Citation: WU Jing-Ke, SHEN Xing-Hai, CHEN Qing-De. Electrochemical Behavior of the System of Uranium(VI) Extraction with CMPO-Ionic Liquid[J]. Acta Physico-Chimica Sinica, 2013, 29(08): 1705-1711. doi: 10.3866/PKU.WHXB201306043
CMPO-离子液体萃取分离铀(VI)体系的电化学性质
研究了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)-离子液体(IL)从硝酸铀酰水溶液中萃取铀(VI)的电化学行为, 离子液体(IL)为1-丁基-3-甲基咪唑双三氟甲基磺酰亚胺盐(C4mimNTf2). 用等摩尔系列法测得萃取过程中CMPO与U(VI)形成摩尔比为3:1的配合物. 用循环伏安法研究了萃取液中U(VI)-CMPO配合物的电化学性质, 结果表明, 在C4mimNTf2中U(VI)-CMPO 配合物经过准可逆还原生成U(V)-CMPO 配合物, U(VI)/U(V)电对的表观氧化还原电势(EΘ, vs Fc/Fc+)为(?0.885±0.008) V. 对萃取液进行控制电位电解, 发现在铂片上有沉淀析出. X射线光电子能谱(XPS) 测试结果表明, 沉积物中只含有U(VI)、U(IV)和氧, 而CMPO和C4mimNTf2没有被夹带析出.
English
Electrochemical Behavior of the System of Uranium(VI) Extraction with CMPO-Ionic Liquid
The electrochemical behavior of U(VI) extracted from an aqueous solution of uranyl nitrate by octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in an ionic liquid was investigated. The hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C4mimNTf2) was used in this study. Using an equimolar series method, we found that CMPO and U(VI) formed a 3:1 molar complex during the extraction process. Cyclic voltammetry was used to investigate the electrochemical behavior of the U(VI)-CMPO complex in C4mimNTf2. The U(VI)-CMPO complex was found to be quasi-reversibly reduced to a U(V)-CMPO complex. The formal redox potential (EΘ, vs Fc/Fc+) for the U(VI)/U(V) couple was determined to be (-0.885±0.008) V. Controlled-potential electrolysis of the extract gave a deposit on the surface of a platinum plate. X-ray photoelectron spectroscopy showed that the deposit contained only U(VI), U(IV), and oxygen, and the CMPO extractant and the ionic liquid were not trapped in the deposit.
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Key words:
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?Uranium
- / Ionicliquid
- / Extraction
- / Cyclicvoltammetry
- / Electrodeposition
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