Issue 24, 2018

Atomic scale reversible opto-structural switching of few atom luminescent silver clusters confined in LTA zeolites

Abstract

Luminescent silver clusters (AgCLs) stabilized inside partially Ag exchanged Na LTA zeolites show a remarkable reversible on–off switching of their green-yellowish luminescence that is easily tuned by a hydration and dehydration cycle, making them very promising materials for sensing applications. We have used a unique combination of photoluminescence (PL), UV-visible-NIR Diffuse Reflectance (DRS), X-ray absorption fine structure (XAFS), Fourier Transform-Infrared (FTIR) and electron spin resonance (ESR) spectroscopies to unravel the atomic-scale structural changes responsible for the reversible optical behavior of the confined AgCLs in LTA zeolites. Water coordinated, diamagnetic, tetrahedral AgCLs [Ag4(H2O)4]2+ with Ag atoms positioned along the axis of the sodalite six-membered rings are at the origin of the broad and intense green-yellowish luminescence in the hydrated sample. Upon dehydration, luminescent [Ag4(H2O)4]2+ clusters are transformed into non-luminescent (dark), diamagnetic, octahedral AgCLs [Ag6(OF)14]2+ with Ag atoms interacting strongly with zeolite framework oxygen (OF) of the sodalite four-membered rings. This highly responsive on–off switching reveals that besides quantum confinement and molecular-size, coordinated water and framework oxygen ligands strongly affect the organization of AgCLs valence electrons and play a crucial role in the opto-structural properties of AgCLs.

Graphical abstract: Atomic scale reversible opto-structural switching of few atom luminescent silver clusters confined in LTA zeolites

Supplementary files

Article information

Article type
Paper
Submitted
19 Apr 2018
Accepted
31 May 2018
First published
04 Jun 2018

Nanoscale, 2018,10, 11467-11476

Atomic scale reversible opto-structural switching of few atom luminescent silver clusters confined in LTA zeolites

S. Aghakhani, D. Grandjean, W. Baekelant, E. Coutiño-Gonzalez, E. Fron, K. Kvashnina, M. B. J. Roeffaers, J. Hofkens, B. F. Sels and P. Lievens, Nanoscale, 2018, 10, 11467 DOI: 10.1039/C8NR03222J

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