Metastable Facet-Controlled Cu₂WS₄ Single Crystals with Enhanced Adsorption Activity for Gaseous Elemental Mercury

Purposively designing environmental advanced materials and elucidating the underlying reactivity mechanism at the atomic level allows for the further optimization of the removal performance for contaminants. Herein, using well facet-controlled I-Cu₂WS₄ single crystals as a model transition metal chalcogenide sorbent, we investigated the adsorption performance of the exposed facets toward gaseous elemental mercury (Hg⁰). We discovered that the decahedron exhibited not only facet-dependent adsorption properties for Hg⁰ but also recrystallization along the preferential [001] growth direction from a metastable state to the steady state. Besides, the metastable crystals with a predominant exposure of {101} facets dominated the promising adsorption efficiency (about 99% at 75 °C) while the saturated adsorption capacity was evaluated to be 2.35 mg·g^-1. Subsequently, comprehensive characterizations and X-ray adsorption fine structure (XAFS), accompanied by density functional theory (DFT) calculations, revealed that it might be owing to the coordinatively unsaturated local environment of W atoms with S defects and the surface relative stability of different facets, which could be affected by the change in surface atom configuration. Hence, the new insight into the facet-dependent adsorption property of transition metal chalcogenide for Hg⁰ may have important implications, and the atomic-level study directly provides instructions for development and design of highly efficient functional materials.