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A Crystalline Catalyst Based on a Porous Metal‐Organic Framework and 12‐Tungstosilicic Acid: Particle Size Control by Hydrothermal Synthesis for the Formation of Dimethyl Ether
Authors:Da‐Dong Liang  Shu‐Xia Liu  Feng‐Ji Ma  Feng Wei  Ya‐Guang Chen
Abstract:The strategy for obtaining a crystalline catalyst based on a porous copper‐based metal‐organic framework and 12‐tungstosilicic acid with different particle sizes is reported. Through the control of hydrothermal synthesis and some simple treatments, catalyst samples with average particle diameters of 23, 105, and 450 μm, respectively, were prepared. This crystal catalyst has both the Brønsted acidity of 12‐tungstosilicic acid and the Lewis acidity of the copper‐based metal‐organic framework, and has high density of accessible acid sites. Its catalytic activity was fully assessed in the dehydration of methanol to dimethyl ether. The effect of particle size on the catalytic activity of catalyst was studied, in order to select the particle size appropriate for avoiding the diffusion limitation in heterogeneous gas‐phase catalysis. In the selective dehydration of methanol to dimethyl ether, this catalyst exhibited higher catalytic activity than the copper‐based metal‐organic framework, γ‐alumina, and γ‐alumina‐supported 12‐tungstosilicic acid catalysts. It showed high catalytic performances, even at higher space velocity or in the presence of excess water. In addition, the catalyst was also preliminarily assessed in the formation of ethyl acetate from acetic acid and ethylene. It also exhibited a high activity which was comparable with that of silica‐supported 12‐tungstosilicic acid catalyst.
Keywords:dimethyl ether  ethyl acetate  heterogeneous catalysis  polyoxometalates  porous metal‐organic frameworks
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