Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, 321004, China.
IBM Thomas J. Watson Research, Yorktown Heights, New York, NY, 10598, USA.
Nat Commun. 2023 Jan 25;14(1):401. doi: 10.1038/s41467-023-35984-5.
Ethylene (CH) purification from multi-component mixtures by physical adsorption is a great challenge in the chemical industry. Herein, we report a GeF anion embedded MOF (ZNU-6) with customized pore structure and pore chemistry for benchmark one-step CH recovery from CH and CO. ZNU-6 exhibits significantly high CH (1.53 mmol/g) and CO (1.46 mmol/g) capacity at 0.01 bar. Record high CH productivity is achieved from CH/CO/CH mixtures in a single adsorption process under various conditions. The separation performance is retained over multiple cycles and under humid conditions. The potential gas binding sites are investigated by density functional theory (DFT) calculations, which suggest that CH and CO are preferably adsorbed in the interlaced narrow channel with high aff0inity. In-situ single crystal structures with the dose of CH, CO or CH further reveal the realistic host-guest interactions. Notably, rare CH clusters are formed in the narrow channel while two distinct CO adsorption locations are observed in the narrow channel and the large cavity with a ratio of 1:2, which accurately account for the distinct adsorption heat curves.
通过物理吸附从多组分混合物中纯化乙烯（CH）是化学工业面临的一大挑战。在此，我们报道了一种具有定制孔结构和孔化学性质的 GeF 阴离子嵌入 MOF（ZNU-6），用于从 CH 和 CO 中基准一步回收 CH。ZNU-6 在 0.01 bar 下表现出显著高的 CH（1.53 mmol/g）和 CO（1.46 mmol/g）容量。在各种条件下，在单一吸附过程中，从 CH/CO/CH 混合物中实现了创纪录的高 CH 生产率。分离性能在多个循环和潮湿条件下得以保留。通过密度泛函理论（DFT）计算研究了潜在的气体结合位点，这表明 CH 和 CO 优选在具有高亲和力的交错狭窄通道中吸附。随着 CH、CO 或 CH 的剂量增加，原位单晶结构进一步揭示了实际的主客体相互作用。值得注意的是，在狭窄通道中形成了罕见的 CH 簇，而在狭窄通道和大空腔中观察到两个不同的 CO 吸附位置，比例为 1:2，这准确地解释了不同的吸附热曲线。
