TY - JOUR

T1 - Metal-Organic Frameworks for Highly Selective Separation of Xylene Isomers and Single-Crystal X-ray Study of Aromatic Guest-Host Inclusion Compounds

AU - Sapianik, Aleksandr A.

AU - Dudko, Evgeny R.

AU - Kovalenko, Konstantin A.

AU - Barsukova, Marina O.

AU - Samsonenko, Denis G.

AU - Dybtsev, Danil N.

AU - Fedin, Vladimir P.

N1 - Funding Information: Synthesis of new heterometallic MOF and its luminescence investigation were supported by the Russian Science Foundation grant (No. 19-73-00171), and X-ray structural analysis and sorption/selectivity investigation were supported by the Russian Science Foundation grant (No. 19-73-20087). The authors thank Dr. P. V. Dorovatovskii and Dr. V. A. Lazarenko for their assistance during synchrotron XRD experiments. Publisher Copyright: © 2021 American Chemical Society. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3/31

Y1 - 2021/3/31

N2 - Separation of hydrocarbon molecules, such as benzene/cyclohexane and o-xylene/m-xylene/p-xylene, is relevant due to their widespread application as chemical feedstock but challenging because of their similar boiling points and close molecular sizes. Physisorption separation could offer an energy-efficient solution to this problem, but the design and synthesis of sorbents that exhibit high selectivity for one of the hydrocarbons remain a largely unmet challenge. Herein, we report a new heterometallic MOF with a unique tortuous shape of channels decorated with aromatic sorption sites [Li2Zn2(bpy)(ndc)3] (NIIC-30(Ph), bpy = 4,4'-bipyridine, ndc2- = naphthalene-1,4-dicarboxylate) and study of its benzene/cyclohexane and xylene vapor and liquid separation. For an equimolar benzene/cyclohexane mixture, it is possible to achieve a 10-fold excess of benzene in the adsorbed phase. In the case of xylenes, microporous framework NIIC-30(Ph) demonstrates outstanding selective sorption properties and becomes a new benchmark for m-/o-xylene separation. In addition, NIIC-30(Ph) is stable enough to carry out at least three separation cycles of benzene/cyclohexane mixtures or ternary o-xylene/m-xylene/p-xylene mixtures both in the liquid and in the vapor phase. Insights into the performance of NIIC-30(Ph) are gained from X-ray structural studies of each aromatic guest inclusion compound.

AB - Separation of hydrocarbon molecules, such as benzene/cyclohexane and o-xylene/m-xylene/p-xylene, is relevant due to their widespread application as chemical feedstock but challenging because of their similar boiling points and close molecular sizes. Physisorption separation could offer an energy-efficient solution to this problem, but the design and synthesis of sorbents that exhibit high selectivity for one of the hydrocarbons remain a largely unmet challenge. Herein, we report a new heterometallic MOF with a unique tortuous shape of channels decorated with aromatic sorption sites [Li2Zn2(bpy)(ndc)3] (NIIC-30(Ph), bpy = 4,4'-bipyridine, ndc2- = naphthalene-1,4-dicarboxylate) and study of its benzene/cyclohexane and xylene vapor and liquid separation. For an equimolar benzene/cyclohexane mixture, it is possible to achieve a 10-fold excess of benzene in the adsorbed phase. In the case of xylenes, microporous framework NIIC-30(Ph) demonstrates outstanding selective sorption properties and becomes a new benchmark for m-/o-xylene separation. In addition, NIIC-30(Ph) is stable enough to carry out at least three separation cycles of benzene/cyclohexane mixtures or ternary o-xylene/m-xylene/p-xylene mixtures both in the liquid and in the vapor phase. Insights into the performance of NIIC-30(Ph) are gained from X-ray structural studies of each aromatic guest inclusion compound.

KW - benzene

KW - heterometallic

KW - metal−organic frameworks

KW - preorganized complexes

KW - separation

KW - sorption

KW - xylenes

UR - http://www.scopus.com/inward/record.url?scp=85103682021&partnerID=8YFLogxK

U2 - 10.1021/acsami.1c02812

DO - 10.1021/acsami.1c02812

M3 - Article

C2 - 33729772

AN - SCOPUS:85103682021

VL - 13

SP - 14768

EP - 14777

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 12

ER -