Zirconium metal–organic frameworks (MOFs) can be promising adsorbents for various applications as they are highly stable in different chemical environments. In this work, a collection of Zr-MOFs comprised of more than 100 materials is screened for CF₄/CH₄, CH₄/H₂, and CH₄/N₂ separations using atomistic-level simulations. The top three MOFs for the CF₄/CH₄ separation are identified as PCN-700-BPDC-TPDC, LIFM-90, and BUT-67 exhibiting CF₄/CH₄ adsorption selectivities of 4.8, 4.6, and 4.7, CF₄ working capacities of 2.0, 2.0, and 2.1 mol kg⁻¹, and regenerabilities of 85.1, 84.2, and 75.7%, respectively. For the CH₄/H₂ separation, MOF-812, BUT-67, and BUT-66 are determined to be the top performing MOFs demonstrating CH₄/H₂ selectivities of 61.6, 36.7, and 46.2, CH₄ working capacities of 3.0, 4.1, and 3.4 mol kg⁻¹, and CH₄ regenerabilities of 70.7, 82.7, and 74.7%, respectively. Regarding the CH₄/N₂ separation, BUT-67, Zr-AbBA, and PCN-702 achieving CH₄/N₂ selectivities of 4.5, 3.4, and 3.8, CH₄ working capacities of 3.6, 3.9, and 3.5 mol kg⁻¹, and CH₄ regenerabilities of 81.1, 84.0, and 84.5%, in successive order, show the best overall separation performances. To further elucidate the adsorption in top performing adsorbents, the adsorption sites in these materials are analyzed using radial distribution functions and adsorbate density profiles. Finally, the water affinities of Zr-MOFs are explored to comment on their practical use in real gas separation applications. Our findings may inspire future studies probing the adsorption/separation mechanisms and performances of Zr-MOFs for different gases.

中文翻译：

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用于 CF4/CH4、CH4/H2 和 CH4/N2 分离的 Zr-MOF：朝着发现稳定有效吸附剂的目标迈进

锆金属有机骨架（MOF）在不同的化学环境中具有高度稳定性，因此可以成为各种应用的有前途的吸附剂。在这项工作中，使用原子级模拟筛选了由 100 多种材料组成的 Zr-MOF 集合，用于 CF ₄ /CH ₄、CH ₄ /H ₂和 CH ₄ /N ₂分离。CF ₄ /CH ₄分离的前三个 MOF被确定为 PCN-700-BPDC-TPDC、LIFM-90 和 BUT-67，它们的 CF ₄ /CH ₄吸附选择性为4.8、4.6和 4.7，CF ₄工作容量为 2.0、2.0 和 2.1 mol kg ^-1和可再生性分别为 85.1、84.2 和 75.7%。对于 CH ₄ /H ₂分离，MOF-812、BUT-67 和 BUT-66 被确定为表现最佳的 MOF，其 CH ₄ /H ₂选择性为 61.6、36.7 和 46.2，CH ₄工作容量为 3.0 、4.1 和 3.4 mol kg ^-1，CH ₄再生率分别为 70.7、82.7 和 74.7%。关于 CH ₄ /N ₂分离，BUT-67、Zr-AbBA 和 PCN-702 实现了 CH ₄ /N ₂选择性为4.5、3.4和 3.8，CH ₄工作容量为3.6、3.9和 3.5 mol kg ^{- 1}和 CH ₄再生率分别为 81.1、84.0 和 84.5%，依次显示出最佳的整体分离性能。为了进一步阐明性能最好的吸附剂中的吸附，使用径向分布函数和吸附物密度分布分析了这些材料中的吸附位点。最后，探索了 Zr-MOF 的水亲和性，以评论它们在实际气体分离应用中的实际应用。我们的发现可能会启发未来的研究，探索 Zr-MOFs 对不同气体的吸附/分离机制和性能。