Two-Step Pressure-Induced Superhydration in Small Pore Natrolite with Divalent Extra-Framework Cations

In situ high pressure X-ray powder diffraction studies of natrolite (NAT) containing the divalent extra-framework cations (EFC) Sr²⁺, Ca²⁺, Pb²⁺, and Cd²⁺ reveal that they can be superhydrated in the presence of water. In the case of Ca-NAT, Sr-NAT, and Pb-NAT pressure-induced hydration (PIH) inserts 40 H₂O/unit cell into the zeolite compared to 32 in superhydrated natrolites containing monovalent EFC. Cd-NAT is superhydrated in one step to a zeolite containing 32 H₂O/unit cell. PIH of Ca-NAT and Sr-NAT occurs in two steps. During PIH of Pb-NAT three distinct steps have been observed. The excess H₂O in natrolites with divalent EFC are accommodated on sites no longer required for charge compensation. Two distinct families with ordered and disordered EFC–water topologies have been found. Our work established the importance of both size and charge of the EFC in PIH

Role of Cation–Water Disorder during Cation Exchange in Small-Pore Zeolite Sodium Natrolite

By combining X-ray diffraction with oxygen K-edge absorption spectroscopy we track changes occurring during the K⁺–Na⁺ cation exchange of Na-natrolite (Na-NAT) as tightly bonded Na⁺ cations and H₂O molecules convert into a disordered K⁺–H₂O substructure and the unit cell expands by ca. 10% after 50% cation exchange. The coordination of the confined H₂O and nonframework cations change from a tetrahedral configuration, similar in ice <i>I</i>_<i>h</i>, with Na⁺ near the middle of the channels in Na-NAT to two-bonded configuration, similar in bulk water, and K⁺ located near the walls of the framework in K-NAT. This is related to the enhanced ion-exchange properties of K-NAT, which, in marked contrast to Na-NAT, permits the exchange of K⁺ by a variety of uni-, di-, and trivalent cations

Pressure-Induced Metathesis Reaction To Sequester Cs

We report here a pressure-driven metathesis reaction where Ag-exchanged natrolite (Ag₁₆Al₁₆Si₂₄O₈₀·16H₂O, Ag-NAT) is pressurized in an aqueous CsI solution, resulting in the exchange of Ag⁺ by Cs⁺ in the natrolite framework forming Cs₁₆Al₁₆Si₂₄O₈₀·16H₂O (Cs-NAT-I) and, above 0.5 GPa, its high-pressure polymorph (Cs-NAT-II). During the initial cation exchange, the precipitation of AgI occurs. Additional pressure and heat at 2 GPa and 160 °C transforms Cs-NAT-II to a pollucite-related, highly dense, and water-free triclinic phase with nominal composition CsAlSi₂O₆. At ambient temperature after pressure release, the Cs remains sequestered in a now monoclinic pollucite phase at close to 40 wt % and a favorably low Cs leaching rate under back-exchange conditions. This process thus efficiently combines the pressure-driven separation of Cs and I at ambient temperature with the subsequent sequestration of Cs under moderate pressures and temperatures in its preferred waste form suitable for long-term storage at ambient conditions. The zeolite pollucite CsAlSi₂O₆·H₂O has been identified as a potential host material for nuclear waste remediation of anthropogenic ¹³⁷Cs due to its chemical and thermal stability, low leaching rate, and the large amount of Cs it can contain. The new water-free pollucite phase we characterize during our process will not display radiolysis of water during longterm storage while maintaining the Cs content and low leaching rate

Pressure-Dependent Structural and Chemical Changes in a Metal–Organic Framework with One-Dimensional Pore Structure

Pressure-dependent structural and chemical changes of the metal–organic framework (MOF) compound MIL-47­(V) have been investigated up to 3 GPa using different pore-penetrating liquids as pressure transmitting media (PTM). We find that at 0.3(1) GPa the terephthalic acid (TPA) template molecules located in the narrow channels of the as-synthesized MIL-47­(V) are selectively replaced by methanol molecules from a methanol–ethanol–water mixture and form a methanol inclusion complex. Further pressure increase leads to a gradual narrowing of the channels up to 1.9(1) GPa, where a second irreversible insertion of methanol molecules leads to more methanol molecules being inserted into the pores. After pressure release methanol molecules remain within the pores and can be removed only after heating to 400 °C. In contrast, when MIL-47­(V) is compressed in water, a reversible replacement of the TPA by H₂O molecules takes place near 1 GPa. The observed structural and chemical changes observed in MIL-47­(V) demonstrate unique high pressure chemistry depending on the size and type of molecules present in the liquid PTM. This allows postsynthetic nonthermal pressure-induced removal and insertion of organic molecules in MOFs forming novel and stable phases at ambient conditions

Atomically Engineered Metal–Insulator Transition at the TiO₂/LaAlO₃ Heterointerface

We demonstrate that the atomic boundary conditions of simple binary oxides can be used to impart dramatic changes of state. By changing the substrate surface termination of LaAlO₃ (001) from AlO₂ to LaO, the room-temperature sheet conductance of anatase TiO₂ films are increased by over 3 orders of magnitude, transforming the intrinsic insulating state to a high mobility metallic state, while maintaining excellent optical transparency