Liu Xing, Zhang Peixin, Xiong Hanting, Zhang Yan, Wu Ke, Liu Junhui, Krishna Rajamani, Chen Jingwen, Chen Shixia, Zeng Zheling, Deng Shuguang, Wang Jun
Chemistry and Chemical Engineering School, Nanchang University, Nanchang, Jiangxi, 330031, China.
Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam, 1098 XH, Netherlands.
Adv Mater. 2023 May;35(20):e2210415. doi: 10.1002/adma.202210415. Epub 2023 Mar 29.
Engineering pore environments exhibit great potential in improving gas adsorption and separation performances but require specific means for acetylene/carbon dioxide (C H /CO ) separation due to their identical dynamic diameters and similar properties. Herein, a novel sulfate-pillared MOF adsorbent (SOFOUR-TEPE-Zn) using 1,1,2,2-tetra(pyridin-4-yl) ethene (TEPE) ligand with dense electronegative pore surfaces is reported. Compared to the prototype SOFOUR-1-Zn, SOFOUR-TEPE-Zn exhibits a higher C H uptake (89.1 cm g ), meanwhile the CO uptake reduces to 14.1 cm g , only 17.4% of that on SOFOUR-1-Zn (81.0 cm g ). The high affinity toward C H than CO is demonstrated by the benchmark C H /CO selectivity (16 833). Furthermore, dynamic breakthrough experiments confirm its application feasibility and good cyclability at various flow rates. During the desorption cycle, 60.1 cm g C H of 99.5% purity or 33.2 cm g C H of 99.99% purity can be recovered by stepped purging and mild heating. The simulated pressure swing adsorption processes reveal that 75.5 cm g C H of 99.5+% purity with a high gas recovery of 99.82% can be produced in a counter-current blowdown process. Modeling studies disclose four favorable adsorption sites and dense packing for C H .
工程孔隙环境在改善气体吸附和分离性能方面具有巨大潜力，但由于乙炔/二氧化碳（C₂H₂/CO₂）具有相同的动力学直径和相似的性质，因此需要特定的方法来实现二者的分离。在此，报道了一种新型的硫酸盐柱撑金属有机框架吸附剂（SOFOUR-TEPE-Zn），其使用1,1,2,2-四（吡啶-4-基）乙烯（TEPE）配体，具有致密的带负电孔隙表面。与原型SOFOUR-1-Zn相比，SOFOUR-TEPE-Zn表现出更高的C₂H₂吸附量（89.1 cm³ g⁻¹），同时CO₂吸附量降至14.1 cm³ g⁻¹，仅为SOFOUR-1-Zn上吸附量（81.0 cm³ g⁻¹）的17.4%。通过基准C₂H₂/CO₂选择性（16 833）证明了其对C₂H₂比对CO₂具有更高的亲和力。此外，动态突破实验证实了其在各种流速下的应用可行性和良好的循环性。在解吸循环过程中，通过分步吹扫和温和加热，可以回收纯度为99.5%的60.1 cm³ g⁻¹的C₂H₂或纯度为99.99%的33.2 cm³ g⁻¹的C₂H₂。模拟的变压吸附过程表明，在逆流排放过程中可以生产出纯度为99.5+%、气体回收率高达99.82%的75.5 cm³ g⁻¹的C₂H₂。建模研究揭示了四个有利于C₂H₂吸附的位点和致密堆积结构。
