Direct Observation of Luminescent Silver Clusters Confined in Faujasite Zeolites

One of the ultimate goals in the study of metal clusters is the correlation between the atomic-scale organization and their physicochemical properties. However, direct observation of the atomic organization of such minuscule metal clusters is heavily hindered by radiation damage imposed by the different characterization techniques. We present direct evidence of the structural arrangement, at an atomic level, of luminescent silver species stabilized in faujasite (FAU) zeolites using aberration-corrected scanning transmission electron microscopy. Two different silver clusters were identified in Ag-FAU zeolites, a trinuclear silver species associated with green emission and a tetranuclear silver species related to yellow emission. By combining direct imaging with complementary information obtained from X-ray powder diffraction and Rietveld analysis, we were able to elucidate the main differences at an atomic scale between luminescent (heat-treated) and nonluminescent (cation-exchanged) Ag-FAU zeolites. It is expected that such insights will trigger the directed synthesis of functional metal nanocluster–zeolite composites with tailored luminescent properties

Determination and Optimization of the Luminescence External Quantum Efficiency of Silver-Clusters Zeolite Composites

We have measured for the first time the external quantum efficiency (EQE) of silver clusters containing zeolites (henceforth referred to as silver-clusters zeolite composites). These materials, fabricated by silver cation exchange followed by a thermal autoreduction process, have EQEs up to 69%. Because of their unique spectral features such as large Stokes shift and high EQE, these materials could be potentially used as phosphors for the fabrication of fluorescent lamps and as wavelength convertors in solar cells. An EQE comparison between less pure commercial silver-loaded zeolites and self-synthesized silver-zeolites showed the importance of the chemical and optical purity of the starting host material. Besides this, the zeolite topology and silver content play an important role on the luminescent performance of such materials. The ability to reliably measure the EQE enabled us to further optimize the synthesis of silver-zeolite composites. A new reduction–oxidation cycle is demonstrated not only to improve the luminescent performance of the silver-zeolite composites but also to enhance their water stability

Confinement of Highly Luminescent Lead Clusters in Zeolite A

Metal clusters confined inside zeolite frameworks display unique electronic, catalytic, and optical properties. However, so far only confined silver clusters have shown peculiar luminescent properties, displaying high photoluminescent quantum efficiencies reaching almost unity. In this study, we demonstrate the self-assembly and confinement of highly luminescent lead (Pb) clusters into the molecular-sized cavities of Linde Type A (LTA) zeolites. These Pb-LTA samples display an intense deep-blue emission with external quantum efficiencies up to 69% in their partially dehydrated state. A tetrahedral lead cluster (Pb₄) with unusually short Pb–Pb distances and hydroxyl ligands was identified as responsible for the luminescence as determined by X-ray absorption fine structure (XAFS) analysis. The in-depth characterization of the Pb-zeolites, reported here, sets the stage for elucidating the structure-to-luminescent relationship of other zeolite-embedded clusters