Innovative solid-phase sorbent technologies are needed to extract radionuclides from harsh media for environmental remediation and in order to close the nuclear fuel cycle. Highly porous inorganic materials with remarkable sorptive properties have been prepared by topotactic transformations of metal–organic frameworks (MOFs) using both basic and acidic solutions. Treatment of Ti and Zr nanoMOFs with NaOH, Na3PO4, and H3PO4 yields Ti and Zr oxides, oxyphosphates, and phosphates via sacrificial removal of the organic ligands. This controlled ligand extraction process results in porous inorganic materials, which preserve the original MOF morphologies and impart useful surface functionalities, but are devoid of organic linkers. Structural investigation by X-ray absorption spectroscopy reveals preservation of the coordination environment of the scattering metal. Changing the MOF template introduces different metal and structural possibilities, while application of different digest solutions allows preparation of metal oxides, metal oxyphosphates, and metal phosphates. The high stability and porosity of these novel materials makes them ideally suited as nanosorbents in severe environments. Their potential for several radionuclide separations is demonstrated, including decontamination of high level nuclear waste, extraction of lanthanides, and remediation of radionuclide-contaminated seawater.

Upon consideration of the hydrogen-bonding properties of the NH(4)(+) cation, we synthesized a new class of compounds, M(3-x)(NH(4))(x)CrO(8) (M = Na, K, Rb, Cs). These magnetic compounds with the simple 3d(1) ground state become ferroelectric. X-ray studies confirmed that the phase transition involves a symmetry change from I42m to Cmc2(1) to P1. The transition temperature depends linearly on the composition variable x. The transitions are of the order-disorder type, with N-H···O bonding playing the central role in the mechanism. Extension of this idea to the introduction of ferroelectricity in several other classes of materials is suggested.

The antiferromagnetic Cr(V) peroxychromates, M(3)Cr(O(2))(4), M = K, Rb, and Cs, become ferroelectric when mixed with NH(4)(+), but the underlying mechanism is not understood. Our dielectric relaxation, Raman scattering, and high-frequency EPR measurements on the M(3-x)(NH(4))(x)Cr(O(2))(4) family clarify this mechanism. At 295 K, (NH(4))(3)Cr(O(2))(4) is tetragonal (I42m), with the NH(4)(+) ions occupying two distinctly different sites, N1 and N2. A ferroelectric transition at T(c1) = 250 K is revealed by λ-type anomalies in C(p) and dielectric constant, and lowering of symmetry to Cmc2(1). Below T(c1), the N1 sites lose their tetrahedral symmetry and thus polarization develops. Raman detection of translational modes involving the NH(4)(+) ions around 193 cm(-1) supports this model. EPR around T(c1) revealed that the [Cr(O(2))(4)](3-) ions reorient by about 10°. A minor peak at T(c2) ≈ 207 K is attributed to a short-range ordering that culminates in a long-range, structural order at T(c3) ≈ 137 K. At T(c3), the symmetry is lowered to P1 with significant changes in the cell parameters. Rb(+) and Cs(+) substitutions that block the N1 and N2 sites selectively show that T(c1) is related to the torsional motion of the N1 site, while T(c2) and T(c3) are governed by the motional slowing down of the N2 site. These data show that the multiferroic behavior of this family is governed by the rotational and translational dynamics of the NH(4)(+) ions and is tunable by their controlled substitutions. Relevance to other classes of possible multiferroics is pointed out.

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