Framework-to-cluster charge transport triggering silver growth in ZIF-8/Ag2SeO3 heterostructures

Heterostructures integrating semiconductor oxides and metal–organic frameworks (MOFs) provide a versatile platform for engineering interfacial charge dynamics and defect-mediated reactivity. In this work, we report a fundamentally new mechanism governing Ag nanoparticle (NP) assembly in ZIF-8/Ag 2 SeO 3 heterostructures under electron irradiation (EI). We demonstrate, for the first time, that Ag NPs nucleate selectively over ZIF-8 particles rather than randomly across the Ag 2 SeO 3 surface. This spatial selectivity is regulated by a framework-to-cluster electron flux, in which ZIF-8 functions as an electron-acceptor and redistributor scaffold that concentrates and channels excess electronic density toward defect-rich [AgO x ] quantum clusters in Ag 2 SeO 3 . The enhanced interfacial electron accumulation promotes Ag + reduction to Ag 0 , generating mobile metallic species that subsequently undergo directed mass transport toward ZIF-8 surfaces, where nucleation and growth are thermodynamically favored. Photoluminescence analysis reveals interfacial defect equilibration and the suppression of radiative recombination, thereby supporting the formation of charge-transfer states across the junction. Time-resolved SEM imaging provides a direct visualization of the sequential process of selective nucleation and nanoparticle growth on MOF crystallites. This two-step mechanism, based on electron-flux-enhanced reduction followed by interfacially driven Ag 0 migration, establishes EI as a precision tool for directing NP assembly through defect-mediated electronic coupling. These findings introduce a new paradigm for designing adaptive MOF/semiconductor heterostructures with controlled plasmonic, catalytic, and interfacial functionalities.