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通过将四乙烯五胺限制在 ZIF-8 的孔内来诱导进一步吸附水和二氧化碳,设计并制备了一种优越的质子导体。

Design and Preparation of a Superior Proton Conductor by Confining Tetraethylenepentamine in the Pores of ZIF-8 To Induce Further Adsorption of Water and Carbon Dioxide.

机构信息

State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering , Nanjing Tech University , Nanjing , Jiangsu 211816 , P. R. China.

Institute for Frontier Materials (IFM) , Deakin University , 75 Pigdons Road , Waurn Ponds , Victoria 3216 , Australia.

出版信息

Inorg Chem. 2019 Nov 4;58(21):14693-14700. doi: 10.1021/acs.inorgchem.9b02358. Epub 2019 Oct 24.

Abstract

In this work, we present a new strategy toward the design and preparation of a metal-organic framework- or porous coordination polymer-based superior proton conductor. We chose a robust metal-organic framework, ZIF-8, as the host and a flexible aliphatic alkylpolyamine, tetraethylenepentamine (TEPA), as the guest, and we successfully prepared an encapsulation compound TEPA@ZIF-8 via the facile insertion of TEPA into the pores of ZIF-8, which was characterized by microanalysis, thermogravimetric analysis, IR spectroscopy, N, water vapor adsorption-desorption, and other methods. Each cage in ZIF-8 is occupied by ∼1.44 TEPA molecules, and the introduced TEPA further adsorbs HO and CO from air to offer a superior proton conductor, TEPA@ZIF-8-HCO, with σ = 2.08 × 10 S cm at 293 K and 99% relative humidity, and excellent proton conduction durability. Regarding ZIF-8, the proton conductivity of TEPA@ZIF-8-HCO increases by 3 orders of magnitude at the same condition, and the activation energy decreases by 0.91 eV. Remarkably, TEPA@ZIF-8-HCO also shows promising features for the detection of aqueous ammonia. This work provides more opportunities to achieve superior protonic conducting materials and suggests that MOF-based proton conductors possess great potential for applications in ammonia sensing.

摘要

在这项工作中,我们提出了一种新的策略,用于设计和制备基于金属-有机骨架或多孔配位聚合物的优异质子导体。我们选择了一种坚固的金属-有机骨架 ZIF-8 作为主体,选择了一种灵活的脂肪族烷基多胺四乙烯五胺(TEPA)作为客体,并通过将 TEPA 插入 ZIF-8 的孔中成功制备了包封化合物 TEPA@ZIF-8,通过微分析、热重分析、IR 光谱、N、水蒸气吸附-解吸等方法进行了表征。ZIF-8 中的每个笼都被约 1.44 个 TEPA 分子占据,而引入的 TEPA 进一步从空气中吸附 HO 和 CO,提供了一种优异的质子导体 TEPA@ZIF-8-HCO,在 293 K 和 99%相对湿度下的电导率为 2.08×10 S cm,质子传导耐久性良好。对于 ZIF-8,在相同条件下,TEPA@ZIF-8-HCO 的质子电导率提高了 3 个数量级,活化能降低了 0.91 eV。值得注意的是,TEPA@ZIF-8-HCO 还在检测水溶液氨方面表现出了有前景的特征。这项工作为实现优异质子导电材料提供了更多机会,并表明基于 MOF 的质子导体在氨传感应用方面具有巨大潜力。

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