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Hydrothermal Synthesis and Structure of Neptunium(V) Oxide

Published online by Cambridge University Press:  19 October 2011

Tori Z. Forbes
Affiliation:
[email protected], University of Notre Dame, Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, Notre Dame, IN, 46556, United States, 574-631-7216
Peter C. Burns
Affiliation:
[email protected], University of Notre Dame, Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, Notre Dame, IN, 46556, United States
L. Soderholm
Affiliation:
[email protected], Argonne National Laboratory, Chemistry Division, Argonne, IL, 60439, United States
S. Skanthakumar
Affiliation:
[email protected], Argonne National Laboratory, Chemistry Division, Argonne, IL, 60439, United States
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Abstract

Single crystals of Np2O5 have been synthesized by low-temperature hydrothermal reaction of a Np5+ stock solution with natural calcite crystals. The structure of Np2O5 was solved by direct methods and refined on the basis of F2 for all unique data collected on a Bruker X-ray diffractometer equipped with an APEX II CCD detector. Np2O5 is monoclinic, space group P2/c, with a = 8.168(2) Å, b = 6.584(1) Å, c = 9.3130(2) Å, β = 116.01(1)˚, V = 449.8(2) Å3, and Z = 1. The structure contains chains of edge-sharing neptunyl pentagonal bipyramids linked into sheets through cation-cation interactions with distorted neptunyl square bipyramids. Additional cation-cation interactions connect the sheets into a three-dimensional framework. The formation of Np2O5 on the surface of calcite crystals has important implications for the precipitation of isolated neptunyl phases in natural aqueous systems.

Type
Research Article
Copyright
Copyright © Materials Research Society 2007

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