High-Temperature Synthesis of a Uranyl Peroxo Complex Facilitated by Hydrothermally In Situ Formed Organic Peroxide.

Because H2O2 is thermally unstable, it seems to be difficult to synthesize peroxides at elevated temperatures. We describe here the in situ generation of peroxide that is incorporated in a new uranyl peroxo complex, HT-UPO1, through the hydrothermal treatment of uranyl nitrate at 150 °C in the presence of organic ligands. In this novel process, a highly conjugated aromatic carboxylate linker, (E)-4-[2-(pyridin-4-yl)vinyl]benzoic acid (HPyVB), plays a crucial role by inducing the reduction of oxygen in air to form peroxide in situ and coordinating with uranyl to promote the preferred formation of thermally stable HT-UPO1. This work expands our knowledge on the speciation and chemistry of uranyl peroxide compounds and also sheds light on the possibility of their synthesis under more harsh conditions.