Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst
Current heterogeneous catalysts lack the fine steric and electronic tuning required for catalyzing the selective dimerization of ethylene to 1-butene, which remains one of the largest industrial processes still catalyzed by homogeneous catalysts. Here, we report that a metal–organic framework cataly...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2017
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| Online Access: | http://hdl.handle.net/1721.1/110550 https://orcid.org/0000-0001-6597-1981 https://orcid.org/0000-0003-1298-2876 https://orcid.org/0000-0002-1262-1264 |
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| author | Metzger, Eric Daniel Brozek, Carl Kavanaugh Comito, Robert J Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Metzger, Eric Daniel Brozek, Carl Kavanaugh Comito, Robert J Dinca, Mircea |
| author_sort | Metzger, Eric Daniel |
| collection | MIT |
| description | Current heterogeneous catalysts lack the fine steric and electronic tuning required for catalyzing the selective dimerization of ethylene to 1-butene, which remains one of the largest industrial processes still catalyzed by homogeneous catalysts. Here, we report that a metal–organic framework catalyzes ethylene dimerization with a combination of activity and selectivity for 1-butene that is premier among heterogeneous catalysts. The capacity for mild cation exchange in the material MFU-4l (MFU-4l = Zn[subscript 5]Cl[subscript 4](BTDD)[subscript 3], H[subscript 2]BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin) was leveraged to create a well-defined and site-isolated Ni(II) active site bearing close structural homology to molecular tris-pyrazolylborate complexes. In the presence of ethylene and methylaluminoxane, the material consumes ethylene at a rate of 41,500 mol per mole of Ni per hour with a selectivity for 1-butene of up to 96.2%, exceeding the selectivity reported for the current industrial dimerization process. |
| first_indexed | 2024-09-23T13:26:56Z |
| format | Article |
| id | mit-1721.1/110550 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:26:56Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1105502022-10-01T15:22:51Z Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst Metzger, Eric Daniel Brozek, Carl Kavanaugh Comito, Robert J Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry Metzger, Eric Daniel Brozek, Carl Kavanaugh Comito, Robert J Dinca, Mircea Current heterogeneous catalysts lack the fine steric and electronic tuning required for catalyzing the selective dimerization of ethylene to 1-butene, which remains one of the largest industrial processes still catalyzed by homogeneous catalysts. Here, we report that a metal–organic framework catalyzes ethylene dimerization with a combination of activity and selectivity for 1-butene that is premier among heterogeneous catalysts. The capacity for mild cation exchange in the material MFU-4l (MFU-4l = Zn[subscript 5]Cl[subscript 4](BTDD)[subscript 3], H[subscript 2]BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin) was leveraged to create a well-defined and site-isolated Ni(II) active site bearing close structural homology to molecular tris-pyrazolylborate complexes. In the presence of ethylene and methylaluminoxane, the material consumes ethylene at a rate of 41,500 mol per mole of Ni per hour with a selectivity for 1-butene of up to 96.2%, exceeding the selectivity reported for the current industrial dimerization process. Saudi Aramco American Society for Engineering Education. National Defense Science and Engineering Graduate Fellowship 3M Company Research Corporation for Science Advancement. Cottrell Scholars Program Alfred P. Sloan Foundation 2017-07-07T18:13:53Z 2017-07-07T18:13:53Z 2016-02 2016-01 Article http://purl.org/eprint/type/JournalArticle 2374-7943 2374-7951 http://hdl.handle.net/1721.1/110550 Metzger, Eric D. et al. “Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst.” ACS Central Science 2.3 (2016): 148–153. © 2016 American Chemical Society https://orcid.org/0000-0001-6597-1981 https://orcid.org/0000-0003-1298-2876 https://orcid.org/0000-0002-1262-1264 en_US http://dx.doi.org/10.1021/acscentsci.6b00012 ACS Central Science 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) ACS |
| spellingShingle | Metzger, Eric Daniel Brozek, Carl Kavanaugh Comito, Robert J Dinca, Mircea Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst |
| title | Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst |
| title_full | Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst |
| title_fullStr | Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst |
| title_full_unstemmed | Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst |
| title_short | Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst |
| title_sort | selective dimerization of ethylene to 1 butene with a porous catalyst |
| url | http://hdl.handle.net/1721.1/110550 https://orcid.org/0000-0001-6597-1981 https://orcid.org/0000-0003-1298-2876 https://orcid.org/0000-0002-1262-1264 |
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