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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The mechanism of the reduction of [AnO_2]~(2+) (An = U, Np, Pu) in aqueous solution, and by Fe(ii) containing proteins and mineral surfaces, probed by DFT calculations
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The mechanism of the reduction of [AnO_2]~(2+) (An = U, Np, Pu) in aqueous solution, and by Fe(ii) containing proteins and mineral surfaces, probed by DFT calculations

机译:通过DFT计算探讨了水溶液中[AnO_2]〜(2 +)(An = U,Np,Pu)以及含有蛋白质和矿物表面的Fe(ii)的还原机理

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The fate of actinyl species in the environment is closely linked to oxidation state, since the reduction of An(vi) to An(iv) greatly decreases their mobility due to the precipitation of the relatively insoluble An(iv) species. Here we study the mechanism of the reduction of [AnO_2]~(2+) (An = U, Np, Pu) both in aqueous solution and by Fe(ii) containing proteins and mineral surfaces, using density functional theory calculations. We find a disproportionation mechanism involving a An(v)-An(v) cation-cation complex, and we have investigated how these complexes are formed in the different environments. We find that the behaviour of U and Pu complexes are similar, but the reduction of Np(v) to Np(iv) would seems to be more difficult, in line with the experimental finding that Np(v) is generally more stable than U(v) or Pu(v). Although the models we have used are somewhat idealised, our calculations suggest that there are strong similarities between the biotic and abiotic reduction pathways.
机译:An系物种在环境中的命运与氧化状态密切相关,因为由于相对不溶的An(iv)物种的沉淀,An(vi)还原为An(iv)大大降低了它们的迁移率。在这里,我们使用密度泛函理论计算研究了水溶液中以及含蛋白质和矿物表面的Fe(ii)还原[AnO_2]〜(2+)(An = U,Np,Pu)的机理。我们发现了涉及An(v)-An(v)阳离子-阳离子配合物的歧化机理,并且我们研究了这些配合物如何在不同的环境中形成。我们发现U和Pu配合物的行为相似,但是将Np(v)还原为Np(iv)似乎更加困难,这与实验发现Np(v)通常比U稳定的实验结果一致(v)或Pu(v)。尽管我们使用的模型有些理想化,但我们的计算表明,生物还原途径与非生物还原途径之间存在强烈相似之处。

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