illustrate that circumventing competitive water adsorption will be critical for electrochemically activating dinitrogen, both anodically and cathodically.