Pu(VI) Oxalate Crystal Structure and Evidence of Photoreduction to Pu(IV) Oxalate.

Abstract

We report the first crystal structure of a Pu(VI)-oxalate compound. This compound, [PuO2(C2O4)(H2O)]·2(H2O) (1), crystallizes in space group P21/c with a = 5.5993(3) Å, b = 16.8797(12) Å, c = 9.3886(6) Å, and β = 98.713(6)°. It is isostructural with the previously reported U(VI) compound, [UO2(C2O4)(H2O)]·2(H2O). Each plutonyl ion (PuO22+) is coordinated in the equatorial plane by two side-on bidentate oxalates, creating an infinite chain along [001]. A coordinated water molecule and twisting of the oxalates lead to a distorted pentagonal bipyramidal geometry of the Pu. A photochemical degradation was observed for 1, which resulted in the formation of a secondary crystalline phase. The absorption spectrum of this secondary phase confirmed the presence of Pu(IV), but it did not match the spectrum of Pu(C2O4)2·6H2O, which is considered to be the primary product of Pu-oxalate precipitation. While compound 1 has previously been proposed to exist in solution, this is the first time it has been isolated via crystallization. Although redox interactions between Pu and oxalate have been documented in the literature, the present study is the first observation of a photochemical reduction of Pu(VI)-oxalate. As a result, this study has expanded on the limited understanding of the Pu(VI)-oxalate system, which is important for nuclear fuel cycle applications.