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辐照下室温离子液体的辐射化学稳定性的阴离子效应。

Anion effect on radiochemical stability of room-temperature ionic liquids under gamma irradiation.

机构信息

CEA Saclay, DEN/DANS/DPC/SECR/LSRM, 91191, Gif-sur-Yvette, France.

出版信息

Dalton Trans. 2009 Aug 21(31):6175-84. doi: 10.1039/b903005k. Epub 2009 Jun 22.

Abstract

Radiochemical stability of imidazolium-based ionic liquids constituted of the BuMeIm(+) cation and associated with four commonly used anions (X(-): Tf(2)N(-), TfO(-), PF(6)(-) and BF(4)(-)) has been investigated under gamma irradiation for high irradiation doses (up to 2.0 MGy). The anion effect has been examined by quantifying the radiolytic yields of disappearance for cation and anions and by identifying corresponding radiolysis products with several analytical techniques. On the one hand, a large number of radiolysis products are formed throughout the irradiation in ionic liquid solutions, resulting from reactions of primary generated species of cation and anion by indirect radiolysis. Primary generated species can react together throughout the irradiation by indirect radiolysis to form numerous radiolysis products in small quantities, indicating that several complex degradation pathways are involved for these radiation doses. This degradation pattern has been confirmed by identification of numerous gaseous radiolytic products. On the other hand, quantitative studies show that radiochemical stabilities of ionic liquids are in the same range of values as systems envisioned in nuclear fuel reprocessing with relatively low hydrogen yields. Indeed, this present work emphasizes the suitability of ionic liquids for applications in the nuclear fuel cycle.

摘要

已研究了由 BuMeIm(+)阳离子和与四种常用阴离子(X(-):Tf(2)N(-)、TfO(-)、PF(6)(-)和 BF(4)(-))构成的基于咪唑鎓的离子液体在高辐照剂量(高达 2.0 MGy)下的放射化学稳定性。通过量化阳离子和阴离子消失的辐解产率,并通过几种分析技术鉴定相应的辐解产物,研究了阴离子的影响。一方面,在离子液体溶液的整个辐照过程中形成了大量的辐解产物,这是由于阳离子和阴离子的初级生成物种通过间接辐射分解反应而产生的。初级生成物种可以通过间接辐射分解在整个辐照过程中相互反应,形成大量少量的辐解产物,这表明在这些辐照剂量下涉及了几个复杂的降解途径。通过鉴定大量气态辐解产物证实了这种降解模式。另一方面,定量研究表明,离子液体的放射化学稳定性与核燃料后处理中设想的系统的值范围相同,其产氢量相对较低。事实上,这项工作强调了离子液体在核燃料循环中的应用的适宜性。

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