Liu Jiaqi, Zhou Kang, Ullah Saif, Miao Jiafeng, Wang Hao, Thonhauser Timo, Li Jing
Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic, 7098 Liuxian Boulevard, Shenzhen, Guangdong, 518055, P. R. China.
Department of Physics and Center for Functional Materials, Wake Forest University, Winston-Salem, NC, 27109, USA.
Small. 2023 Oct;19(42):e2304460. doi: 10.1002/smll.202304460. Epub 2023 Jun 19.
The purification of C H from C H /C H /C H mixtures is of great significance in the chemical industry for C H production but remains a daunting task. Guided by powerful reticular chemistry principles, herein a systematic study is carried out to engineer pore dimensions and pore functionality of fcu-type Y-based metal-organic frameworks (Y-MOFs) through the construction of a series of eight new structures using linear dicarboxylate linkers with different length and functional groups. This study illustrates how delicate changes in pore size and pore surface chemistry can effectively influence the adsorption preference of C H , C H , and C H by the MOFs. Importantly, clear relations between pore size/pore surface polarity and C adsorption selectivities of this series of MOFs are established. In particular, HIAM-326 built on a linker decorated with trifluoromethoxy group shows notably preferential adsorption of C H and C H over C H , with balanced C H /C H and C H /C H selectivities. This endows the compound with the capability of one-step purification of C H from C H /C H /C H ternary mixtures, which is validated by breakthrough measurements where high purity C H (99.9%+) can be obtained directly from the separation column. Its adsorption thermodynamics and underlying selective adsorption mechanisms are further revealed by ab initio calculations.
从C₂H₆/C₂H₄/C₂H₂混合物中提纯C₂H₂在化学工业生产C₂H₂过程中具有重要意义，但仍是一项艰巨的任务。在强大的网状化学原理指导下，本文开展了一项系统研究，通过使用具有不同长度和官能团的线性二羧酸连接体构建一系列八个新结构，对fcu型Y基金属有机框架（Y-MOFs）的孔径和孔功能进行设计。该研究阐明了孔径和孔表面化学的细微变化如何有效影响MOFs对C₂H₆、C₂H₄和C₂H₂的吸附偏好。重要的是，建立了该系列MOFs的孔径/孔表面极性与C₂H₂吸附选择性之间的明确关系。特别是，基于装饰有三氟甲氧基的连接体构建的HIAM-326对C₂H₂和C₂H₄的吸附明显优于C₂H₆，具有平衡的C₂H₂/C₂H₆和C₂H₂/C₂H₄选择性。这赋予了该化合物从C₂H₆/C₂H₄/C₂H₂三元混合物中一步提纯C₂H₂的能力，这在突破测量中得到了验证，在该测量中可直接从分离柱获得高纯度C₂H₂（99.9%以上）。通过从头算计算进一步揭示了其吸附热力学和潜在的选择性吸附机制。
