Binder-Free Nickel Borate/Nickel Hydroxide Bifunctional Catalyst for Coupled Nitrate Reduction and Glycerol Oxidation...

The accumulation of nitrate (NO₃^-) from agricultural runoff poses a growing threat to ecosystems and public health. Converting nitrate into ammonia (NH₃) through the electrochemical nitrate reduction reaction (NO₃RR) offers a promising strategy to mitigate environmental contamination while creating a sustainable circular route to fertilizer production. However, achieving high NH₃ production and energy efficiency remains challenging. Here, we report a binder-free mixed-phase nickel borate/nickel hydroxide bifunctional electrocatalyst directly grown on Ni foam that enables efficient NO₃RR without using an external Ni precursor. The optimized catalyst achieves a high NH₃ yield rate of 1.49 ± 0.04 mmol h^-1 cm^-2 and a Faradaic efficiency for ammonia (FE_NH3) of 81 ± 4.8% at -0.55 V vs RHE. To further reduce the energy input, we couple NO₃RR with glycerol oxidation reaction at the anode, replacing the energy-intensive oxygen evolution reaction. The integrated NO₃RR||GOR system operates at a low cell voltage of 1.47 V (10 mA cm^-2), producing a NH₃ yield rate of ∼0.029 mmol h^-1 cm^-2 (∼63% FE_NH3), and ∼0.101 mmol h^-1 cm^-2 of HCOO^- (∼73% Faradaic efficiency of formate). The hybrid electrolyzer enables a potential energy-saving of ∼13% compared to NO₃RR||OER. This work advances the development of electrochemical platforms for sustainable ammonia synthesis by highlighting the cost-effective, energy-saving, and environmental benefits of coupling reaction.