物理化学学报 >> 2016, Vol. 32 >> Issue (8): 2101-2107.doi: 10.3866/PKU.WHXB201604146

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γ辐射下CMPO/[C2mim][NTf2]的辐解及其对Eu3+萃取的影响

袁威津1,2,董珍1,2,赵龙1,2,*(),于天麟3,翟茂林3   

  1. 1 湖北科技学院非动力核技术研究中心,湖北咸宁437100
    2 上海交通大学核科学与工程学院,上海200240
    3 北京大学化学与分子工程学院,北京分子科学国家实验室,北京100871
  • 收稿日期:2016-03-08 发布日期:2016-07-29
  • 通讯作者: 赵龙 E-mail:ryuuchou@sjtu.edu.cn; ryuuchou@hotmail.com
  • 基金资助:
    国家自然科学基金(11475112);湖北省2011非动力核技术协同创新计划项目资助

γ-Ray-Induced Radiolysis of CMPO/[C2mim][NTf2] and Its Effect on Eu3+ Extraction

Wei-Jin YUAN1,2,Zhen DONG1,2,Long ZHAO1,2,*(),Tian-Lin YU3,Mao-Lin ZHAI3   

  1. 1 Non-power Nuclear Technology Research & Development Center, Hubei University of Science & Technology, Xianning 437100, Hubei Province, P. R. China
    2 School of Nuclear Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China
    3 Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
  • Received:2016-03-08 Published:2016-07-29
  • Contact: Long ZHAO E-mail:ryuuchou@sjtu.edu.cn; ryuuchou@hotmail.com
  • Supported by:
    the National Natural Science Foundation of China(11475112);Hubei 2011 Non-power Nuclear Technology Collaborative Innovation Plan, China

摘要:

主要考察了辛基(苯基)-N, N-二异丁基胺甲酰基甲基氧化膦(CMPO)在1-乙基-3-甲基咪唑双三氟甲基磺酰胺酸盐([C2mim][NTf2])中的γ辐解行为,同时考察辐射对CMPO/[C2mim][NTf2]萃取能力的影响。通过超高效液相色谱-四极杆飞行时间质谱联用仪(UPLC/Q-TOF-MS)进行定量分析、辐解产物认定以及产物半定量分析。CMPO/正十二烷作为对比条件进行了相同研究。结果表明:CMPO在[C2mim][NTf2]中的辐解率低于其在正十二烷中,并且辐解路径不同。在正十二烷体系中,CMPO主要发生C―P、C―N键的断链,而在离子液体体系中CMPO主要发生异丁基脱除反应,并与[C2mim]、·CF3等离子液体产生的自由基发生取代反应。综合辐解研究结果,我们提出CMPO/[C2mim][NTf2]的辐解路径,这加深了CMPO在离子液体中辐解机理的认识。最后,通过萃取实验发现,当硝酸浓度为0.01 mol·L-1,辐照剂量为800 kGy时,CMPO/[C2mim][NTf2]对Eu3+的萃取率依旧达到99%以上。

关键词: CMPO, 离子液体, 萃取, 辐解研究, 半定量分析

Abstract:

Theγ-radiolysis of octylphenyl-(N, N-(diisobutyl)carbamoyl-methyl) phosphine oxide (CMPO) in 1-ethyl-3-methylimidazoliumbis (trifluoromethylsulfonyl) imide ([C2mim][NTf2]) was studied. The effect of radiation on CMPO/[C2mim][NTf2] extractability was also investigated. Quantitative analysis of CMPO in irradiated CMPO/ [C2mim][NTf2] systems, identification and semi-quantitative analysis of the radiolytic products were performed using ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC/Q-TOF-MS). For comparison, CMPO/dodecane was also studied under the same conditions. The radiolysis ratio of CMPO in [C2mim][NTf2] was found to be lower than in dodecane, because of the different radiolysis pathways. The radiolysis pathway of CMPO in molecular solvent was mainly chain scission of C―P and C―N, while that in [C2mim][NTf2] was the elimination of isobutyl, as well as substitution reactions with [C2mim] and ·CF3 generated from solvent [C2mim][NTf2]. Based on the radiolysis study, we propose a radiolysis pathway for CMPO/[C2mim] [NTf2], providing a deeper understanding of the radiolytic mechanism of CMPO in ionic liquids. Finally, the Eu3+ partitioning of CMPO/[C2mim][NTf2] from 0.01 mol·L-1 HNO3 was higher than 99% at 800 kGy.

Key words: CMPO, Ionic liquid, Extraction, Radiolysis study, Semi-quantitative analysis

MSC2000: 

  • O644