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Title: Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst

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. In this paper, we report detailed X-ray absorption spectroscopy studies of Co- and Ni-MFU-4$$l$$, 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.

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [1];  [3];  [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
Saudi Aramco; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1601882
Grant/Contract Number:  
DMR-1452612; EEC-1647722; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ethylene dimerization; catalyst deactivation; heterogeneous catalysis; catalyst lifetime; X-ray absorption spectroscopy

Citation Formats

Metzger, Eric D., Comito, Robert J., Wu, Zhenwei, Zhang, Guanghui, Dubey, Romain C., Xu, Wei, Miller, Jeffrey T., and Dincă, Mircea. Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst. United States: N. p., 2019. Web. doi:10.1021/acssuschemeng.8b05703.
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Metzger, Eric D., Comito, Robert J., Wu, Zhenwei, Zhang, Guanghui, Dubey, Romain C., Xu, Wei, Miller, Jeffrey T., & Dincă, Mircea. Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst. United States. https://doi.org/10.1021/acssuschemeng.8b05703
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Metzger, Eric D., Comito, Robert J., Wu, Zhenwei, Zhang, Guanghui, Dubey, Romain C., Xu, Wei, Miller, Jeffrey T., and Dincă, Mircea. Tue . "Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst". United States. https://doi.org/10.1021/acssuschemeng.8b05703. https://www.osti.gov/servlets/purl/1601882.
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@article{osti_1601882,
title = {Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst},
author = {Metzger, Eric D. and Comito, Robert J. and Wu, Zhenwei and Zhang, Guanghui and Dubey, Romain C. and Xu, Wei and Miller, Jeffrey T. and Dincă, Mircea},
abstractNote = {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. In this paper, we report detailed X-ray absorption spectroscopy studies of Co- and Ni-MFU-4$l$, 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.},
doi = {10.1021/acssuschemeng.8b05703},
journal = {ACS Sustainable Chemistry & Engineering},
number = 7,
volume = 7,
place = {United States},
year = {Tue Mar 05 00:00:00 EST 2019},
month = {Tue Mar 05 00:00:00 EST 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acssuschemeng.8b05703
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Figures / Tables:

Figure 1 Figure 1: A) Related Ni2+ and Co2+ sites in 1 and 2 respectively. B) Ni2+ site in 3. C) Three-dimensional structure of 3. Extra-framework anions were removed for clarity.
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