Electrochemical Nitrate-to-Ammonia Conversion Enabled by Carbon-Decoration of Ni―GaOOH Synthesized via Plasma-Assisted CO2 Reduction

The release of nitrates into the environment leads to contaminated soil and water that poses a health risk to humans and animals. Due to the transition to renewable energy-based technologies, an electrochemical approach is an emerging option that can selectively produce valuable ammonia from nitrate sources. However, traditional metal-based electrocatalysts often suffer from low nitrate adsorption that reduces NH3 production rates. Here, a Ni-GaOOH-C/Ga electrocatalyst for electrochemical nitrate conversion into NH3 is synthesized via a low energy atmospheric-pressure plasma process that reduces CO2 into highly dispersed activated carbon on dispersed NiGaOOH particles produced from a liquid metal GaNi alloy precursor. Nitrate conversion rates of up to 26.3 mu g h(-1) mg(cat)(-1) are achieved with good stability of up to 20 h. Critically, the presence of carbon centers is central to improved performance where both NiC and NiOC interfaces act as NO3- adsorption and reduction centers during the reaction. Density functional theory (DFT) calculations indicate that the NiOC and NiC reaction sites reduce the Gibbs free energy required for NO3- reduction to NH3 compared to NiO and Ni. Importantly, catalysts without carbon centers do not produce NH3, emphasizing the unique effects of incorporating carbon nanoparticles into the electrocatalyst.