Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal-Organic Frameworks

Ken Ichi Otake; Sol Ahn; Julia Knapp; Joseph T. Hupp; Justin M. Notestein; Omar K. Farha

doi:10.1021/acs.inorgchem.0c03364

Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal-Organic Frameworks

Ken Ichi Otake, Sol Ahn, Julia Knapp, Joseph T. Hupp, Justin M. Notestein, Omar K. Farha^*

^*Corresponding author for this work

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

20 Scopus citations

Abstract

Heterogeneous catalysts supported on metal-organic frameworks (MOFs), which possess uniform porosity and crystallinity, have attracted significant interest for recent years due to the ease of active-site characterization via X-ray diffraction and the subsequent relation of the active site structure to the catalytic activity. We report the syntheses, structures, and oxidation catalytic activities of single-ion iron catalysts incorporated into the zirconium MOF NU-1000. Single-ion iron catalysts with different counteranions were anchored onto the Zr node through postsynthetic solvothermal deposition. Crystallographic characterization of the resulting MOFs (NU-1000-Fe-Cl and NU-1000-Fe-NO3) revealed that, while both frameworks have similar Fe coordination, the distance between Fe and the Zr6 node differs significantly between the two. The product rate profiles of the two catalysts for vapor-phase cyclohexene epoxidation demonstrate different initial rates and product formations, likely originating from the different Fe-O distances.

Original language	English (US)
Pages (from-to)	2457-2463
Number of pages	7
Journal	Inorganic chemistry
Volume	60
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.0c03364
State	Published - Feb 15 2021

Funding

The authors gratefully acknowledge the Northwestern University Institute for Catalysis in Energy Processes (ICEP), funded by the DOE, Office of Basic Energy Sciences (award number DE-FG02-03ER15457), for the synthesis of the catalysts. K.O. acknowledges Early-Career Scientists (JP19K15584) from the Japan Society of the Promotion of Science for financial support. S.A. acknowledges financial support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702), for the catalysis part. This work made use of the IMSERC X-ray facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Also, this work made use of the Keck-II facility of Northwestern University\u2019s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. MOFkey: Zr.HVCDAMXLLUJLQZ.MOFkey-v1.csq ( NU-1000 ).

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.inorgchem.0c03364

Cite this

@article{277f8764642c45e48fb0d9114fe63542,

title = "Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal-Organic Frameworks",

abstract = "Heterogeneous catalysts supported on metal-organic frameworks (MOFs), which possess uniform porosity and crystallinity, have attracted significant interest for recent years due to the ease of active-site characterization via X-ray diffraction and the subsequent relation of the active site structure to the catalytic activity. We report the syntheses, structures, and oxidation catalytic activities of single-ion iron catalysts incorporated into the zirconium MOF NU-1000. Single-ion iron catalysts with different counteranions were anchored onto the Zr node through postsynthetic solvothermal deposition. Crystallographic characterization of the resulting MOFs (NU-1000-Fe-Cl and NU-1000-Fe-NO3) revealed that, while both frameworks have similar Fe coordination, the distance between Fe and the Zr6 node differs significantly between the two. The product rate profiles of the two catalysts for vapor-phase cyclohexene epoxidation demonstrate different initial rates and product formations, likely originating from the different Fe-O distances.",

author = "Otake, {Ken Ichi} and Sol Ahn and Julia Knapp and Hupp, {Joseph T.} and Notestein, {Justin M.} and Farha, {Omar K.}",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = feb,

day = "15",

doi = "10.1021/acs.inorgchem.0c03364",

language = "English (US)",

volume = "60",

pages = "2457--2463",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal-Organic Frameworks

AU - Otake, Ken Ichi

AU - Ahn, Sol

AU - Knapp, Julia

AU - Hupp, Joseph T.

AU - Notestein, Justin M.

AU - Farha, Omar K.

PY - 2021/2/15

Y1 - 2021/2/15

N2 - Heterogeneous catalysts supported on metal-organic frameworks (MOFs), which possess uniform porosity and crystallinity, have attracted significant interest for recent years due to the ease of active-site characterization via X-ray diffraction and the subsequent relation of the active site structure to the catalytic activity. We report the syntheses, structures, and oxidation catalytic activities of single-ion iron catalysts incorporated into the zirconium MOF NU-1000. Single-ion iron catalysts with different counteranions were anchored onto the Zr node through postsynthetic solvothermal deposition. Crystallographic characterization of the resulting MOFs (NU-1000-Fe-Cl and NU-1000-Fe-NO3) revealed that, while both frameworks have similar Fe coordination, the distance between Fe and the Zr6 node differs significantly between the two. The product rate profiles of the two catalysts for vapor-phase cyclohexene epoxidation demonstrate different initial rates and product formations, likely originating from the different Fe-O distances.

AB - Heterogeneous catalysts supported on metal-organic frameworks (MOFs), which possess uniform porosity and crystallinity, have attracted significant interest for recent years due to the ease of active-site characterization via X-ray diffraction and the subsequent relation of the active site structure to the catalytic activity. We report the syntheses, structures, and oxidation catalytic activities of single-ion iron catalysts incorporated into the zirconium MOF NU-1000. Single-ion iron catalysts with different counteranions were anchored onto the Zr node through postsynthetic solvothermal deposition. Crystallographic characterization of the resulting MOFs (NU-1000-Fe-Cl and NU-1000-Fe-NO3) revealed that, while both frameworks have similar Fe coordination, the distance between Fe and the Zr6 node differs significantly between the two. The product rate profiles of the two catalysts for vapor-phase cyclohexene epoxidation demonstrate different initial rates and product formations, likely originating from the different Fe-O distances.

UR - http://www.scopus.com/inward/record.url?scp=85100772601&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85100772601&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.0c03364

DO - 10.1021/acs.inorgchem.0c03364

M3 - Article

C2 - 33497212

AN - SCOPUS:85100772601

SN - 0020-1669

VL - 60

SP - 2457

EP - 2463

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 4

ER -

Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal-Organic Frameworks

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 2036844: Experimental Crystal Structure Determination

CCDC 2036845: Experimental Crystal Structure Determination

Cite this

Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal-Organic Frameworks

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2036844: Experimental Crystal Structure Determination

CCDC 2036845: Experimental Crystal Structure Determination

Cite this