Luminescence Properties and Theoretical Modeling of the Ag₃ Cluster Confined inside the D6r Cavity of Faujasite Zeolite: Implications for the Design of Tunable Emission Phosphor

Faujasite (FAU) zeolites with abundant exchangeable sites are ideal hosts for the intake of Ag + and the stabilization of highly luminescent silver nanoclusters (Ag NCs), while theoretical calculations on the spectral characteristics, charge states, and electronic energies of Ag NCs that are confined inside FAU zeolite were seldom reported. In this research, the Na-type FAU zeolites with varying silicon-to-aluminum (Si/Al) ratios were first synthesized with the hydrothermal method and then applied as matrixes to stabilize Ag NCs to obtain tunable emissions. With the decrease in the Si/Al ratio, the Ag NCs show red-shifted emission from 515 to 548 nm and broadened photoluminescence of excitation (PLE) and photoluminescence (PL) spectral profile. The time-dependent density functional theory (TD-DFT) method was carried out to probe the effect of Al substitution on the charge states and the optical properties of Ag NCs confined inside the double-six ring (D6r) cavity. The simulated results of the absorption spectra and energy levels suggest that the S 1 → S 0 transition of the monovalent Ag 3 + cluster is responsible for the visible emission, and the increased full width at half-maximum (fwhm) of the PLE and PL spectra in the low Si/Al ratio FAU zeolites is due to the inhomogeneous broadening brought by the increased isomer numbers of the Al-substituted neutral zeolite framework. It is noted that the peak of the simulated absorption spectra red-shifted with the decrease in the Si/Al ratio, which is consistent with the experimental observation. This research provided an effective method for the manipulation of Ag NC emission in FAU zeolites through framework cation substitution and meanwhile theoretically explained the Si/Al ratio dependence of tunable emission properties, which may benefit the design of zeolite-confined Ag NCs with desirable optical performances.