Enhanced 133cs Triple-Quantum Excitation in Solid-State NMR of Cs-Bearing Zeolites

Abstract: Geopolymers are aluminosilicate materials that integrate an amorphous phase with crystalline zeolitic domains. Geopolymers exhibit effective immobilization properties for low-level radioactive nuclear waste, and more specifically for the immobilization of radioactive cesium. The identification of the cesium-binding sites and their distribution between the different phases making up the geopolymeric matrix can be obtained using solid-state NMR measurements of the quadrupolar spin 133Cs, which is a surrogate for 134Cs and 137Cs species present in radioactive waste streams. For quadrupolar nuclei, acquiring two-dimensional multiple-quantum experiments allows the acquisition of more dispersed spectra when multiple sites overlap. However, Cs has a spin-7/2 and one of the smallest quadrupole moments, making multiple-quantum excitation highly challenging. In this work we present pulse schemes that enhance the excitation efficiency of 133Cs triple quantum coherences by a factor of ~2 with respect to a two-pulse excitation scheme. The new schemes were developed by using numerical simulation and verified experimentally. We show via nutation experiments as well as two-dimensional triple-quantum solid-state NMR experiments that in hydrated zeolites A and X, which are a simplified model of geopolymer matrices, the cesium binding sites are heterogeneous, and have small (<20 kHz) quadrupolar coupling constants.