Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity
Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity
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DOI：
10.1016/j.jcat.2011.04.015
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发表时间：
2011-07-01
影响因子：
7.3
通讯作者：
Kapteijn, Freek
中科院分区：
文献类型：
--
作者：
Goesten, Maarten G.;Juan-Alcaniz, Jana;Kapteijn, Freek
发展了一种新的金属有机骨架(MOF)的后官能化方法，以引入酸性用于催化。用三元酸酐和硫酸的混合物处理后，化学稳定的MOF结构MIL-101(Cr)和MIL-53(Al)可以被硫酸盐化，导致Bronsted亚磺酸基团连接到该结构的50%的芳香对苯二甲酸酯连接基上。用固体核磁共振、XANES和FTIR光谱对硫酸盐化样品进行了广泛的表征。功能化的酸性骨架在正丁醇和醋酸的酯化反应中表现出与Nafion(R)等酸性聚合物相似的催化活性(TOF类似于343K下1min(-1))。在S-MIL-53(Al)的一维孔道中，水被强吸附，每个亚磺酸基团最多吸附4个分子，在较低的温度下，另外2个分子被吸附。高水含量和B酸度为S-MIL-53(Al)结构提供了在中等温度下的高质子电导率。(C)2011 Elsevier Inc.保留所有权利。
A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Bronsted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion (R) display in the esterification of n-butanol with acetic acid (TOF similar to 1 min(-1) @ 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Bronsted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures. (C) 2011 Elsevier Inc. All rights reserved.