Abstract
AbstractHerein, we report the discovery of a toroidal inorganic cluster of zirconium(IV) oxysulfate of unprecedented size with the formula Zr70(SO4)58(O/OH)146⋅x(H2O) (Zr70), which displays different packing of ring units and thus several polymorphic crystal structures. The ring measures over 3 nm across, has an inner cavity of 1 nm and displays a pseudo‐10‐fold rotational symmetry of Zr6 octahedra bridged by an additional Zr in the outer rim of the ring. Depending on the co‐crystallizing species, the rings form various crystalline phases in which the torus units are connected in extended chain and network structures. One phase, in which the ring units are arranged in layers and form one‐dimensional channels, displays high permanent porosity (BET surface area: 241 m2 g−1), and thus demonstrates a functional property for potential use in, for example, adsorption or heterogeneous catalysis.
Highlights
We report the discovery of a toroidal inorganic cluster of zirconium(IV) oxysulfate of unprecedented size with the formula Zr70(SO4)58(O/OH)146·x(H2O) (Zr70), which displays different packing of ring units and several polymorphic crystal structures
All MII nitrates direct to a monoclinic or closely related triclinic phase in which the Zr70 rings are fused to each neighboring unit with two bridging sulfate anions, and the resulting chains packed in a herringbone pattern
An important requirement for widespread application of a material is the ability to control its phase and morphology, by identifying the factors that govern it. One such example is provided with “POMzites”, which consists of ring-shaped POMs (P8W48O184)40À linked by transition metal ions which direct different network structures.[14]
Summary
Zr70-tIs,n Zr70-tIs Zr70-oP-Nas,n Zr70-oP-Als,n Zr70-mP-Mgs,n Zr70-aP-Mns Zr70-mP-Nim Zr70-mP-Cus,n Zr70-aP-Zns,n Zr70-mP-Zns. All MII nitrates direct to a monoclinic (mP) or closely related triclinic (aP) phase in which the Zr70 rings are fused to each neighboring unit with two bridging sulfate anions, and the resulting chains packed in a herringbone pattern. Nitrates of sodium and aluminum direct to an orthorhombic (oP) structure in which each torus is close to perpendicular to its nearest neighbor, but without directly bridging units. In all of these cases, metal ions (as aqua-complexes) and water molecules occupy the interstitial space between the Zr70 units. A thin layer of the Zr70 tetragonal phase was detected, oriented very closely along the [001] viewing direction, showing the arrangement of the stacked rings
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