Verma Parveen K, Bhattacharyya Arunasis, Samanta Soumen, Mohapatra Prasanta K
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085, India.
Technical Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085, India.
Dalton Trans. 2024 Aug 13;53(32):13583-13590. doi: 10.1039/d4dt01650e.
AgBiO is reported for the exclusive oxidation of Am → AmO at near-neutral pH conditions. Literature methods of AmO generation are generally two-step processes; , Am → AmO oxidation followed by AmO → AmO reduction. These methods for Am → AmO oxidation use high temperatures (80-100 °C) and/or several reagents, causing the presence of the AmO-complex rather than the AmO ions. This not only interferes with the much-needed Am-Cm selectivity but also limits the use of AmO in any other experimental study. The single-step Am → AmO oxidation in the present work using AgBiO is done at 25 °C in a non-complexing medium at pH ∼4, making it a first-of-its-kind report. Am-Eu and Am-Cm separation in a single contact, with a separation factor >10, was achieved using the present method, which is unprecedented among aqueous feed solutions. The AmO generated using the present method under non-complexing pH conditions makes it also suitable for exploring the fundamental chemistry of the higher valent americyl ion. A complexation study using the thus-generated AmO ion with acetate ion supports the concept.
据报道，AgBiO可在近中性pH条件下将镅（Am）专一性氧化为镅酰离子（AmO）。文献中生成AmO的方法通常是两步过程，即先将Am氧化为AmO，然后再将AmO还原为AmO。这些将Am氧化为AmO的方法使用高温（80 - 100°C）和/或多种试剂，导致生成的是AmO络合物而非AmO离子。这不仅干扰了急需的Am - Cm选择性，还限制了AmO在任何其他实验研究中的应用。本工作中使用AgBiO将Am一步氧化为AmO是在25°C、pH约为4的非络合介质中进行的，这是同类研究中的首次报道。使用本方法在单次接触中实现了Am - Eu和Am - Cm的分离，分离因子>10，这在水性进料溶液中是前所未有的。在非络合pH条件下使用本方法生成的AmO也适用于探索高价镅酰离子的基础化学。使用如此生成的AmO离子与醋酸根离子进行的络合研究支持了这一概念。
