3D integrated non-noble metal oxides nano arrays for enhanced nitrate electroreduction to ammonia.

The electrochemical nitrate reduction reaction (eNO 3 RR) to ammonia (NH 3) is a promising alternative method to the Haber-Bosch process that requires high temperature and pressure. In this contribution, the integrated Co 3 O 4 nanowire arrays on Ni foam (Co 3 O 4 /NF) are reported to exhibit the outstanding performance with a high NH 3 yield rate of 117.01 mg h−1cm−2, a superior NH 3 Faradaic efficiency of 99.28 %, a high effective current density of 1475.71 mA cm−2, and a good operation durability during 40 consecutive recycling tests (40 h) in 1.0 M NaOH (0.1 M NaNO 3). The high-valence metal cations as electron-deficient centers can act as Lewis-acid sites, favorably interacting with the Lewis base NO 3 −, and accordingly boosting the NO 3 − adsorption and activation. Moreover, the in-situ growth array configuration provides the substantial active sites and constructs a fast electron-transport channel, thus facilitating the conversion of NO 3 −-to-NH 3. Density functional theory (DFT) calculations also reveal that the Co atoms as the active sites are preferred to adsorb NO 3 −, implying that the NO 3 − electroreduction dominates the cathodic reaction rather than hydrogen evolution reaction. This study provides a viable method to design integrated electrodes with enhanced eNO 3 RR activity and selectivity, which might have broad prospects in the application of renewable energy. The efficient nitrate-to-ammonium conversion is achieved by the integrated Co 3 O 4 nanowire arrays rich in electron-deficient centers. Benefitted from the massive exposed active sites, improved conductivity and charge transfer efficiency, as well as the abundant Lewis acid sites, Co 3 O 4 nanowire arrays present the brilliant nitrate electroreduction performance, including 117.01 mg h−1 cm−2 NH 3 yield rate and 99.28 % Faradaic efficiency in 1.0 M NaOH with 0.1 M NO 3 −. [Display omitted] • High-valence metal cations are favorable to boost NO 3 − adsorption and activation. • Integrated nanowire arrays configuration can provide massive exposed active sites. • Co 3 O 4 /NF can provide a fast electron-transport channel and excellent conductivity. • Co 3 O 4 /NF presents the considerable activity and stability towards eNO 3 RR process. [ABSTRACT FROM AUTHOR]