Achieving Near-Unity Glyoxylate Selectivity in Ethylene Glycol Oxidation by Spatiotemporal Coupling of Pulsed Electrolysis and Interface Engineering.

Electrochemical cascade reactions suffer from suboptimal selectivity toward high-value intermediates due to the uncontrollable sequential conversion inherent in conventional steady-state electrolysis. To transcend the intrinsic limitations of one-dimensional control, we propose a spatiotemporal synergy strategy for precision electrocatalysis. In this framework, the temporal dimension is governed by pulsed electrolysis, facilitating the rhythmic generation and rapid liberation of target intermediates. Simultaneously, the spatial dimension is engineered via molecular steric modifiers (p-toluidine) to create a persistent hydrophobic interface that effectively suppresses deleterious hydration-driven overoxidation pathways. Synergistically, this dual-dimensional orchestration achieves unprecedented precision, as evidenced by a dramatic leap in glyoxylate selectivity from 25.5% to >99.0%. This work demonstrates a promising and transferable design principle for precision electrocatalysis in complex reaction networks. The spatiotemporal decoupling strategy, integrating temporal pulsed electrolysis for intermediate release and spatial interface engineering for overconsumption suppression, is demonstrated here for ethylene glycol oxidation and provides a rational basis for addressing similar selectivity challenges in other electrocatalytic systems.