TY - JOUR

T1 - A Series of Mesoporous Metal-Organic Frameworks with Tunable Windows Sizes and Exceptionally High Ethane over Ethylene Adsorption Selectivity

AU - Lysova, Anna A.

AU - Samsonenko, Denis G.

AU - Kovalenko, Konstantin A.

AU - Nizovtsev, Anton S.

AU - Dybtsev, Danil N.

AU - Fedin, Vladimir P.

N1 - Funding Information: The work was supported by the Russian Foundation for Basic Research (project N o 18‐29‐04001). Diffraction data for single crystals of NIIC‐20‐Bu , NIIC‐20‐Pe , NIIC‐20‐Gl were obtained in the framework of the Russian Science Foundation project N o 19‐73‐20087. The authors thank Dr. P. V. Dorovatovskii and Dr. V. A. Lazarenko for their assistance during the synchrotron XRD experiments. The Siberian Supercomputer Center SB RAS is gratefully acknowledged for providing computational resources

PY - 2020/11/9

Y1 - 2020/11/9

N2 - The NIIC-20 (NIIC stands for Nikolaev Institute of Inorganic Chemistry) is a family of five isostructural metal-organic frameworks (MOFs) based on dodecanuclear wheel-shaped carboxylate building blocks {Zn12(RCOO)12(glycol)6} (glycol is deprotonated diatomic alcohol: ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol or glycerol), quantitatively crystallized from readily available starting chemicals. The crystal structures contain large mesoporous cages of 25 Å connected through {Zn12} rings, of which inner diameter and chemical nature depend solely on the chosen glycol. The NIIC-20 compounds feature high surface area and rarely observed inversed adsorption affinity for saturated hydrocarbon (ethane) over the unsaturated ones (ethylene, acetylene). The corresponding IAST (Ideal Adsorbed Solution Theory) adsorption selectivity factors reach as much as 15.4 for C2H6/C2H4 and 10.9 for C2H6/C2H2 gas mixtures at ambient conditions, exceeding those for any other porous MOF reported so far. The remarkable combination of high adsorption uptakes and high adsorption selectivities makes the NIIC-20 series a new benchmark of porous materials designed for ethylene separation applications.

AB - The NIIC-20 (NIIC stands for Nikolaev Institute of Inorganic Chemistry) is a family of five isostructural metal-organic frameworks (MOFs) based on dodecanuclear wheel-shaped carboxylate building blocks {Zn12(RCOO)12(glycol)6} (glycol is deprotonated diatomic alcohol: ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol or glycerol), quantitatively crystallized from readily available starting chemicals. The crystal structures contain large mesoporous cages of 25 Å connected through {Zn12} rings, of which inner diameter and chemical nature depend solely on the chosen glycol. The NIIC-20 compounds feature high surface area and rarely observed inversed adsorption affinity for saturated hydrocarbon (ethane) over the unsaturated ones (ethylene, acetylene). The corresponding IAST (Ideal Adsorbed Solution Theory) adsorption selectivity factors reach as much as 15.4 for C2H6/C2H4 and 10.9 for C2H6/C2H2 gas mixtures at ambient conditions, exceeding those for any other porous MOF reported so far. The remarkable combination of high adsorption uptakes and high adsorption selectivities makes the NIIC-20 series a new benchmark of porous materials designed for ethylene separation applications.

KW - adsorption

KW - alkanes

KW - alkenes

KW - mesoporous materials

KW - metal-organic frameworks

KW - DESIGN

KW - HYDROCARBONS

KW - PERFORMANCE

KW - MOFS

KW - ETHANE/ETHYLENE

KW - IRMOF-8

KW - BASIS-SETS

KW - SEPARATION

KW - COORDINATION FRAMEWORK

UR - http://www.scopus.com/inward/record.url?scp=85090300763&partnerID=8YFLogxK

U2 - 10.1002/anie.202008132

DO - 10.1002/anie.202008132

M3 - Article

C2 - 32729186

AN - SCOPUS:85090300763

VL - 59

SP - 20561

EP - 20567

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 46

ER -