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There is a growing need to develop novel technologies that reduce reactive nitrogen concentrations in wastewater streams and decrease our reliance on fossil fuel energy required to produce N-based chemicals and fertilizers. This study conducts a techno-economic analysis (TEA) and a life cycle assessment (LCA) of the electrochemical conversion of nitrate ions (NO3–) present in wastewater to hydroxylamine (NH2OH), a valuable chemical intermediate. We employ experimental data and modeling assumptions to determine NH2OH production costs and life cycle emissions for a small-scale facility (producing 1500 kg-NH2OH/day) and a large-scale facility (producing 50,000 kg-NH2OH/day) integrated into a wastewater treatment plant. The present NH2OH production costs for the small- and large-scale facilities are estimated at $6.14/kg-NH2OH and $5.37/kg-NH2OH, respectively. The parameters dominating the electrochemical reactor cost are electrolyte, separations, and fixed cost, with their values as $1.48, $0.96, and $0.53/kg. Future cost reduction projections indicate that the present NH2OH production costs for the small- and large-scale facilities can be reduced to $2.79/kg-NH2OH and $2.06/kg-NH2OH (NH2OH market price = $1.72/kg), respectively, with improvements in the sensitivity analysis parameters. LCA results indicate that the proposed electrochemical pathway to produce NH2OH has lower life cycle impacts than the conventional pathway. 

Water electrolysis using renewable energy inputs is being actively pursued as a green route for hydrogen production. However, it is limited by the high energy consumption due to the sluggish anodic oxygen evolution reaction (OER) and safety issues associated with H2 and O2 mixing. Here, we replaced OER with an electrocatalytic oxidative dehydrogenation (EOD) of aldehydes for bipolar H2 production and achieved industrial-level current densities at cell voltages much lower than during water electrolysis. Experimental and computational studies suggest a reasonable barrier for C-H dissociation on Cu surfaces, mainly through a diol intermediate, with a potential-dependent competition with the solution-phase Cannizzaro reaction. The kinetics of EOD reaction was further enhanced by a porous CuAg catalyst prepared from a galvanic replacement method. Through Ag incorporation and its modification of the Cu surface, the geometric current density and electrocatalyst durability were significantly improved. Finally, we engineered a bipolar H2 production system in membrane-electrode assembly-based flow cells to facilitate mass transport, achieving a maximum current density of 248 and 390 mA cm−2 at cell voltages of 0.4 V and 0.6 V, respectively. The faradaic efficiency of H2 from both cathode and anode reactions both attained ~100%. Taking advantage of the bipolar H2 production without the issues associated with H2/O2 mixing, an inexpensive, easy-to-manufacture dialysis porous membrane was demonstrated to substitute the costly anion exchange membrane, achieving an energy-efficient and cost-effective process in a simple reactor for H2 production. The estimated H2 price of $2.51/kg from an initial technoeconomic assessment is competitive with US DoE’s “Green H2” targets.