title: Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.
abstract: Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1% acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups.
authors.affiliation: Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, 32 Shangsan Road, Fuzhou, 350007, P. R. China.
authors.forename: Zizhu
authors.initials: Z
authors.lastname: Yao
authors.affiliation: Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, 32 Shangsan Road, Fuzhou, 350007, P. R. China.
authors.forename: Zhangjing
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, 32 Shangsan Road, Fuzhou, 350007, P. R. China.
authors.forename: Lizhen
authors.initials: L
authors.lastname: Liu
authors.affiliation: Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, 32 Shangsan Road, Fuzhou, 350007, P. R. China.
authors.forename: Ziyin
authors.initials: Z
authors.lastname: Li
authors.affiliation: NIST Center for Neutron Research, Gaithersburg, Maryland, 20899-6102, USA.
authors.forename: Wei
authors.initials: W
authors.lastname: Zhou
authors.affiliation: Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.|Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, P. R. China.
authors.forename: Yunfeng
authors.initials: Y
authors.lastname: Zhao
authors.affiliation: Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Yu
authors.initials: Y
authors.lastname: Han
authors.affiliation: Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas, 78249-0698, USA.
authors.forename: Banglin
authors.initials: B
authors.lastname: Chen
authors.affiliation: Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam, 1098 XH, The Netherlands.
authors.forename: Rajamani
authors.initials: R
authors.lastname: Krishna
authors.affiliation: Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, 32 Shangsan Road, Fuzhou, 350007, P. R. China. scxiang@fjnu.edu.cn.
authors.forename: Shengchang
authors.identifier: http://orcid.org/0000-0001-6016-2587
authors.initials: S
authors.lastname: Xiang
keywords: column breakthrough; metal-organic frameworks; open O donors; selective gas adsorption; structural diversity