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

M. Hassan Beyzavi; Nicolaas A. Vermeulen; Kainan Zhang; Monica So; Chung Wei Kung; Joseph T. Hupp; Omar K. Farha

doi:10.1002/cplu.201600046

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

M. Hassan Beyzavi, Nicolaas A. Vermeulen, Kainan Zhang, Monica So, Chung Wei Kung, Joseph T. Hupp^*, Omar K. Farha

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

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/CO₂insertion 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 CO₂insertion than the bulk crystalline MOF samples.

Original language	English (US)
Pages (from-to)	708-713
Number of pages	6
Journal	ChemPlusChem
Volume	81
Issue number	8
DOIs	https://doi.org/10.1002/cplu.201600046
State	Published - Aug 1 2016

Keywords

cyclic carbonates
epoxidation
liquid-phase epitaxy
metal–organic frameworks
tandem catalysis

ASJC Scopus subject areas

General Chemistry

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10.1002/cplu.201600046

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

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/CO2insertion 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 CO2insertion than the bulk crystalline MOF samples.",

keywords = "cyclic carbonates, epoxidation, liquid-phase epitaxy, metal–organic frameworks, tandem catalysis",

author = "Beyzavi, {M. Hassan} and Vermeulen, {Nicolaas A.} and Kainan Zhang and Monica So and Kung, {Chung Wei} and Hupp, {Joseph T.} and Farha, {Omar K.}",

note = "Funding Information: We gratefully acknowledge funding from the Army Research Office (project number W911NF-13-1-0229). Contributions by O.K.F. to this project were funded by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah, under grant no. 23-130-36-HiCi. M.C.S. thanks the Bill and Melinda Gates Foundation for support as a Gates Millennial Scholar. We thank Dr. Ben Klahr for the ellipsometry measurements. M.H.B thanks the DFG for a Postdoctoral Research Fellowship Award. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

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doi = "10.1002/cplu.201600046",

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AU - Beyzavi, M. Hassan

AU - Vermeulen, Nicolaas A.

AU - Zhang, Kainan

AU - So, Monica

AU - Kung, Chung Wei

AU - Hupp, Joseph T.

AU - Farha, Omar K.

N1 - Funding Information: We gratefully acknowledge funding from the Army Research Office (project number W911NF-13-1-0229). Contributions by O.K.F. to this project were funded by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah, under grant no. 23-130-36-HiCi. M.C.S. thanks the Bill and Melinda Gates Foundation for support as a Gates Millennial Scholar. We thank Dr. Ben Klahr for the ellipsometry measurements. M.H.B thanks the DFG for a Postdoctoral Research Fellowship Award. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2016/8/1

Y1 - 2016/8/1

N2 - 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/CO2insertion 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 CO2insertion than the bulk crystalline MOF samples.

AB - 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/CO2insertion 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 CO2insertion than the bulk crystalline MOF samples.

KW - cyclic carbonates

KW - epoxidation

KW - liquid-phase epitaxy

KW - metal–organic frameworks

KW - tandem catalysis

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

Abstract

Keywords

ASJC Scopus subject areas

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