Functionalizing Micro‐to‐Mesoscopic Electrode Architectures for Regulating Electron Transfer Behaviors in Electrocatalysis

ABSTRACT

Electrocatalysis is central to sustainable energy and environmental remediation, yet its efficiency is fundamentally governed by electron transfer dynamics. While conventional research predominantly relies on the molecular‐level design of active sites, this approach often falls short in overcoming the sluggish electron‐transfer kinetics across complex multi‐phase interfaces. Breaking away from traditional active‐site‐centric paradigms, this review innovatively reframes electrocatalyst design through the lens of micro‐to‐mesoscopic electrode architectures, explicitly targeting the manipulation of electron transfer behaviors. We systematically unveil how strategic interface and spatial engineering, encompassing defect confinement, built‐in electric fields (BIEFs), and structurally tailored zero‐to‐three‐dimensional (0D‐3D) architectures, can steer electron transfer pathways, amplify local electron density, and drastically lower kinetic barriers. By decoding the intricate structure‐activity‐electron transfer relationships, this review establishes a pioneering framework for functionalizing electrode microenvironments. Ultimately, mastering these electron transfer dynamics will pave the way for transcending current performance limits in heterogeneous electrocatalysis, offering transformative solutions for the food‐energy‐water nexus toward a sustainable future.