Atomic-Scale Insights into Electron-Driven Ag Migration and Growth Across Zeolitic Imidazolate Framework-8/Ag2SeO3 Interfaces: A Theoretical and Experimental Study

Abstract The ZIF-8/Ag2SeO3 heterostructure was designed to combine the adsorption capacity and porous architecture of zeolitic imidazolate framework-8 (ZIF-8) with the multifunctional response of Ag2SeO3 (ASO), seeking synergistic interactions that could yield a material with enhanced, complementary functionalities. We report the synthesis and interfacial evolution of ZIF-8/ASO heterostructures and the in situ formation of metallic Ag nanoparticles (NPs) under electron irradiation. X-ray diffraction confirms the coexistence of cubic ZIF-8 (I43m) and monoclinic ASO (P21/c) phases, with a microstructure consisting of ZIF-8 NPs uniformly anchored on ASO microrods in intimate interfacial contact. Time-resolved electron microscopy directly captures the nucleation and growth of Ag NPs on the ZIF-8 surface during electron irradiation, as confirmed by HRTEM-SAED and elemental maps, indicating spatially confined cubic Ag NPs with exposed (111) and (200) planes. Photoluminescence measurements show pronounced emission quenching and spectral redistribution, indicating modified optoelectronic behavior following heterostructure formation. First-principles calculations identify the ZIF-8/ASO(010) interface as a favorable configuration, characterized by strong interfacial interaction and significant charge redistribution. These results are consistent with the experimentally observed localized formation of Ag NPs and suggest that interfacial electronic interactions contribute to Ag+ reduction. Overall, the ZIF-8/ASO heterostructure provides an electron-responsive platform for localized Ag NP formation and interfacial optoelectronic modulation, offering insights into electron-beam-induced processes in ZIF-8-based heterostructures.