MOF-Based Catalysts for Selective Hydrogenolysis of Carbon–Oxygen Ether Bonds

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• 作者：Vitalie Stavila ; Ramakrishnan Parthasarathi ; Ryan W. Davis ; Farid El Gabaly ; Kenneth L. Sale ; Blake A. Simmons ; Seema Singh ; Mark D. Allendorf
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：6
• 期：1
• 页码：55-59
• 全文大小：330K
• ISSN：2155-5435

文摘

We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H₂ and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg²⁺ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.