Fuel Chemistry Division, ‡Theoretical Chemistry Section, Bhabha Atomic Research Centre , Trombay, Mumbai-400085, India.
Anal Chem. 2017 Aug 1;89(15):8156-8161. doi: 10.1021/acs.analchem.7b01973. Epub 2017 Jul 11.
Reduction of UO ions to U ions is difficult due to involvement of two axially bonded oxygen atoms, and often requires a catalyst to lower the activation barrier. The noble metal nanoparticles (NPs) exhibit high electrocatalytic activity, and could be employed for the sensitive and rapid quantifications of U0 ions in the aqueous matrix. Therefore, the Pd, Ru, and Rh NPs decorated glassy carbon electrode were examined for their efficacy toward electrocatalytic reduction of UO ions and observed that Ru NPs mediate efficiently the electro-reduction of UO ions. The mechanism of the electroreduction of UO by the RuNPs/GC was studied using density functional theory calculations which pointed different approach of 5f metal ions electroreduction unlike 4p metal ions such as As(III). RuNP decorated on the glassy carbon would be hydrated, which in turn assist to adsorb the uranyl sulfates through hydrogen bonding thus facilitated electro-reduction. Differential pulse voltammetric (DPV) technique, was used for rapid and sensitive quantification of UO ions. The RuNPs/GC based DPV technique could be used to determine the concentration of uranyl in a few minutes with a detection limit of 1.95 ppb. The RuNPs/GC based DPV was evaluated for its analytical performance using seawater as well lake water and groundwater spiked with known amounts of UO.
UO 离子还原为 U 离子由于涉及两个轴向键合的氧原子而变得困难,通常需要催化剂来降低活化能垒。贵金属纳米粒子 (NPs) 表现出高电催化活性,可用于在水相基质中对 U0 离子进行灵敏和快速的定量。因此,研究了 Pd、Ru 和 Rh NPs 修饰的玻碳电极对 UO 离子电催化还原的效果,观察到 Ru NPs 有效地介导了 UO 离子的电还原。使用密度泛函理论计算研究了 RuNPs/GC 对 UO 电化学还原的机制,该计算指出了 5f 金属离子还原的不同途径,与 As(III)等 4p 金属离子不同。修饰在玻碳上的 RuNP 会被水合,从而通过氢键帮助吸附硫酸铀酰,从而促进电还原。差分脉冲伏安法 (DPV) 技术用于快速灵敏地定量 UO 离子。基于 RuNPs/GC 的 DPV 技术可在几分钟内确定铀酰的浓度,检测限为 1.95 ppb。基于 RuNPs/GC 的 DPV 技术还用于评估其在海水以及湖水和地下水中的分析性能,这些水样中已知添加了一定量的 UO。