Deciphering the Crystal Structure of a Scarce 1D Polymeric Thorium Peroxo Sulfate

Abstract

The preparation and structural characterization of an original Th peroxo sulfate dihydrate, crystallizing at room temperature in the form of stable 1D polymeric microfibres is described. A combination of laboratory and synchrotron techniques allowed solution of the structure of the Th(O2)(SO4)(H2O)2 compound, which crystallizes in a new structure type in the space group Pna21 of the orthorhombic crystal system. Particularly, the peroxide ligand coordinates to the Th cations in an unusual μ3‐η2:η2:η2 bridging mode, forming an infinite 1D chain decorated with sulfato ligands exhibiting simultaneously monodentate and bidentate coordination modes.

Characterization of a Hexanuclear Plutonium(IV) Nanostructure in an Acetate Solution via Visible–Near Infrared Absorption Spectroscopy, Extended X-ray Absorption Fine Structure Spectroscopy, and Density Functional Theory

“…Experimentally, this type of Pu–Pu interaction may be measurable only if the FT range extends beyond 12 Å –1 , according to those calculations (Figure b). This quenching effect is similar to what has been reported for the solid phase on ThSiO 4 nanoparticles and on a polymeric thorium peroxo sulfate structure where the An–An scattering path is annihilated. The same effect was also reported for an iron aqueous solution, where a mixture of monomer and dimer annihilated the Fe–Fe interaction .…”

Synthesis and multi-scale properties of PuO2 nanoparticles: recent advances and open questions

“…The mechanism was evidenced to combine the physical effects of ultrasound, in situ generation of H 2 O 2 and complexation properties of sulfates which further enabled the accumulation of a neo-formed thorium peroxo sulfate with 1D morphology. 216,217 The transposition of this work to nanoscale PuO 2 is an on-going study that demonstrated interesting preliminary results. 123 Moreover, the enhanced reactivity of AnO 2 nanoparticles is particularly interesting since the experimental conditions used for the preparation of several nanostructured PuO 2 samples are similar to the ones used for its industrial preparation dedicated to MOX nuclear fuel.…”

Coprecipitation of actinide peroxide salts in the U–Th and U–Pu systems and their thermal decomposition

“…These two signals fall within the range of typical vibrational bands of free nitrate and coordinated nitrate ligands, but excluding the bidentate chelating fashion [60]. The absorption band ρ r (H 2 O) = 716 cm -1 suggests the presence of coordinated water [57,61], as present in the studtite. The infrared spectra of the other filtered solids of the  series displays similar vibration bands as presented in the Supplementary Information (Figure S5) for the  n°4 and  n°5 powders, confirming the precipitation of studtite and plutonium peroxo-nitrate salt.…”

“…Figure 2 displays the IR spectrum of the  n°3 precipitate which evidences the absorption bands of uranyl (ν UO 2 2+ at 897 cm -1 ) and peroxide (ν O 2 2-= 864 cm -1 ) functional groups. The absorption band at ν = 716 cm -1 can be ascribed to the presence of coordinated water molecules [57,61] which are present in studtite. In line with the results of Jere et al [20], no specific band can be associated to peroxide ligand in the thorium peroxide salt.…”

“…These two signals fall within the range of typical vibrational bands of free nitrate and coordinated nitrate ligands, but exclude the bidentate chelating fashion. 60 The absorption band ρ r (H 2 O) = 716 cm −1 suggests the presence of coordinated water molecules, 57,61 as present in the studtite.…”