Shedding Light on Electron-Driven Ag Formation at ZIF-8/α-Ag ₂ WO ₄ Interfaces

High Resolution Image Download MS PowerPoint Slide The formation of metallic silver nanoparticles (Ag NPs) under electron irradiation in Ag-based semiconductors represents a fundamental process governed by atomic-scale structural and electronic rearrangements. Density functional tight-binding (DFTB) simulations reveal that electron injection induces a highly localized charge redistribution, preferentially at undercoordinated [AgO x ] clusters of α-Ag 2 WO 4, increasing the electron density around Ag cations, which promotes Ag–O bond weakening and the formation of Ag cations with low coordination to oxygen anions, which act as precursors for metallic Ag nucleation. Surface-dependent behavior of α-Ag 2 WO 4 is observed, with the (010) and (001) facets exhibiting enhanced charge accumulation and structural flexibility, while the (101) surface favors charge delocalization. Electron microscopy analyses directly confirm the electron irradiation-induced reduction, nucleation, and growth of Ag NPs, particularly on the ZIF-8 surface, thereby evidencing a directed interfacial migration mechanism from α-Ag 2 WO 4 to ZIF-8. Notably, these processes are strongly dependent on both the electron irradiation exposure time and the applied electron dose. In this article, we report the emergence of a novel phenomenon in which electron irradiation enables the synergistic integration of Ag NPs onto the ZIF-8 surface. This study offers new insights into the rational design of α-Ag 2 WO 4 and ZIF-8-based heterostructure for the next generation of multifunctional materials.