Solid-state nuclear magnetic resonance investigation of cation siting in LiNaLSX zeolites

The location of Li⁺ and Na⁺ cations in a series of dehydrated low-silica LiNaX zeolites (LiNaLSX, framework Si/Al ratio=1.0) were characterized by ⁷Li and ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. Depending on the Li⁺ content, up to three lines were observed in the ⁷Li MAS NMR spectra attributed to Li⁺ cations on SI′, SII and SIII sites. The ²³Na MAS NMR spectra of the pure sodium form NaLSX and of LiNaLSX samples with low Li⁺ contents contain up to five lines belong to Na⁺ cations located on SI, SI′, SII, and two different SIII′ sites. LiNaLSX zeolites containing more than 40% of Li⁺ show only a single narrow line in the ²³Na MAS NMR spectra attributed to mobile sodium cations. The populations of the different cation sites were determined from the relative line intensities of the MAS NMR spectra. Below about 70% Li⁺ exchange, lithium cations are located only on sites SI′ and SII. Between 70% and 100% Li⁺ content these sites are fully occupied by Li⁺, and the population of site SIII by Li⁺ increases. It was found that the nitrogen-adsorption capacity correlates well with the occupation of Li⁺ at site SIII.