Amorphous K-Co-Mo-S x Chalcogel: A Synergy of Surface Sorption and Ion-Exchange.

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. Here, the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K 2 CoMo 2 S 10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo 5+ 2 and Mo 4+ 3 clusters in the vicinity of di/polysulfides which are covalently linked by Co 2+ ions. The ionically bound K + ions remain in the percolating pores of the Co-Mo-S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO 2 2+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO 2 2+ ] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.