Three Series of Sulfo-Functionalized Mixed-Linker CAU-10 Analogues: Sorption Properties, Proton Conductivity, and Catalytic Activity.
Three Series of Sulfo-Functionalized Mixed-Linker CAU-10 Analogues: Sorption Properties, Proton Conductivity, and Catalytic Activity.
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DOI：
10.1002/chem.201501502
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发表时间：
2015-08
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影响因子：
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通讯作者：
N. Reimer;B. Bueken;S. Leubner;Christopher F. Seidler;M. Wark;D. D. De Vos-D.;N. Stock
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文献类型：
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作者：
N. Reimer;B. Bueken;S. Leubner;Christopher F. Seidler;M. Wark;D. D. De Vos-D.;N. Stock
合成了10个具有CAU-10型结构的混联金属有机骨架[Al(OH)(m-BDC-X)(1-y)(m-BDC-SO3H)y](H_2BDC=1，3-苯二甲酸；X=H，NO2，OH)。根据所用配体的组合，这些化合物可以分为三个系列。采用不同比例的m-H_2BDC-X和m-H_2BDC-SO_3Li合成了三个系列的化合物。所得到的化合物，表示为CAU-10-H/SX，-N/SX和-O/SX，对高达350°C的磺化材料表现出极高的热稳定性。对极性和酸性进行了详细的表征，并通过对几种气体和水蒸气的吸附亲和力/容量的变化清楚地证明了额外的SO3H基的影响。此外，还对所选样品的质子导电性以及作为乙醇气相脱水制乙烯催化剂的性能进行了评价。虽然只观察到很低的质子电导率，但催化活性得到了显著的提高。在250℃和300℃下反应40h以上，没有观察到脱磺反应和结晶度损失，乙醇转化率稳定。这表明这种材料具有很高的稳定性。
Ten mixed-linker metal-organic frameworks [Al(OH)(m-BDC-X)(1-y)(m-BDC-SO3H)y] (H2BDC = 1,3-benzenedicarboxylic acid; X = H, NO2, OH) exhibiting the CAU-10-type structure were synthesized. The compounds can be grouped into three series according to the combination of ligands employed. The three series of compounds were obtained by employing different ratios of m-H2 BDC-X and m-H2BDC-SO3Li. The resulting compounds, which are denoted CAU-10-H/Sx, -N/Sx and -O/Sx, show exceptionally high thermal stability for sulfonated materials of up to 350 °C. Detailed characterization with special focus on polarity and acidity was performed, and the impact of the additional SO3H groups is clearly demonstrated by changes in the sorption affinities/capacities towards several gases and water vapor. In addition, selected samples were evaluated for proton conductivity and as catalysts for the gas-phase dehydration of ethanol to ethylene. While only very low proton conductivities were observed, a pronounced increase in catalytic activity was achieved. Although reactions were performed at temperatures of 250 and 300 °C for more than 40 h, no desulfonation and no loss of crystallinity were observed, and stable ethanol conversion resulted. This demonstrates the high stability of this material.