Metal-Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature

Timothy A. Goetjen; Xuan Zhang; Jian Liu; Joseph T. Hupp; Omar K. Farha

doi:10.1021/acssuschemeng.8b05524

Metal-Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature

Timothy A. Goetjen, Xuan Zhang, Jian Liu, Joseph T. Hupp^*, Omar K. Farha

^*Corresponding author for this work

Chemistry

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

66 Scopus citations

Abstract

A chemically and thermally stable, mesoporous, crystalline metal-organic framework, NU-1000, serves as a structurally well-defined support for catalytic reactions. Depositing chromium(III), a metal widely used in homogeneous ethylene oligomerization catalysts, onto the Zr ₆ node of NU-1000 allows for the atomically precise determination of the structure of the Cr ³⁺ catalyst through single-crystal X-ray diffraction studies. Chromium modification of NU-1000 was accomplished via solvothermal deposition in MOFs (SIM); termed Cr-SIM-NU-1000, the elaborated material features individual Cr atoms directed in single-site fashion into the mesopore of NU-1000. It was found that NU-1000 serves to stabilize the catalyst against both the typical chemical deactivation of homogeneous systems and leaching from heterogeneous systems. Cr-SIM-NU-1000 exhibits superior catalytic activity, as compared to Cr ₂ O ₃ , for ethylene oligomerization, with 20% conversion at a turnover frequency of about 60 h ^-1 and products ranging from C ₈ -C ₂₈ . Given that this catalysis occurs at low temperature (ambient) and low pressure (1 bar C ₂ H ₄ ), along with minimal quantity of cocatalyst, the high activity shown by Cr-SIM-NU-1000 enables significant reduction in materials usage and waste. Postcatalytic characterization reveals Cr-SIM-NU-1000 remains intact with no leaching under the reaction conditions.

Original language	English (US)
Pages (from-to)	2553-2557
Number of pages	5
Journal	ACS Sustainable Chemistry and Engineering
Volume	7
Issue number	2
DOIs	https://doi.org/10.1021/acssuschemeng.8b05524
State	Published - Jan 22 2019

Keywords

Ethylene oligomerization
Heterogeneous catalysis
Metal-organic frameworks
Single-crystal

ASJC Scopus subject areas

General Chemistry
Environmental Chemistry
General Chemical Engineering
Renewable Energy, Sustainability and the Environment

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acssuschemeng.8b05524

Cite this

@article{046b594fd6854dd78f8eb6d18b1659fa,

title = "Metal-Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature",

abstract = " A chemically and thermally stable, mesoporous, crystalline metal-organic framework, NU-1000, serves as a structurally well-defined support for catalytic reactions. Depositing chromium(III), a metal widely used in homogeneous ethylene oligomerization catalysts, onto the Zr 6 node of NU-1000 allows for the atomically precise determination of the structure of the Cr 3+ catalyst through single-crystal X-ray diffraction studies. Chromium modification of NU-1000 was accomplished via solvothermal deposition in MOFs (SIM); termed Cr-SIM-NU-1000, the elaborated material features individual Cr atoms directed in single-site fashion into the mesopore of NU-1000. It was found that NU-1000 serves to stabilize the catalyst against both the typical chemical deactivation of homogeneous systems and leaching from heterogeneous systems. Cr-SIM-NU-1000 exhibits superior catalytic activity, as compared to Cr 2 O 3 , for ethylene oligomerization, with 20% conversion at a turnover frequency of about 60 h -1 and products ranging from C 8 -C 28 . Given that this catalysis occurs at low temperature (ambient) and low pressure (1 bar C 2 H 4 ), along with minimal quantity of cocatalyst, the high activity shown by Cr-SIM-NU-1000 enables significant reduction in materials usage and waste. Postcatalytic characterization reveals Cr-SIM-NU-1000 remains intact with no leaching under the reaction conditions. ",

keywords = "Ethylene oligomerization, Heterogeneous catalysis, Metal-organic frameworks, Single-crystal",

author = "Goetjen, {Timothy A.} and Xuan Zhang and Jian Liu and Hupp, {Joseph T.} and Farha, {Omar K.}",

note = "Funding Information: This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0012702). This work made use of the Clean Catalysis facility at Northwestern University, which acknowledges funding from the Department of Energy (DE-SC0001329) used for the purchase of the Parr reactor equipment. This work also made use of the Electron Probe Instrumentation Center (EPIC) and Keck-II facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental Center (NUANCE), 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. This work made use of the IMSERC facility at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); SHyNE Resource (NSF NNCI-1542205); the State of Illinois and IIN. ICP-OES measurements were performed at the North-western University Quantitative Bioelement Imaging Center (QBIC). T.A.G. thanks Prof. Neil Schweitzer, operations director of the core facility Clean Catalysis (CleanCat) at Northwestern University, for his helpful discussions regarding experimental setup. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = jan,

day = "22",

doi = "10.1021/acssuschemeng.8b05524",

language = "English (US)",

volume = "7",

pages = "2553--2557",

journal = "ACS Sustainable Chemistry and Engineering",

issn = "2168-0485",

publisher = "American Chemical Society",

number = "2",

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TY - JOUR

T1 - Metal-Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature

AU - Goetjen, Timothy A.

AU - Zhang, Xuan

AU - Liu, Jian

AU - Hupp, Joseph T.

AU - Farha, Omar K.

N1 - Funding Information: This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0012702). This work made use of the Clean Catalysis facility at Northwestern University, which acknowledges funding from the Department of Energy (DE-SC0001329) used for the purchase of the Parr reactor equipment. This work also made use of the Electron Probe Instrumentation Center (EPIC) and Keck-II facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental Center (NUANCE), 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. This work made use of the IMSERC facility at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); SHyNE Resource (NSF NNCI-1542205); the State of Illinois and IIN. ICP-OES measurements were performed at the North-western University Quantitative Bioelement Imaging Center (QBIC). T.A.G. thanks Prof. Neil Schweitzer, operations director of the core facility Clean Catalysis (CleanCat) at Northwestern University, for his helpful discussions regarding experimental setup. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/1/22

Y1 - 2019/1/22

N2 - A chemically and thermally stable, mesoporous, crystalline metal-organic framework, NU-1000, serves as a structurally well-defined support for catalytic reactions. Depositing chromium(III), a metal widely used in homogeneous ethylene oligomerization catalysts, onto the Zr 6 node of NU-1000 allows for the atomically precise determination of the structure of the Cr 3+ catalyst through single-crystal X-ray diffraction studies. Chromium modification of NU-1000 was accomplished via solvothermal deposition in MOFs (SIM); termed Cr-SIM-NU-1000, the elaborated material features individual Cr atoms directed in single-site fashion into the mesopore of NU-1000. It was found that NU-1000 serves to stabilize the catalyst against both the typical chemical deactivation of homogeneous systems and leaching from heterogeneous systems. Cr-SIM-NU-1000 exhibits superior catalytic activity, as compared to Cr 2 O 3 , for ethylene oligomerization, with 20% conversion at a turnover frequency of about 60 h -1 and products ranging from C 8 -C 28 . Given that this catalysis occurs at low temperature (ambient) and low pressure (1 bar C 2 H 4 ), along with minimal quantity of cocatalyst, the high activity shown by Cr-SIM-NU-1000 enables significant reduction in materials usage and waste. Postcatalytic characterization reveals Cr-SIM-NU-1000 remains intact with no leaching under the reaction conditions.

AB - A chemically and thermally stable, mesoporous, crystalline metal-organic framework, NU-1000, serves as a structurally well-defined support for catalytic reactions. Depositing chromium(III), a metal widely used in homogeneous ethylene oligomerization catalysts, onto the Zr 6 node of NU-1000 allows for the atomically precise determination of the structure of the Cr 3+ catalyst through single-crystal X-ray diffraction studies. Chromium modification of NU-1000 was accomplished via solvothermal deposition in MOFs (SIM); termed Cr-SIM-NU-1000, the elaborated material features individual Cr atoms directed in single-site fashion into the mesopore of NU-1000. It was found that NU-1000 serves to stabilize the catalyst against both the typical chemical deactivation of homogeneous systems and leaching from heterogeneous systems. Cr-SIM-NU-1000 exhibits superior catalytic activity, as compared to Cr 2 O 3 , for ethylene oligomerization, with 20% conversion at a turnover frequency of about 60 h -1 and products ranging from C 8 -C 28 . Given that this catalysis occurs at low temperature (ambient) and low pressure (1 bar C 2 H 4 ), along with minimal quantity of cocatalyst, the high activity shown by Cr-SIM-NU-1000 enables significant reduction in materials usage and waste. Postcatalytic characterization reveals Cr-SIM-NU-1000 remains intact with no leaching under the reaction conditions.

KW - Ethylene oligomerization

KW - Heterogeneous catalysis

KW - Metal-organic frameworks

KW - Single-crystal

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DO - 10.1021/acssuschemeng.8b05524

M3 - Article

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JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

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ER -

Metal-Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

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CCDC 1874677: Experimental Crystal Structure Determination

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Metal-Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1874677: Experimental Crystal Structure Determination

Cite this