Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst
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 detai...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/128212 |
| _version_ | 1826215873047691264 |
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| author | Metzger, Eric Daniel Comito, Robert J Wu, Zhenwei Zhang, Guanghui Dubey, Romain Xu, Wei Miller, Jeffrey T. Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Metzger, Eric Daniel Comito, Robert J Wu, Zhenwei Zhang, Guanghui Dubey, Romain Xu, Wei Miller, Jeffrey T. Dinca, Mircea |
| author_sort | Metzger, Eric Daniel |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T16:38:23Z |
| format | Article |
| id | mit-1721.1/128212 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T16:38:23Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1282122022-10-03T07:19:54Z Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst Metzger, Eric Daniel Comito, Robert J Wu, Zhenwei Zhang, Guanghui Dubey, Romain Xu, Wei Miller, Jeffrey T. Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry 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. 2020-10-26T21:22:50Z 2020-10-26T21:22:50Z 2019-03 2019-03 2020-10-21T15:25:06Z Article http://purl.org/eprint/type/JournalArticle 2168-0485 2168-0485 https://hdl.handle.net/1721.1/128212 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 en http://dx.doi.org/10.1021/acssuschemeng.8b05703 ACS Sustainable Chemistry & Engineering 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. application/pdf American Chemical Society (ACS) Prof. Dinca via Ye Li |
| spellingShingle | Metzger, Eric Daniel Comito, Robert J Wu, Zhenwei Zhang, Guanghui Dubey, Romain Xu, Wei Miller, Jeffrey T. Dinca, Mircea Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst |
| title | Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst |
| title_full | Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst |
| title_fullStr | Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst |
| title_full_unstemmed | Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst |
| title_short | Highly Selective Heterogeneous Ethylene Dimerization with a Scalable and Chemically Robust MOF Catalyst |
| title_sort | highly selective heterogeneous ethylene dimerization with a scalable and chemically robust mof catalyst |
| url | https://hdl.handle.net/1721.1/128212 |
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