Role of Electronic Structure on Nitrate Reduction to Ammonium: A Periodic Journey

Electrocatalysis is a promising approach to convert waste nitrate to ammonia and help close the nitrogen cycle. This renewably powered ammonia production process sources hydrogen from water (as opposed to methane in the thermal Haber-Bosch process) but requires a delicate balance between a catalyst's activity for the hydrogen evolution reaction (HER) and the nitrate reduction reaction (NO₃RR), influencing the Faradaic efficiency (FE) and selectivity to ammonia/ammonium over other nitrogen-containing products. We measure ammonium FEs ranging from 3.6 ± 6.6% (on Ag) to 93.7 ± 0.9% (on Co) across a range of transition metals (TMs; Ti, Fe, Co, Ni, Ni_0.68Cu_0.32, Cu, and Ag) in buffered neutral media. To better understand these competing reaction kinetics, we develop a microkinetic model that captures the voltage-dependent nitrate rate order and illustrates its origin as competitive adsorption between nitrate and hydrogen adatoms (H*). NO₃RR FE can be described via competition for electrons with the HER, decreasing sharply for TMs with a high work function and a correspondingly high HER activity (e.g., Ni). Ammonium selectivity nominally increases as the TM d-band center energy (E_d) approaches and overcomes the Fermi level (E_F), but is exceptionally high for Co compared to materials with similar E_d. Density functional theory (DFT) calculations indicate Co maximizes ammonium selectivity via (1) strong nitrite binding enabling subsequent reduction and (2) promotion of nitric oxide dissociation, leading to selective reduction of the nitrogen adatom (N*) to ammonium.