(Invited) Probing the Reaction Microenvironment during Electrochemical Nitrate Reduction to Ammonia

Abstract

Nitrate pollution of wastewater from agricultural runoff and industrial waste streams is common around the globe. Nitrate negatively impacts the environment through harmful algal blooms and can be dangerous for human consumption. Strict limits have been set on nitrate discharge and the concentration in drinking water (< 50 ppm). Nitrate is currently removed from water by conversion to nitrogen through a biological process that requires chemical inputs (e.g., methanol) and post-treatment to remove biomass and organics.Electrochemical reduction of nitrate (NO3RR) to ammonia can remove nitrate from water and is an alternative to Haber-Bosch (HB) ammonia production, a significant source of global CO2 emissions. Ammonia is an important chemical precursor with potential applications in sustainable energy as a fuel or H2 carrier, or can be used as a fertilizer in the form of ammonium sulfate. This research addresses the water–energy nexus by converting nitrate to a valuable product, off-setting the cost of water treatment, and reducing demand for HB.NO3RR can be done from small to large scales, use renewable electricity, and eliminate the need for expensive and hazardous chemicals. However, NO3RR processes must exhibit selectivity toward ammonia to avoid the formation of other undesired products and occur at a low overpotential to minimize operating costs from electricity. To address these challenges, we must understand the reaction environment at the electrode–electrolyte interface, where heterogeneous electrochemical reactions occur. We use in situ attenuated total reflectance–surface-enhanced infrared adsorption spectroscopy (ATR–SEIRAS) to investigate the adsorbed reactants, intermediates, and interfacial pH. We studied the repeatability of the technique for in situ interfacial pH measurement and recommend controls to the community when using this method. The ATR–SEIRAS results are correlated with electrochemical experiments measuring NO3RR selectivity, activity, and efficiency. NO3RR products are measured by ion chromatography and gas chromatography. Our results relate bulk electrolyte properties with interfacial properties, and interfacial properties with reaction activity and selectivity. This understanding could lead to the development of electrolyte engineering strategies to optimize ammonia production in electrochemical NO3RR.