In principle, porous physisorbents are attractive candidates for the removal of volatile organic compounds such as benzene by virtue of their low energy for the capture and release of this pollutant. Unfortunately, many physisorbents exhibit weak sorbate–sorbent interactions, resulting in poor selectivity and low uptake when volatile organic compounds are present at trace concentrations. Herein, we report that a family of double-walled metal–dipyrazolate frameworks, BUT-53 to BUT-58, exhibit benzene uptakes at 298 K of 2.47–3.28 mmol g⁻¹ at <10 Pa. Breakthrough experiments revealed that BUT-55, a supramolecular isomer of the metal–organic framework Co(BDP) (H₂BDP = 1,4-di(1H-pyrazol-4-yl)benzene), captures trace levels of benzene, producing an air stream with benzene content below acceptable limits. Furthermore, BUT-55 can be regenerated with mild heating. Insight into the performance of BUT-55 comes from the crystal structure of the benzene-loaded phase (C₆H₆@BUT-55) and density functional theory calculations, which reveal that C–H···X interactions drive the tight binding of benzene. Our results demonstrate that BUT-55 is a recyclable physisorbent that exhibits high affinity and adsorption capacity towards benzene, making it a candidate for environmental remediation of benzene-contaminated gas mixtures.

原则上，多孔物理吸附剂因其捕获和释放这种污染物的低能量而成为去除挥发性有机化合物（如苯）的有吸引力的候选者。不幸的是，许多物理吸附剂表现出较弱的吸附剂-吸附剂相互作用，当挥发性有机化合物以痕量浓度存在时，导致选择性差和吸收率低。在这里，我们报告了一个双壁金属-二吡唑酯框架家族，BUT-53 到 BUT-58，在 <10 Pa 时在 298 K 下表现出 2.47-3.28 mmol g ^-1的苯吸收。突破性实验表明 BUT-55 , 金属有机骨架 Co(BDP) 的超分子异构体 (H ₂ BDP = 1,4-di(1 H-pyrazol-4-yl)benzo)，捕获痕量苯，产生苯含量低于可接受限度的气流。此外，BUT-55 可以通过温和加热进行再生。对BUT-55性能的洞察来自苯负载相（C ₆ H ₆ @BUT-55）的晶体结构和密度泛函理论计算，表明C-H···X相互作用驱动紧密结合苯。我们的研究结果表明，BUT-55 是一种可回收的物理吸附剂，对苯表现出高亲和力和吸附能力，使其成为苯污染气体混合物环境修复的候选者。