Selective adsorptive capture and separation of chemically inert krypton (Kr) and xenon (Xe) noble gases with very low ppmv concentrations in air and industrial off-gases constitute an important technological challenge. Here, using a synergistic combination of experiment and theory, the microporous crystalline vanadomolybdates (MoVO_x) as highly selective Kr sorbents are studied in detail. By varying the Mo/V ratios, we show for the first time that their one-dimensional (1D) pores can be fine-tuned for the size-selective adsorption of Kr over the larger Xe with selectivities reaching >100. Using extensive electronic structure calculations and grand canonical Monte Carlo simulations, the competition between Kr uptake with CO₂ and N₂ was also investigated. As most materials reported so far are selective toward the larger, more polarizable Xe than Kr, this work constitutes an important step toward robust Kr-selective sorbent materials. This work highlights the potential use of porous crystalline transition metal oxides as energy-efficient and selective noble gas capture sorbents for industrial applications.

中文翻译：

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微调结晶钒钼酸盐框架的微孔率，用于 Kr 与 Xe 的选择性吸附分离


选择性吸附捕获和分离空气和工业废气中 ppmv 浓度极低的化学惰性氪 （Kr） 和氙 （Xe） 惰性气体是一项重要的技术挑战。在这里，通过实验和理论的协同结合，详细研究了微孔结晶钒钼酸盐 （MoVO_x） 作为高选择性的 Kr 吸附剂。通过改变 Mo/V 比率，我们首次表明它们的一维 （1D） 孔可以微调 Kr 在较大 Xe 上的尺寸选择性吸附，选择性达到 >100。使用广泛的电子结构计算和大正则蒙特卡洛模拟，还研究了 Kr 摄取与 CO₂ 和 N₂ 之间的竞争。由于迄今为止报道的大多数材料都对比 Kr 更大、更易极化的 Xe 具有选择性，因此这项工作是朝着稳健的 Kr 选择性吸附剂材料迈出的重要一步。这项工作强调了多孔结晶过渡金属氧化物作为工业应用中节能和选择性惰性气体捕获吸附剂的潜在用途。