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Liquid‐Phase Epitaxially Grown Metal–Organic Framework Thin Films for Efficient Tandem Catalysis Through Site‐Isolation of Catalytic Centers
Author(s) -
Beyzavi M. Hassan,
Vermeulen Nicolaas A.,
Zhang Kainan,
So Monica,
Kung ChungWei,
Hupp Joseph T.,
Farha Omar K.
Publication year - 2016
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201600046
Subject(s) - catalysis , tandem , metal organic framework , epitaxy , substrate (aquarium) , materials science , porphyrin , epoxide , monolayer , olefin fiber , layer (electronics) , silicon , phase (matter) , styrene , chemical engineering , combinatorial chemistry , chemistry , nanotechnology , photochemistry , organic chemistry , copolymer , optoelectronics , composite material , oceanography , polymer , adsorption , geology , engineering
Abstract 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/CO 2 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 CO 2 insertion than the bulk crystalline MOF samples.