NaBH4-assisted reconstruction of binary micro-domains on a Cu electrode for the selective production of green ammonia†
Abstract
It is of both ecological and economic benefit to convert the pollutant nitrate (NO3−) into valuable NH3 via electrochemical nitrate reduction (NO3RR) technology. Here, a grain-assembled Cu2O–Cu nanowires/copper foam (Cu2O–Cu NWs/CF) electrode for NO3RR was developed via a NaBH4-assisted reconstruction process. The optimized Cu2O–Cu NWs/CF showed a superb NH3 yield of 318.46 μmol h−1 cm−2 with a faradaic efficiency up to 98.53%, surpassing the performance of other Cu electrodes. The grain-assembled Cu2O–Cu NWs/CF with larger surface areas caused more NO2− to be further converted into NH3, and thus, the selectivity toward NH3 remained near 100% in consecutive recycling. More importantly, in situ ATR-FTIR spectroscopy and density functional theory (DFT) calculations were executed for real-time tracking of the NO3RR intermediates and for exploring the catalytic mechanism over the Cu electrode. The vital intermediate *NO, which is involved in the NH3 selectivity, was hydrogenated to form *NOH with a much lower ΔG at Cu2O–Cu sites (0.096 eV) than Cu–Cu2O sites (0.617 eV). The Cu phase in the Cu2O–Cu NWs/CF predominated in the NO3RR, whereas Cu2O phase favored the dissociation of H2O into H* for deoxygenation and hydrogenation in NO3RR. This work developed an advanced Cu electrode assembly for selective NH3 production and shed light on the tandem mechanism at binary domains in NO3RR catalysis.