Katada Naonobu, Tamura Hayato, Matsuda Takuya, Kawatani Yuya, Moriwaki Yu, Matsuo Manami, Kato Ryota
Center for Research on Green Sustainable Chemistry, Faculty of Engineering, Tottori University, 4-101 Koyama-cho Minami, Tottori 680-8552, Japan.
Tottori University Junior High School, 4-101 Koyama-cho Minami, Tottori 680-0945, Japan.
Langmuir. 2024 Sep 17;40(37):19324-19331. doi: 10.1021/acs.langmuir.4c00801. Epub 2024 Aug 21.
The ion exchange function of zeolite is useful for such a purpose as the removal of radioactive Cs species from water. In the very early days of zeolite science, the affinity of zeolites for metal cations was explained based on geometry. After the explanation presented above was proposed, many new zeolites and related materials were discovered or synthesized. Furthermore, it has become clear that the chemical nature of the ion exchange sites is strongly dependent on the framework topology. In this study, the ion exchange behavior between Na-form zeolites with different framework topologies and Cs-containing aqueous solutions was analyzed, and the equilibrium constant was calculated based on the Langmuir type equation to investigate the influence of the chemical nature of the zeolite framework on ion selectivity. The equilibrium constants at room temperature were in the order < < < < . This order is the same as the order of Bro̷nsted acid strengths in the corresponding proton form zeolites. It is suggested that the delocalization of charge around the ion exchange site stabilizes a large cation whose charge is delocalized. In contrast, the equilibrium constant was not related to the pore and cavity size. This opens new insight into the influence of the chemical nature of zeolite on the affinity to cation.
沸石的离子交换功能对于从水中去除放射性铯物种等目的很有用。在沸石科学的早期,基于几何形状解释了沸石对金属阳离子的亲和力。在提出上述解释之后,发现或合成了许多新型沸石和相关材料。此外,已经清楚离子交换位点的化学性质强烈依赖于骨架拓扑结构。在本研究中,分析了具有不同骨架拓扑结构的钠型沸石与含铯水溶液之间的离子交换行为,并基于朗缪尔型方程计算了平衡常数,以研究沸石骨架的化学性质对离子选择性的影响。室温下的平衡常数顺序为< < < < 。这个顺序与相应质子型沸石中的布朗斯特酸强度顺序相同。这表明离子交换位点周围电荷的离域稳定了电荷离域的大阳离子。相比之下,平衡常数与孔和腔的大小无关。这为沸石化学性质对阳离子亲和力的影响开辟了新的见解。