TY - JOUR

T1 - Butane isomers mobility and framework dynamics in UiO-66 (Zr) MOF: Impact of the hydroxyl groups in zirconia cluster

AU - Khudozhitkov, Alexander E.

AU - Arzumanov, Sergei S.

AU - Kolokolov, Daniil I.

AU - Stepanov, Alexander G.

N1 - Funding Information: This work was supported by Ministry of Science and Higher Education of the Russian Federation (project АААА-А21-121011390053-4 for Boreskov Institute of Catalysis) and in part by the Russian Foundation for Basic Research (RFBR) (Grant no. 19-33-90026 ). Publisher Copyright: © 2022 Elsevier Inc.

PY - 2022/4

Y1 - 2022/4

N2 - UiO-66 (Zr) is a metal-organic framework (MOF) known for its thermal and chemical stability and wide range of adsorption-based applications. This MOF exhibits high separation selectivity for butane isomers. It has been earlier inferred that the separation performance of the material depends on the hydroxylation state of the zirconia cluster. In this contribution, we apply 2H solid-state NMR to characterize the dynamics of both the MOF organic framework itself and butane isomers in hydroxylated and dehydroxylated forms of UiO-66. It is established that the rate of π-flipping and the amplitude of the phenylene ring plane librations in the framework are higher for the dehydroxylated form. Self-diffusion coefficients of butane isomers have been estimated for both forms of UiO-66. The diffusivity is higher for n-butane in the dehydroxylated form, whereas the diffusion of isobutane is not affected by the presence of OH groups in the zirconia cluster of the MOF. Higher diffusivity of n-butane in dehydroxylated form is accounted for by the larger effective diameter of the window between the adjacent cages in this form, which arises from faster rotation and larger amplitude of framework linker libration. This rationalizes the higher efficiency of the dehydroxylated form of UiO-66(Zr) material for butane isomers separation.

AB - UiO-66 (Zr) is a metal-organic framework (MOF) known for its thermal and chemical stability and wide range of adsorption-based applications. This MOF exhibits high separation selectivity for butane isomers. It has been earlier inferred that the separation performance of the material depends on the hydroxylation state of the zirconia cluster. In this contribution, we apply 2H solid-state NMR to characterize the dynamics of both the MOF organic framework itself and butane isomers in hydroxylated and dehydroxylated forms of UiO-66. It is established that the rate of π-flipping and the amplitude of the phenylene ring plane librations in the framework are higher for the dehydroxylated form. Self-diffusion coefficients of butane isomers have been estimated for both forms of UiO-66. The diffusivity is higher for n-butane in the dehydroxylated form, whereas the diffusion of isobutane is not affected by the presence of OH groups in the zirconia cluster of the MOF. Higher diffusivity of n-butane in dehydroxylated form is accounted for by the larger effective diameter of the window between the adjacent cages in this form, which arises from faster rotation and larger amplitude of framework linker libration. This rationalizes the higher efficiency of the dehydroxylated form of UiO-66(Zr) material for butane isomers separation.

KW - H solid-state NMR

KW - Butane isomers separation

KW - Butane mobility

KW - Diffusivity

KW - Framework dynamics

KW - UiO-66 (Zr)

UR - http://www.scopus.com/inward/record.url?scp=85125619356&partnerID=8YFLogxK

U2 - 10.1016/j.ssnmr.2022.101784

DO - 10.1016/j.ssnmr.2022.101784

M3 - Article

C2 - 35247850

AN - SCOPUS:85125619356

VL - 118

JO - Solid State Nuclear Magnetic Resonance

JF - Solid State Nuclear Magnetic Resonance

SN - 0926-2040

M1 - 101784

ER -