Leloire Maëva, Nerisson Philippe, Pourpoint Frédérique, Huvé Marielle, Paul Jean-François, Cantrel Laurent, Loiseau Thierry, Volkringer Christophe
Univ. Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille, France.
Institut de Radioprotection et de Sureté Nucléaire (IRSN), PSN-RES/SEREX, Saint-Paul Lez Durance, 13115, France.
Dalton Trans. 2022 Nov 1;51(42):16170-16180. doi: 10.1039/d2dt02371g.
Ru is a radioactive isotope usually generated by the nuclear industry within power plant reactors. During a nuclear accident, Ru reacts with oxygen, leading to the production of highly volatile ruthenium tetroxide RuO. The combination of volatility and radioactivity makes RuO, one of the most radiotoxic species and justifies the development of a specific setup for its capture and immobilization. In this study, we report for the first time the capture and immobilization of gaseous RuO within a porous metal-organic framework (UiO-66-NH). We used specific installation for the production of gaseous RuO as well as for the quantification of this gas trapped within the filtering medium. We proved that UiO-66-NH has remarkable affinity for RuO capture, as this MOF exhibited the worldwide highest RuO decontamination factor (DF of 5745), hundreds of times higher than the DF values of sorbents daily used by the nuclear industry (zeolites or activated charcoal). The efficiency of UiO-66-NH can be explained by its pore diameters well adapted to the capture and immobilization of RuO as well as its conversion into stable RuO within the pores. This conversion corresponds to the reactivity of RuO with the MOF organic sub-network, leading to the oxidation of terephthalate ligands. As proved by powder X-ray diffraction and NMR techniques, these modifications did not decompose the MOF structure.
钌是一种放射性同位素，通常由核电站反应堆内的核工业产生。在核事故中，钌与氧气反应，生成极易挥发的四氧化钌RuO₄。挥发性和放射性的结合使RuO₄成为毒性最强的放射性物质之一，这也促使人们开发一种特定装置来捕获和固定它。在本研究中，我们首次报道了在多孔金属有机框架（UiO-66-NH₂）中捕获和固定气态RuO₄的情况。我们使用了特定装置来生产气态RuO₄以及对捕获在过滤介质中的这种气体进行定量。我们证明了UiO-66-NH₂对RuO₄的捕获具有显著的亲和力，因为这种金属有机框架展现出了全球最高的RuO₄去污系数（去污系数为5745），比核工业日常使用的吸附剂（沸石或活性炭）的去污系数值高出数百倍。UiO-66-NH₂的高效性可以通过其孔径来解释，这些孔径非常适合捕获和固定RuO₄，并且能使其在孔内转化为稳定的RuO₂。这种转化对应于RuO₄与金属有机框架有机子网络的反应性，导致对苯二甲酸酯配体的氧化。粉末X射线衍射和核磁共振技术证明，这些修饰并没有分解金属有机框架的结构。
