Pentavalent Uranium Oxide via Reduction of [UO2]2+ Under Hydrothermal Reaction Conditions

被引:71
作者
Belai, Nebebech [1 ]
Frisch, Mark [1 ]
Ilton, Eugene S. [2 ]
Ravel, Bruce [3 ]
Cahill, Christopher L. [1 ,4 ]
机构
[1] George Washington Univ, Dept Chem, Washington, DC 20052 USA
[2] Pacific NW Natl Lab, Div Chem & Mat Sci, Richland, WA 99352 USA
[3] Natl Inst Stand & Technol, Gaithersburg, MD 20899 USA
[4] Carnegie Inst Sci, Geophys Lab, Washington, DC 20015 USA
基金
美国国家科学基金会;
关键词
D O I
10.1021/ic801534m
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis, crystal structure, and spectroscopic characterization of [U-V(H2O)(2)((UO2)-O-VI)(2)O-4(OH)](H2O)(4) (1), a mixed-valent U-V/U-VI oxide material, are reported. The hydrothermal reaction of UO22+ with Zn and hydrazine at 120 degrees C for three days yields 1 in the form of a dark red crystalline solid. Compound 1 has been characterized by a combination of single-crystal and powder X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The structure consists of an extended sheet of edge and corner shared U-VI pentagonal bipyramids that are further connected by edge sharing to square bipyramidal U-V units. The overall topology is similar to the mineral ianthinite. The uranium L-III-edge XAS revealed features consistent with those observed by single-crystal X-ray diffraction. High resolution XPS data analysis of the U4f region confirmed the oxidation states of U as originally assigned from XRD analysis and bond valence summations.
引用
收藏
页码:10135 / 10140
页数:6
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