Liquid-Phase Epitaxially Grown Metal-Organic Framework Thin Films for Efficient Tandem Catalysis Through Site-Isolation of Catalytic Centers

详细信息    查看全文

• 作者：Dr. M. Hassan Beyzavi ; Dr. Nicolaas A. Vermeulen ; Dr. Kainan Zhang ; Prof. Monica So ; Chung-Wei Kung ; Prof. Joseph T. Hupp and Prof. Omar K. Farha
• 刊名：ChemPlusChem
• 出版年：2016
• 出版时间：August 2016
• 年：2016
• 卷：81
• 期：8
• 页码：708-713
• 全文大小：1674K
• ISSN：2192-6506

文摘

A functional metal–organic framework (MOF) composed of robust porphyrinic material (RPM) based on the pillared-paddlewheel topology is prepared with large 3 D channels, and is used to perform a tandem epoxidation/CO₂ insertion reaction. The designated system benefits from two metalloporphyrins: 1) a Mn-porphyrin, which catalyzes the epoxidation of an olefin substrate, and 2) a Zn-porphyrin, which catalyzes the epoxide opening. By using an automated liquid-phase epitaxial growth system, the RPM-MOF is also prepared in layer-by-layer fashion as an ultrathin film on a self-assembled-monolayer-coated silicon platform. Deployed as a tandem catalyst, the film version yields a substantially higher catalytic turnover number for tandem methoxy-styrene epoxidation followed by CO₂ insertion than the bulk crystalline MOF samples.