Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst
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acssuschemeng.8b05703.pdf
Description
Accepted version
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2.49 MB
Format
Adobe PDF
Checksum (MD5)
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Author(s)
Metzger, Eric Daniel
Comito, Robert J
Wu, Zhenwei
Zhang, Guanghui
Dubey, Romain
Xu, Wei
Miller, Jeffrey T.
Dinca, Mircea
Date Issued
March 2019
Journal
ACS Sustainable Chemistry & Engineering
Publisher
American Chemical Society (ACS)
Citation
Metzger, Eric D. et al. "Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst." ACS Sustainable Chemistry & Engineering 7, 7 (March 2019): 6654–6661 © 2019 American Chemical Society
Version
Author's final manuscript
Abstract
Metal-organic frameworks (MOFs) hold great promise as structurally tunable catalysts capable of high selectivity in the solid state, yet their comparatively high cost and often limited stability remain significant concerns for their commercialization as heterogeneous catalysts. Here, we report detailed X-ray absorption spectroscopy studies of Co- and Ni-MFU-4l, a class of highly selective MOF catalysts for olefin upgrading, and reveal mechanisms that lead to their deactivation. We further show that Ni-CFA-1, a more scalable and economical alternative to Ni-MFU-4l, reproduces both the local coordination structure and the high selectivity of the latter in ethylene dimerization catalysis. Under optimal conditions, Ni-CFA-1 activated by MMAO-12 achieves a turnover frequency of 37100 per hour and a selectivity of 87.1% for 1-butene, a combination of activity, selectivity, and affordability that is unmatched among heterogeneous ethylene dimerization catalysts. Ni-CFA-1 retains its high activity for at least 12 h in a one-liter semibatch reactor, offering a strategy toward robust and scalable MOFs for industrial catalysis.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1021/acssuschemeng.8b05703
