Steering Pulsed Electrochemistry Selectivity Toward Singlet Oxygen via Dynamic Intermediate Management

Abstract The electrocatalytic generation of singlet oxygen ( 1 O 2 ) from molecular oxygen activation offers a green and selective route for water decontamination. However, its practical application is fundamentally constrained by the sluggish desorption of key * OOH intermediates, leading to a pervasive “selectivity‐efficiency” trade‐off. Herein, we design a pulse excitation electrocatalytic system based on a copper electrode featuring tailored nanotip architecture (Cu‐T) that synergistically integrates spatial electric field enhancement with dynamic potential control. Under optimized pulsed operation, the system achieves exceptional 1 O 2 selectivity (>90%) and oxygen conversion efficiency (>73%), significantly outperforming conventional potentiostatic methods. In situ spectroscopic analyses and multiphysics simulations reveal that the pulsed protocol coupling with tip effect promotes O 2 adsorption, stabilizes key * OOH intermediates, and facilitates their recombination into 1 O 2 , thereby bypassing the rate‐limiting * OOH desorption step. The system also demonstrates broad applicability across diverse organic pollutants and complex water matrices, alongside robust stability in continuous‐flow operation. This work establishes a general spatiotemporal strategy to steer electrocatalytic pathways toward highly selective and energy‐efficient O 2 activation.