Electrochemical nitrite (NO₂⁻) reduction offers a sustainable route for ammonia (NH₃) synthesis while simultaneously removing contaminants in wastewater. However, its efficiency is often limited by low catalytic efficiency and the competitive hydrogen evolution reaction at low NO₂⁻ concentrations. Herein, we report an intermittent pulsed electrolysis (IPE) strategy using copper oxide (Cu_xO) nanowires, which significantly enhances the NH₃ yield rate and Faradaic efficiency (FE) at lower reactant concentrations. In situ experiments and theoretical calculations reveal that alternating between open-circuit and cathodic potentials modulates the copper oxidation states, stabilizing the catalytically active cuprous oxide (Cu₂O). Consequently, the IPE approach provides an outstanding NH₃ yield rate of 115.10 mg·h⁻¹·cm⁻² and FE of 91.14% in the presence of 25 mM NO₂⁻, markedly outperforming conventional constant potential electrolysis.

In response to the ongoing energy crisis, advancing the field of electrocatalytic water splitting is of utmost significance, necessitating the urgent development of high-performance, cost-effective, and durable hydrogen evolution reaction catalysts. But the generated gas bubble adherence to the electrode surface and sluggish separation contribute to significant energy loss, primarily due to the insufficient exposure of active sites, thus substantially hindering electrochemical performance. Here, we successfully developed a superaerophobic catalytic electrode by loading phosphorus-doped nickel metal (NiP_x) onto various conductive substrates via an electrodeposition method. The electrode exhibits a unique surface structure, characterized by prominent surface fissures, which not only exposes additional active sites but also endows the electrode with superaerophobic properties. The NiP_x/Ti electrode demonstrates superior electrocatalytic activity for hydrogen evolution reaction, significantly outperforming a platinum plate, displaying an overpotential of mere 216 mV to achieve a current density of −500 mA cm⁻² in 1 M KOH. Furthermore, the NiP_x/Ti electrode manifests outstanding durability and robustness during continuous electrolysis, maintaining stability at a current density of −10 mA cm⁻² over a duration of 2000 h. Owing to the straightforward and scalable preparation methods, this highly efficient and stable NiP_x/Ti electrocatalyst offers a novel strategy for the development of industrial water electrolysis.