Pulsed Electrocatalysis: A Novel Paradigm of Nitrate Reduction.

Abstract

Electrocatalytic nitrate (NO3 -) reduction reaction (eNO3RR) offers a promising route for NO3 - pollution control and nitrogen resource recovery. However, under conventional potentiostatic electrolysis, limited product selectivity and catalyst deactivation still hinder its practical application. Pulsed electrolysis provides a new strategy to dynamically regulate the complex interfacial reaction processes in eNO3RR. Nevertheless, its effectiveness strongly depends on rational parameter design, as inappropriate pulse settings may increase energy consumption and induce undesired catalyst structural evolution. More importantly, the relationship between pulse parameters and interfacial reaction mechanisms remains unclear. Thereby, current parameter optimization lacks generalizable design principles. In this review, we summarize recent advances in pulsed electrolysis for eNO3RR, focusing on its mechanistic roles in dynamic catalyst reconstruction, interfacial microenvironment regulation, and reaction pathway modulation. We then outline design considerations for key pulse parameters and analyze their effects on catalyst stability, mass transport, Faradaic efficiency, and product selectivity. We further discuss the potential of pulsed strategies for value-added C─N coupling transformations. Finally, we examine the key challenges facing pulsed eNO3RR in energy efficiency, stability, and practical scale-up. This review aims to provide mechanistic insights and design guidance for pulsed eNO3RR systems and to support their transition from laboratory studies toward sustainable practical applications.