Investigation of cation environment and framework changes in silicotitanate exchange materials using solid-state 23Na, 29Si, and 133Cs MAS NMR*1

Abstract

Crystalline silicotitanate (CST), HNa3Ti4Si2O14·4H2O and the Nb-substituted CST (Nb-CST), HNa2Ti3NbSi2O14·4H2O, are highly selective Cs+ sorbents, which makes them attractive materials for the selective removal of radioactive species from nuclear waste solutions. The structural basis for the improved Cs+ selectivity in the niobium analogs was investigated through a series of solid-state magic angle spinning (MAS) NMR experiments. Changes in the local environment of the Na+ and Cs+ cations in both CST and Nb-CST materials as a function of weight percent cesium exchange were investigated using 23Na and 133Cs MAS NMR. Framework changes induced by Cs+ loading and hydration state were investigated with 29Si MAS NMR. Multiple Cs+ environments were observed in the CST and Nb-CST material. The relative population of these different Cs+ environments varies with the extent of Cs+ loading. Marked changes in the framework Si environment were noted with the initial incorporation of Cs+, however with increased Cs+ loading the impact to the Si environment becomes less pronounced. The Cs+ environment and Si framework structure were influenced by the Nb-substitution and were greatly affected by the amount of water present in the materials. The increased Cs+ selectivity of the Nb-CST materials arises from both the chemistry and geometry of the tunnels and pores.