Xiang-Jing Kong, Ming-Ming Xu, Tao He, Lin-Hua Xie, Yu-Hui Liu, Xin Zhang, Hao-Tian Wang, Jian-Rong Li
{"title":"氢键定义的孔窗使超微多孔金属有机框架中丙烯与丙烷的筛分分离成为可能","authors":"Xiang-Jing Kong, Ming-Ming Xu, Tao He, Lin-Hua Xie, Yu-Hui Liu, Xin Zhang, Hao-Tian Wang, Jian-Rong Li","doi":"10.1021/acs.chemmater.4c02251","DOIUrl":null,"url":null,"abstract":"Tailoring a MOF with suitable pore windows for the sieving C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation is attractive but challenging, where controlling the local framework flexibility by introducing functionality provides a solution. In this work, four isoreticular ultramicroporous Zn–triazolate–dicarboxylate frameworks, <b>Zn-ATZ-IP(R)</b> (R = −F, −OH, −NH<sub>2</sub>, and −CH<sub>3</sub>) (HATZ = 3-amino-1,2,4-triazole; H<sub>2</sub>IP-R = R group functionalized isophthalic acid) with variable pore apertures, were targeted as platforms to study the effect of functional groups on their separation performance. Single-component adsorption isotherms uncovered the potential of <b>Zn-ATZ-IP(OH)-a</b> with hydroxyl groups as a sieving adsorbent. Single X-ray diffraction (SXRD) measurements revealed that strong intraframework hydrogen bonds hinder the free torsion of ATZ<sup>–</sup> ligand in <b>Zn-ATZ-IP(OH)-a</b>, defining rigid pore windows that admit C<sub>3</sub>H<sub>6</sub> while exclude C<sub>3</sub>H<sub>8</sub>, whereas other groups give adaptive larger pores that allow both C<sub>3</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub> in. Further, <i>in situ</i> XRD measurements suggested that temperature alters the strength of hydrogen bonds, making <b>Zn-ATZ-IP(OH)-a</b> ideal for room-temperature sieving of C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub>. This work highlights the superiority of customizing sieving pores sustained by hydrogen bonds, which advances the rational design of smart adsorbents for energy-efficient light hydrocarbon separations.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hydrogen Bonds Defined Pore Windows Enable Sieving Separation of Propylene from Propane in an Ultramicroporous Metal–Organic Framework\",\"authors\":\"Xiang-Jing Kong, Ming-Ming Xu, Tao He, Lin-Hua Xie, Yu-Hui Liu, Xin Zhang, Hao-Tian Wang, Jian-Rong Li\",\"doi\":\"10.1021/acs.chemmater.4c02251\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Tailoring a MOF with suitable pore windows for the sieving C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation is attractive but challenging, where controlling the local framework flexibility by introducing functionality provides a solution. In this work, four isoreticular ultramicroporous Zn–triazolate–dicarboxylate frameworks, <b>Zn-ATZ-IP(R)</b> (R = −F, −OH, −NH<sub>2</sub>, and −CH<sub>3</sub>) (HATZ = 3-amino-1,2,4-triazole; H<sub>2</sub>IP-R = R group functionalized isophthalic acid) with variable pore apertures, were targeted as platforms to study the effect of functional groups on their separation performance. Single-component adsorption isotherms uncovered the potential of <b>Zn-ATZ-IP(OH)-a</b> with hydroxyl groups as a sieving adsorbent. Single X-ray diffraction (SXRD) measurements revealed that strong intraframework hydrogen bonds hinder the free torsion of ATZ<sup>–</sup> ligand in <b>Zn-ATZ-IP(OH)-a</b>, defining rigid pore windows that admit C<sub>3</sub>H<sub>6</sub> while exclude C<sub>3</sub>H<sub>8</sub>, whereas other groups give adaptive larger pores that allow both C<sub>3</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub> in. Further, <i>in situ</i> XRD measurements suggested that temperature alters the strength of hydrogen bonds, making <b>Zn-ATZ-IP(OH)-a</b> ideal for room-temperature sieving of C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub>. This work highlights the superiority of customizing sieving pores sustained by hydrogen bonds, which advances the rational design of smart adsorbents for energy-efficient light hydrocarbon separations.\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-10-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.chemmater.4c02251\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acs.chemmater.4c02251","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Hydrogen Bonds Defined Pore Windows Enable Sieving Separation of Propylene from Propane in an Ultramicroporous Metal–Organic Framework
Tailoring a MOF with suitable pore windows for the sieving C3H6/C3H8 separation is attractive but challenging, where controlling the local framework flexibility by introducing functionality provides a solution. In this work, four isoreticular ultramicroporous Zn–triazolate–dicarboxylate frameworks, Zn-ATZ-IP(R) (R = −F, −OH, −NH2, and −CH3) (HATZ = 3-amino-1,2,4-triazole; H2IP-R = R group functionalized isophthalic acid) with variable pore apertures, were targeted as platforms to study the effect of functional groups on their separation performance. Single-component adsorption isotherms uncovered the potential of Zn-ATZ-IP(OH)-a with hydroxyl groups as a sieving adsorbent. Single X-ray diffraction (SXRD) measurements revealed that strong intraframework hydrogen bonds hinder the free torsion of ATZ– ligand in Zn-ATZ-IP(OH)-a, defining rigid pore windows that admit C3H6 while exclude C3H8, whereas other groups give adaptive larger pores that allow both C3H6 and C3H8 in. Further, in situ XRD measurements suggested that temperature alters the strength of hydrogen bonds, making Zn-ATZ-IP(OH)-a ideal for room-temperature sieving of C3H6/C3H8. This work highlights the superiority of customizing sieving pores sustained by hydrogen bonds, which advances the rational design of smart adsorbents for energy-efficient light hydrocarbon separations.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.