Impact of lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation.

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙+ from 10-40 °C, giving the activation energy (Ea = 17.43 ± 1.64 kJ mol-1) and pre-exponential factor (A = (2.36 ± 0.05) × 1013 M-1 s-1). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙+, relative to the non-complexed ligand: k([LnIII(TODGA)3(NO3)3] + RH˙+) = (8.99 ± 0.93) × 1010, (2.88 ± 0.40) × 1010, and (1.53 ± 0.34) × 1010 M-1 s-1, for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations-based on a model [LnIII(TOGDA)]3+ complex system-indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [LnIII(TEGDA)3(NO3)3], toward electrophilic attack is for the coordinated nitrate (NO3-) counter anions. Therefore, it is possible that radical reactions with the complexed NO3- counter anions dominate the differences in rates seen for the [LnIII(TODGA)3(NO3)3] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

Radiolytic Evaluation of 3,4,3-LI(1,2-HOPO) in Aqueous Solutions.

The octadentate hydroxypyridinone ligand 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO) has been identified as a promising candidate for both chelation and f-element separation technologies, two applications that require optimal performance in radiation environments. However, the radiation robustness of HOPO is currently unknown. Here, we employ a combination of time-resolved (electron pulse) and steady-state (alpha self-radiolysis) irradiation techniques to elucidate the basic chemistry of HOPO and its f-element complexes in aqueous radiation environments. Chemical kinetics were measured for the reaction of HOPO and its Nd(III) ion complex ([NdIII(HOPO)]-) with key aqueous radiation-induced radical transients (eaq-, H• atom, and •OH and NO3• radicals). The reaction of HOPO with the eaq- is believed to proceed via reduction of the hydroxypyridinone moiety, while transient adduct spectra indicate that reactions with the H• atom and •OH and NO3• radicals proceeded by addition to HOPO's hydroxypyridinone rings, potentially allowing for the generation of an extensive suite of addition products. Complementary steady-state 241Am(III)-HOPO complex ([241AmIII(HOPO)]-) irradiations showed the gradual release of 241Am(III) ions with increasing alpha dose up to 100 kGy, although complete ligand destruction was not observed.

Electrochemical behaviour of uranium at a tripolyphosphate modified ITO electrode.

UO22+ binds to the surface of a tripolyphosphate modified mesoporous indium tin-doped oxide electrode (nanoITO|P3). Electrochemical studies reveal that nITO|P3 electrodes catalyze the 2-electron interconversion between UO22+ and U4+ with the P3-ligand assisting in the rate-limiting proton-coupled reduction of U(V) to U(IV), based on the kinetic isotope effect (1.8). Product composition between nITO|P3(U4+) and surface adsorbed UO2 can be controlled by adjusting the proton concentration and/or scan rate in voltammograms. These studies with uranium suggest that nITO|P3 electrodes are good candidates for redox transformations with other actinides including neptunium, plutonium, and americium.

Indium Tin-Doped Oxide (ITO) as a High Activity Water Oxidation Photoanode.

Photochemical water oxidation was carried out at a mesoporous nanoparticle film composed of indium tin-doped oxide (nanoITO). Annealing nanoITO at temperatures above 250 °C affects both conducting and semiconducting properties. Impressive photoelectrochemical activity was observed at this degenerate n-type semiconductor electrode, outperforming the traditional semiconductor titanium dioxide (TiO2) under the same conditions. In a 0.1 M HNO3 solution, the nanoITO electrode sustained photocurrents of 1.0 mA/cm2 at an Eapplied = 1.5 V vs saturated calomel electrode (SCE) (η = 0.55 V) under a 90 mW/cm2 UV illumination (375 nm). This activity is compared to ∼0.3 mA/cm2 with a traditional TiO2 electrode under the same potential and conditions. Evidence for oxygen generation in the photolysis experiments was quantified using the collector-generator method, and >70% photocurrent efficiency for O2 production was confirmed at this nanoITO photoanode.

Electrochemical oxidation of trivalent americium using a dipyrazinylpyridine modified ITO electrode.

We present here the electrochemical oxidation of Am(iii) to AmVO2+ and AmVIO22+ in pH 1 nitric acid using a mesoporous tin-doped indium oxide electrode modified with a covalently attached dipyrazinylpyridine ligand. The applied potential affects the distribution of Am oxidation products. At potential 1.8 V, only Am(v) is observed, while increasing the potential to as much as 2.0 V, results in oxidation of Am(iii) to Am(v) and subsequent oxidation of Am(v) to Am(vi). At applied potentials >2.0 V, Am(iii) is oxidized to Am(v), while Am(vi) is reduced to Am(v). The latter reduction reaction is likely due to the increased rate of hydrogen peroxide formation from the 2-electron oxidation of water at the electrode at these high potentials. The development of future ligand modified electrodes for actinide oxidations must consider how they facilitate Am oxidations while disfavoring unwanted or competing reactions.