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Vanadium Catalyst on Isostructural Transition Metal, Lanthanide, and Actinide Based Metal–Organic Frameworks for Alcohol Oxidation

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journal contribution
posted on 13.05.2019, 20:29 by Xingjie Wang, Xuan Zhang, Peng Li, Ken-ichi Otake, Yuexing Cui, Jiafei Lyu, Matthew D. Krzyaniak, Yuanyuan Zhang, Zhanyong Li, Jian Liu, Cassandra T. Buru, Timur Islamoglu, Michael R. Wasielewski, Zhong Li, Omar K. Farha
The understanding of the catalyst–support interactions has been an important challenge in heterogeneous catalysis since the supports can play a vital role in controlling the properties of the active species and hence their catalytic performance. Herein, a series of isostructural mesoporous metal–organic frameworks (MOFs) based on transition metals, lanthanides, and actinides (Zr, Hf, Ce, Th) were investigated as supports for a vanadium catalyst. The vanadium species was coordinated to the oxo groups of the MOF node in a single-ion fashion, as determined by single-crystal X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, and diffuse reflectance UV–vis spectroscopy. The support effects of these isostructural MOFs were then probed using the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The turnover frequency was found to be correlated with the electronegativity and oxidation state of the metal cations on the supporting MOF nodes, highlighting an important consideration when designing catalyst supports.