Univ. Lille, CNRS, ENSCL, Centrale Lille, Univ. Artois, UMR 8181-UCCS - Unité de Catalyse et de Chimie du Solide, F-59000 Lille, France.
Phys Chem Chem Phys. 2018 Jun 20;20(24):16770-16776. doi: 10.1039/c8cp01950a.
Radioactive gaseous ruthenium tetroxide (RuO4) can be released into the environment in the case of a severe nuclear accident. Using periodic dispersion corrected density functional theory calculations, we have investigated for the first time the adsorption behavior of RuO4 into prototypical porous materials, Metal-Organic Frameworks (MOFs) and zeolites, with the aim of mitigating ruthenium releases to the outside. For the MOFs, we have screened a set of six structures (MIL-53(Al), MIL-120(Al), HKUST-1(Cu), UiO-66(Zr), UiO-67(Zr) and UiO-68(Zr)), while for the zeolites two structures have been selected: mordenite (MOR) with Si/Al ratios of 11 and 5, and faujasite (FAU) with a Si/Al ratio of 2.4. The DFT calculations show that the nature of the porous materials does not have a significant effect on the adsorption energy of RuO4 compounds and that the main interaction is due to the formation of hydrogen bonds. For the tested materials, computational results show that the interaction energies of RuO4 reach their maximum with the hydrated form of HKUST-1(Cu) (-114 kJ mol-1) due to the presence of strong hydrogen bonds between the water molecules and the oxygen atoms of RuO4.
放射性气态四氧化钌（RuO4）在严重核事故的情况下可能会释放到环境中。我们首次使用周期性分散修正密度泛函理论计算，研究了 RuO4 进入典型多孔材料（金属有机骨架（MOFs）和沸石）的吸附行为，目的是减轻钌向外部的释放。对于 MOFs，我们筛选了一组六种结构（MIL-53(Al)、MIL-120(Al)、HKUST-1(Cu)、UiO-66(Zr)、UiO-67(Zr) 和 UiO-68(Zr))，而对于沸石，选择了两种结构：硅铝比为 11 和 5 的丝光沸石（MOR）和硅铝比为 2.4 的八面沸石（FAU）。DFT 计算表明，多孔材料的性质对 RuO4 化合物的吸附能没有显著影响，主要的相互作用是由于氢键的形成。对于测试的材料，计算结果表明，由于 RuO4 与水分子之间存在氢键，水合形式的 HKUST-1(Cu)（-114 kJ mol-1）的相互作用能最大。
