Submicrometer‐Sized ZIF‐71 Filled Organophilic Membranes for Improved Bioethanol Recovery: Mechanistic Insights by Monte Carlo Simulation and FTIR Spectroscopy
Submicrometer‐Sized ZIF‐71 Filled Organophilic Membranes for Improved Bioethanol Recovery: Mechanistic Insights by Monte Carlo Simulation and FTIR Spectroscopy
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DOI：
10.1002/adfm.201402972
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发表时间：
2015
影响因子：
19
通讯作者：
Lik H. Wee;Yanbo Li;Kang Zhang;P. Davit;S. Bordiga;Jianwen Jiang;I. Vankelecom;J. Martens
中科院分区：
文献类型：
--
作者：
Lik H. Wee;Yanbo Li;Kang Zhang;P. Davit;S. Bordiga;Jianwen Jiang;I. Vankelecom;J. Martens
无模板自组装合成纳米金属有机骨架(MOF)是金属有机骨架研究的热点，因为具有独特性质的有序纳米结构可用于许多先进的应用领域。在这项工作中，报告了不同粒度(140290或430 nm)的粗壮的亚微米尺寸的ZIF-71晶体的简便合成，具有高的永久微孔率(SBET=827cm2 g−1)和合成产率高达80%(以克尺度的锌为基础)。扫描电子显微镜证实，这些细小的ZIF-71粒子是制备更薄、更均匀的聚二甲基硅氧烷(PDMS)混合基膜(MMM)的理想填料，具有优异的填料分散性和高达40wt%的填料-聚合物粘附性。使用这些亚微米尺寸的ZIF-71填充的MMM进行的渗透汽化测试表明，生物乙醇的回收有显著的改善。首次用傅里叶变换红外光谱研究了乙醇-乙醇氢气相中可逆的乙醇-乙醇氢相互作用和乙醇与α-笼和八方柱笼中-Cl官能团的不可逆氢相互作用现象。与分子模拟结果完全一致，从根本上解释了ZIF-71填充MMMS的渗透汽化性能。
Template‐free self‐assembly synthesis of nano‐sized metal‐organic frameworks (MOFs) is of particular interest in MOF research since organized nanostructures possessing distinctive properties are useful for many advanced applications. In this work, the facile room temperature synthesis of robust submicrometer‐sized ZIF‐71 crystals with different particle sizes (140, 290, or 430 nm), having a high permanent microporosity (SBET = 827 cm2 g−1) and synthesis yield up to 80% based on Zn on a gram‐scale, is reported. These small ZIF‐71 particles are ideal filler for the fabrication of thinner and homogeneous polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) with excellent filler dispersion and filler‐polymer adhesion at high loading up to 40 wt%, as confirmed by scanning electron microscopy. Pervaporation tests using these submicrometer‐sized ZIF‐71 filled MMMs show significant improvement for bioethanol recovery. Interesting phenomena of i) reversible ethanol‐ethanol hydrogen interaction in the ethanol liquid‐phase and ii) irreversible hydrogen interaction of ethanol and –Cl functional group in the α‐cages and octagonal prismatic cages of ZIF‐71 in ethanol vapor‐phase are discovered for the first time by a Fourier transform infrared spectroscopy (FTIR) study. In full agreement with molecular simulation results, these explain fundamentally the ZIF‐71 filled MMMs pervaporation performance.