Efficient electrocatalytic reduction of nitric oxide (NO) to ammonia (NH3) on metal-free B4@g-C3N4 nanosheet

Abstract

The combustion of fossil fuels releases substantial amounts of nitric oxide (NO), posing serious environmental and health risks. Addressing NO pollution effectively is, therefore, a pressing need. Conversion of NO into valuable chemicals is an appealing strategy with dual benefits, including waste utilization and sustainable energy transformation. In this study, we investigate the metal-free electrocatalytic reduction of NO (NORR) to NH3 on a B4 atomic cluster supported by a g-C3N4 nanosheet (B4@g-C3N4) using density functional theory (DFT). Our findings reveal that NO is efficiently activated on the B4@g-C3N4 catalyst, favoring side-on and N end-on adsorption configurations. Significant electron transfer and strong adsorption energies confirm the chemisorption of NO. The NORR exhibits an impressively low limiting potential (UL) of −0.29 V in the gas phase, which decreases further under solvent effects and varying charge states (−2e-, −1e-, +1e-, +2e-). Additionally, the high negative UL values for competing side reactions such as H2 (−0.42 V), N2 (−0.29 V), and N2O (−0.72 V) underscore the selectivity of B4@g-C3N4 for ammonia synthesis. These results highlight the promising potential of B4@g-C3N4 nanosheets for eco-friendly ammonia production from NO, providing a theoretical basis for future experimental efforts to combat NO pollution.