99TcO4– Separation through Selective Crystallization Assisted by Polydentate Benzene-Aminoguanidinium Ligands
99TcO4– Separation through Selective Crystallization Assisted by Polydentate Benzene-Aminoguanidinium Ligands
复制标题
99TcO4â 通过多齿苯-氨基胍配体辅助选择性结晶分离
DOI：
10.1021/acs.inorgchem.1c00187
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发表时间：
2021
影响因子：
4.6
通讯作者：
Shuao Wang
中科院分区：
文献类型：
--
作者：
Rongzhen Xie;Nannan Shen;Xijian Chen;Jie Li;Yaxing Wang;Chao Zhang;Chengliang Xiao;Zhifang Chai;Shuao Wang
99 Tc是使用过的核燃料中最丰富的放射性毒性同位素之一，具有高裂变产额和长半衰期。有效去除水溶液中的高锝酸盐（TcO 4-）对于核废物的分离和修复具有重要意义。在此，我们报告了一系列容易获得的苯连接的胍，可以沉淀TcO 4-和它的非放射性替代ReO 4-从高浓度的酸性溶液通过自组装结晶。所得的过氯酸盐和高锝酸盐固体表现出异常低的水溶性。苯连接的胍盐在先前报道的材料中具有最高的TcO 4-去除能力（1279 mg g-1）之一，并且在Cl-存在下对ReO 4-的去除率为59%。单晶结构和密度泛函理论计算表明，TcO 4-通过电荷辅助氢键相互作用被捕获，并通过π-π堆积层稳定化。此外，去除过程易于回收，并且不会引入有毒的有机试剂。本工作为从高放废物中初步分离TcO_4 ~-提供了一条绿色途径。
99Tc is one of the most abundant radiotoxic isotopes in used nuclear fuel with a high fission yield and a long half-life. Effective removal of pertechnetate (TcO4–) from an aqueous solution is important for nuclear waste separation and remediation. Herein, we report a series of facilely obtained benzene-linked guanidiniums that could precipitate TcO4–and its nonradioactive surrogate ReO4–from a high-concentration acidic solution through self-assembly crystallization. The resulting perrhenate and pertechnetate solids exhibit exceptionally low aqueous solubility. The benzene-linked guanidiniums hold one of the highest TcO4–removal capacities (1279 mg g–1) among previously reported materials and possess a removal percentage of 59% for ReO4–in the presence of Cl–over 50 times. The crystallization mechanism was clearly illustrated by the single-crystal structures and density functional theory calculations, indicating that TcO4–is captured through a charge-assisted hydrogen bonding interaction and stabilized by π–π stacking layers. In addition, the removal process is easily recycled and no toxic organic reagents are introduced. This work provides a green approach to preliminarily separate TcO4–from high-level nuclear wastes.