Single crystal polarization-orientation Raman spectroscopy of zeolite LTA with confined S3− anions - High dielectric constant nanoporous material

Abstract

We apply polarization-orientation Raman spectroscopy, as an alternative to X-ray diffraction, to LTA single crystals containing S3− in sodalite cages additionally to S8 rings in large cavities. The sample was obtained via sulfur vapor adsorption at ∼550 °C (LTA-S-550). We show that S3− is located in the (110) plane with its 2-fold axis along the LTA 4-fold axis. The anion position suggests strong interaction of its terminal atoms with Na+ localized in LTA 6-membered rings. The anions display optical absorption band at ∼590 nm (2.1 eV) and resonant Raman enhancement. We observe a record-high S3− bond-bending mode frequency ∼274 cm−1 due to a strong bond-angle contraction. This leads to the Fermi resonance of its overtone with the symmetric bond-stretching mode in the frequency range of 544–552 cm−1. An anomalous Raman downshift of the S3− bond-stretching modes with a decrease of temperature is observed and attributed to partial compressive stress relaxation. Luminescence band at ∼845 nm is observed suggesting considering LTA-S-550 as an interesting light-emitting material. We discuss a role of S3− in the high dielectric constant up to ∼160 and a possible contribution of the anion to the ion-exchange selectivity to Sr2+/Cs+ enhancements of LTA with sulfur.