Alexander E. Khudozhitkov , Sergei S. Arzumanov , Daniil I. Kolokolov , Alexander G. Stepanov
{"title":"UiO-66 (Zr) MOF中丁烷异构体的迁移率和骨架动力学:氧化锆簇中羟基的影响","authors":"Alexander E. Khudozhitkov , Sergei S. Arzumanov , Daniil I. Kolokolov , Alexander G. Stepanov","doi":"10.1016/j.ssnmr.2022.101784","DOIUrl":null,"url":null,"abstract":"<div><p><span>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 </span><sup>2</sup>H 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 <em>n</em><span>-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 </span><em>n</em>-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.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8000,"publicationDate":"2022-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"2","resultStr":"{\"title\":\"Butane isomers mobility and framework dynamics in UiO-66 (Zr) MOF: Impact of the hydroxyl groups in zirconia cluster\",\"authors\":\"Alexander E. Khudozhitkov , Sergei S. Arzumanov , Daniil I. Kolokolov , Alexander G. Stepanov\",\"doi\":\"10.1016/j.ssnmr.2022.101784\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span>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 </span><sup>2</sup>H 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 <em>n</em><span>-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 </span><em>n</em>-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.</p></div>\",\"PeriodicalId\":21937,\"journal\":{\"name\":\"Solid state nuclear magnetic resonance\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2022-04-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"2\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Solid state nuclear magnetic resonance\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926204022000133\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Solid state nuclear magnetic resonance","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926204022000133","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Butane isomers mobility and framework dynamics in UiO-66 (Zr) MOF: Impact of the hydroxyl groups in zirconia cluster
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.
期刊介绍:
The journal Solid State Nuclear Magnetic Resonance publishes original manuscripts of high scientific quality dealing with all experimental and theoretical aspects of solid state NMR. This includes advances in instrumentation, development of new experimental techniques and methodology, new theoretical insights, new data processing and simulation methods, and original applications of established or novel methods to scientific problems.