Mark J. Sarsfield

A rare structural characterisation of the phosphomolybdate lacunary anion, [PMo11O39]7−. Crystal structures of the Ln(III) complexes, (NH4)11[Ln(PMo11O39)2]·16H2O (Ln = CeIII, SmIII, DyIII or LuIII)

The syntheses and the crystal structures of (NH4)11[LnIII(PMo11O39)2]·16H2O (LnIII = Ce (1), Sm (2), Dy (3) or Lu (4)) are reported in which an LnIII cation is sandwiched between two ‘lacunary’ [PMo11O39]7− anions to give a complex with eight oxygen atoms coordinated to the lanthanide centre in a twisted square antiprismatic geometry. This analogous series of complexes represents only the second time that the [PMo11O39]7− anion has been fully crystallographically characterised. All four compounds are synthesised in high yield and characterised by a range of physical and spectroscopic techniques. 31P NMR, Raman and UV/Vis/nIR spectroscopies give a clear indication that the [LnIII(PMo11O39)2]11− anion is also stable in solution. As LnIII contracts across the lanthanide series the Ln–O bond distances decrease and the splitting of the νP–O vibrational mode within the [PMo11O39]7− unit increases. The relative stability of this species in solution may have importance in elucidating the speciation of Ln(III) and An(III) cations in nuclear waste solutions where phosphopolymolybdate anions are known to form.

Plutonium Loading of Prospective Grouped Actinide Extraction (GANEX) Solvent Systems based on Diglycolamide Extractants

The Grouped Actinide Extraction (GANEX) process is being developed for actinide recycling within future nuclear fuel cycles. Interactions between potential solvents and macro-concentrations of plutonium are one of the most important issues in defining the GANEX process. Surprisingly, plutonium loading of diglycolamide (DGA) based solvents such as tetra-octyl DGA (TODGA) causes precipitation rather than a conventional third phase, in direct contrast to results with U(VI), Th(IV) or lanthanide ions. Various DGA based solvent systems have been screened for their plutonium loading capacity and 0.2 M TODGA with 0.5 M DMDOHEMA in a kerosene diluent is selected as the optimum solvent formulation of those tested. Plutonium can be relatively easily stripped from this solvent using aqueous acetohydroxamic acid but this is very acid dependent in the low acidity region.

Plutonium(IV) complexation by diglycolamide ligands—coordination chemistry insight into TODGA-based actinide separations

Complexation of Pu(IV) with TMDGA, TEDGA, and TODGA diglycolamide ligands was followed by vis-NIR spectroscopy. A crystal structure determination reveals that TMDGA forms a 1 : 3 homoleptic Pu(IV) complex with the nitrate anions forced into the outer coordination sphere.

Development of a New Flowsheet for Co-Separating the Transuranic Actinides: The "Euro-GANEX" Process

A flowsheet for a novel GANEX (Grouped ActiNide EXtraction) process has been tested in a spiked flowsheet trial in a 32 stage plutonium-active centrifugal contactor rig with a simulant feed that contained 10 g/L plutonium as well as some fission products and other transuranic actinides. The solvent system used was a combination of 0.2 mol/L N,N,N’,N’-tetraoctyl diglycolamide (TODGA) and 0.5 mol/L N,N’-(dimethyl-N,N’-dioctylhexylethoxy-malonamide (DMDOHEMA) in a kerosene diluent that co-extracted actinides and lanthanides. Actinides were subsequently selectively co-stripped away from the lanthanides using a sulphonated and, therefore, hydrophilic bis-triazinyl pyridine (BTP) complexant in conjunction with acetohydroxamic acid (AHA). Plutonium and americium recoveries were high with decontamination factors across the strip contactors of ˜14,000 and ˜390, respectively. However, approximately 30% of neptunium was lost to the aqueous raffinate which was due to recycling within the first extract-scrub section causing a large build-up of neptunium. Some accumulation of strontium was also observed but in this case it was fully directed to the raffinate stream. In the stripping section, a small fraction of europium (taken as a model lanthanide ion), ca. 7%, was found in the actinide product stream. Modelling of selected data using the PAREX code has shown that even with a relatively simplistic treatment, reasonable agreement between modelling and experiment can be obtained, giving confidence in the use of modelling to refine the GANEX flowsheet design prior to further testing with irradiated fast reactor fuel.

Progress towards the Full Recovery of Neptunium in an Advanced PUREX Process

To meet the needs of future closed fuel cycles, the complete recovery of minor actinides, including neptunium, may be required. Neptunium can be fully recovered by modifications to the Plutonium URanium Extraction (PUREX) process but this requires careful control of the Np(V)-(VI) redox reaction in the first solvent extraction contactor to avoid losses to the highly active aqueous raffinate, as occurs in current reprocessing plants. As part of the on-going development of an Advanced PUREX process we report a series of solvent extraction experiments aimed at optimizing neptunium recovery in a process that is based on centrifugal contactors as the extraction equipment. Suitable experimental conditions for Np(V) oxidation were identified through simple stirred 2-phase experiments and single stage mini-centrifugal contactor experiments. A U/Np-active proof-of-principle flowsheet test in a multi-stage centrifugal contactor cascade then demonstrated > 99% extraction of neptunium, thus suggesting the aims for neptunium recovery in advanced fuel cycles can be met by an Advanced PUREX process.

The first uranyl–methine carbon bond; a complex with out-of-plane uranyl equatorial coordination

Treatment of [UO2Cl2(thf)3] in thf with one equivalent of [Na(CH(Ph2P = NSiMe3)2)] yields an unusual uranyl chloro-bridged dimer containing a uranium(VI)-carbon bond as part of a tridentate bis(iminophosphorano)methanide chelate complex. The methine carbon is displaced significantly from the uranyl equatorial plane.

Neptunium(V) disproportionation and cation-cation interactions in TBP/kerosene solvent

Summary In 30% TBP/OK Np(V) is unstable and disproportionates to Np(IV) and Np(VI). Np(V) readily coordinates to Np(IV) in solution to form a “cation–cation” complex by bonding through an axial oxo group on Np(V). The rate of disproportionation in 30% TBP/OK is >500 times that in aqueous solution.

Extraction of Neptunium (IV) Ions into 30% Tri‐Butyl Phosphate from Nitric Acid

The distribution of Np(IV) between 0.08–4.5 M HNO3(aq,eqm) and ∼30% tributyl phosphate has been modelled, accounting for the formation of 1:1 and 1:2 nitrate complexes and Np(IV) hydrolysis in the aqueous phase and the extraction of Np(NO3)4(TBP)2 into TBP. The potential formation and extraction of NpOH(NO3)3(TBP)2 and Np(NO3)4(TBP)2.HNO3 species, including spectroscopic evidence, and oxidations of Np(IV) to Np(V) and Np(VI) in the solvent phase have also been considered. The model highlights some key gaps in the available thermodynamic data.

Probing the 5f electrons in a plutonyl(VI) cluster complex

We report the structural, spectroscopic and preliminary magnetic characterisation of a tri-metallic plutonyl(VI) polyoxometalate complex, K(11)[K(3)(PuO(2))(3)(GeW(9)O(34))(2)] x 12 H(2)O.

Trivalent lanthanide lacunary phosphomolybdate complexes: a structural and spectroscopic study across the series [Ln(PMo11O39)2]11−

We report the syntheses and crystal structures of (NH4)11[Ln(III)(PMo11O39)2.xH2O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo11O39]7- anions sandwich an 8-coordinate Ln(III) cation to yield the complex anion, [LnIII(PMo11O39)2]11-. The 14 salts crystallise in two different space groups, C2/c or P1, but the LnIII containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution 31P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo11O39)2]11- in aqueous solution. As expected, the LnIII cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the nu(P-O) mode within the [PMo11O39]7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density LnIII cation as the series is traversed. For the 31P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W11O39)2]11- complexes.