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Materials Data on ZrP by Materials Project

ZrP is Molybdenum Carbide MAX Phase-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Zr3+ is bonded to six P3- atoms to form a mixture of edge, face, and corner-sharing ZrP6 octahedra. The corner-sharing octahedra tilt angles range from 0–46°. There are three shorter (2.59 Å) and three longer (2.73 Å) Zr–P bond lengths. There are two inequivalent P3- sites. In the first P3- site, P3- is bonded to six equivalent Zr3+ atoms to form a mixture of distorted edge and corner-sharing PZr6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 4°. In the second P3- site, P3- is bonded to six equivalent Zr3+ atoms to form a mixture of edge and corner-sharing PZr6 octahedra.

36 MATERIALS SCIENCE↗

Materials Data on ZrP by Materials Project

ZrP is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Zr3+ is bonded to six equivalent P3- atoms to form a mixture of edge and corner-sharing ZrP6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Zr–P bond lengths are 2.65 Å. P3- is bonded to six equivalent Zr3+ atoms to form a mixture of edge and corner-sharing PZr6 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗

Superconductivity in single crystals of ZrP 1.27 Se 0.73

Results are reported for single crystals of the PbFCl-type layered compound ZrP 1.27 Se 0.73 that were produced using the iodine vapor transport method. Electrical transport, magnetization, and heat capacity measurements reveal disordered metallic behavior and the occurrence of bulk superconductivity, with a transition temperature (T c ) of 7.1 K and an anisotropic orbitally limited upper critical field. 31 P nuclear magnetic resonance measurements provide additional microscopic information, where the line shape, Knight shift, and spin-lattice relaxation data are consistent with the superconductivity originating from the corrugated Zr-P(2c)/Se plane. This suggests that the superconductivity first forms in the corrugated plane and the bulk superconductivity eventually occurs via coupling between the square planar layers. These data also show that either there are multiple superconducting gaps or there is a single gap that does not fully open across the entire Fermi surface. Finally, these results clarify the superconducting state in this material and will enable further measurements that require single-crystal specimens.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Uptake and Binding of At‐211 Into K‐ and Cs‐Derivatives of Alpha‐Zirconium Phosphate Nanoplatelets for Use as a Targeted Alpha Therapy Delivery Platform

The ion exchange behavior of K- and Cs-derivatives of α-zirconium phosphate, A-ZrP, with the targeted alpha therapy (TAT) radionuclide 211 At, as At + and AtO + , has been investigated. The K-ZrP shows strong affinity for both At+ and AtO + , ≥99% uptake. The affinity to Cs-ZrP was less pronounced, 87%–94% uptake, favoring At + . The binding strength was tested against several leaching solutions, including carbonate, phosphate buffered saline (PBS), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffers, and ethylenediaminetetraacetic acid (EDTA) solutions at various concentrations (0.1–10 mM). K-ZrP retained 211 At in all buffer and EDTA solutions up to 1 mM (<0.5% leaching). The Cs-ZrP showed no leaching of At + , while AtO + leached (1%–3%) in the carbonate and HEPES buffers, along with all of the EDTA solutions, with complete retention only in the PBS buffer. In all cases, when the EDTA concentration reached 10 mM, 211 At leaching was observed. Once incorporated into the ZrP nanoplatelets, significant shielding of the α-particles was observed, not only attenuating the intensity of the emission but also reducing the energy of the α-particles themselves exiting the nanoplatelets. These properties provide the basis for K-ZrP, and to a lesser extent, Cs-ZrP to be further considered as potentially promising candidates for a delivery mechanism of 211 At for application in TAT.

astatine-211↗

Uptake and binding of La 3+ and Cr 3+ ions by alkali metal substituted alpha-zirconium phosphate

The conversion of alpha-zirconium phosphate, Zr(HPO 4 ) 2 ·H 2 O, to the K-, Rb-, and Cs-phases and the subsequent ion exchange behavior of these alkali metal phases, A-ZrP, with La 3+ and Cr 3+ have been investigated. The conversion to the A-ZrP phases was achieved by reaction with metal chloride, metal hydroxide solution, and confirmed through various techniques, including X-ray powder diffraction, thermogravimetry analysis, IR spectroscopy, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The effect of material hydration, which increased the interlayer distance, was also examined. The ion exchange behavior of the A-ZrP showed strong affinity for both La 3+ , a representative for trivalent lanthanide metals, and Cr 3+ , a representative for the trivalent transition metals, with a rapid, near quantitative removal of the M 3+ ions at a pH of 3 when the ion concentration was ≤25% of the ion exchange capacity of the materials. Additionally, the ion affinity was shown to be pH and concentration-dependent, decreasing with a decrease in pH or an increase in ion concentration. Lastly, the binding strength of La- and Cr-loaded ZrP materials was examined through a series of leaching experiments in a carbonate buffer, phosphate buffer, HEPES buffer, and a series of EDTA solutions at various concentrations. No observable leaching occurred in the carbonate buffer, phosphate buffer, HEPES buffer, or when the EDTA concentration was below 0.1 mM. These results highlight the potential for the A-ZrP materials to provide a platform for trivalent transition metal and trivalent lanthanide radionuclide capture for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Materials Data on ZrPCN(OF)3 by Materials Project

ZrP(OF)3CN crystallizes in the triclinic P-1 space group. The structure is two-dimensional and consists of two hydrogen cyanide molecules and one ZrP(OF)3 sheet oriented in the (0, 1, 0) direction. In the ZrP(OF)3 sheet, there are two inequivalent Zr3+ sites. In the first Zr3+ site, Zr3+ is bonded in an octahedral geometry to two equivalent O2- and four F1- atoms. Both Zr–O bond lengths are 2.22 Å. There are two shorter (1.99 Å) and two longer (2.01 Å) Zr–F bond lengths. In the second Zr3+ site, Zr3+ is bonded in an octahedral geometry to four O2- and two equivalent F1- atoms. There are two shorter (2.15 Å) and two longer (2.16 Å) Zr–O bond lengths. Both Zr–F bond lengths are 1.97 Å. P5+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There is two shorter (1.52 Å) and one longer (1.53 Å) P–O bond length. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Zr3+ and one P5+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Zr3+ and one P5+ atom. In the third O2- site, O2- is bonded in a distorted linear geometry to one Zr3+ and one P5+ atom. There are three inequivalent F1- sites. In the first F1- site, F1- is bonded in a single-bond geometry to one Zr3+ atom. In the second F1- site, F1- is bonded in a single-bond geometry to one Zr3+ atom. In the third F1- site, F1- is bonded in a single-bond geometry to one Zr3+ atom.

36 MATERIALS SCIENCE↗

Studies of Reactive Amorphous Compounds and Surfaces: Their Pathways to Crystallinity and Surface Functionality

This project was originally headed by Dr. Abraham Clearfield (Texas A&M University, ret.) and focused on developing structural models of zirconium phosphate (ZrP) based materials at different stages of crystalline order using PDF techniques developed by co-PI Dr. Simon Billinge (Columbia University). When Dr. Clearfield retired, the project was taken over by Dr. Hong-Cai Zhou (Texas A&M University). The project proposed looking at defective metal-organic frameworks (MOFs) supported on the surface of the ZrP materials. During the project, the personnel conducted studies of the dispersion of different phosphate ligands in mixed organic phosphonates, and how they could be utilized to incorporate different metals within the ZrP interlayer spacing.

36 MATERIALS SCIENCE↗