CO[subscript 2] hydrogenation to formic acid on Ni(111)
Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO[subscript 2] hydrogenation on Ni(111). CO[subscript 2] hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically, and the respective microscopic re...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2015
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| Online Access: | http://hdl.handle.net/1721.1/95962 https://orcid.org/0000-0002-9989-6622 |
| _version_ | 1826200136562245632 |
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| author | Peng, Guowen Sibener, S. J. Schatz, George C. Mavrikakis, Manos Ceyer, Sylvia |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Peng, Guowen Sibener, S. J. Schatz, George C. Mavrikakis, Manos Ceyer, Sylvia |
| author_sort | Peng, Guowen |
| collection | MIT |
| description | Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO[subscript 2] hydrogenation on Ni(111). CO[subscript 2] hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically, and the respective microscopic reaction mechanisms are elucidated. We show that on Ni(111) CO[subscript 2] hydrogenation to formate intermediate is more favorable than to carboxyl intermediate. The hydrogenation to formate goes through the unidentate structure that rapidly transforms into the bidentate structure. Further hydrogenation from formate to formic acid is energetically more difficult than formate formation. Formation of adsorbed formic acid from adsorbed CO[subscript 2] and surface hydrogen is an endothermic reaction. Because subsurface H in Ni(111) is substantially less stable compared to surface H, its reaction with adsorbed CO[subscript 2] to adsorbed formic acid is an exothermic one. Our results may have significant implications for the synthesis of liquid fuels from CO[subscript 2] and for catalytic hydrogenation reactions in general. |
| first_indexed | 2024-09-23T11:31:45Z |
| format | Article |
| id | mit-1721.1/95962 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:31:45Z |
| publishDate | 2015 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/959622022-10-01T04:11:19Z CO[subscript 2] hydrogenation to formic acid on Ni(111) Peng, Guowen Sibener, S. J. Schatz, George C. Mavrikakis, Manos Ceyer, Sylvia Massachusetts Institute of Technology. Department of Chemistry Ceyer, Sylvia Ceyer, Sylvia Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO[subscript 2] hydrogenation on Ni(111). CO[subscript 2] hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically, and the respective microscopic reaction mechanisms are elucidated. We show that on Ni(111) CO[subscript 2] hydrogenation to formate intermediate is more favorable than to carboxyl intermediate. The hydrogenation to formate goes through the unidentate structure that rapidly transforms into the bidentate structure. Further hydrogenation from formate to formic acid is energetically more difficult than formate formation. Formation of adsorbed formic acid from adsorbed CO[subscript 2] and surface hydrogen is an endothermic reaction. Because subsurface H in Ni(111) is substantially less stable compared to surface H, its reaction with adsorbed CO[subscript 2] to adsorbed formic acid is an exothermic one. Our results may have significant implications for the synthesis of liquid fuels from CO[subscript 2] and for catalytic hydrogenation reactions in general. National Science Foundation (U.S.) (Center for Energetic Non-Equilibrium Chemistry at Interfaces. Grant 0943639) United States. Dept. of Energy. Office of Biological and Environmental Research United States. Dept. of Energy. Office of Science (Contract DE-AC02-06CH11357) United States. Dept. of Energy. Office of Science (Contract DEAC05-00OR22725) United States. Dept. of Energy. Office of Science (Contract AC02-05CH11231) 2015-03-11T19:43:59Z 2015-03-11T19:43:59Z 2011-12 2011-12 Article http://purl.org/eprint/type/JournalArticle 1932-7447 1932-7455 http://hdl.handle.net/1721.1/95962 Peng, Guowen, S. J. Sibener, George C. Schatz, Sylvia T. Ceyer, and Manos Mavrikakis. “ CO[subscript 2] Hydrogenation to Formic Acid on Ni(111) .” The Journal of Physical Chemistry C 116, no. 4 (February 2, 2012): 3001–3006. https://orcid.org/0000-0002-9989-6622 en_US http://dx.doi.org/10.1021/jp210408x Journal of Physical Chemistry C 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) Ceyer |
| spellingShingle | Peng, Guowen Sibener, S. J. Schatz, George C. Mavrikakis, Manos Ceyer, Sylvia CO[subscript 2] hydrogenation to formic acid on Ni(111) |
| title | CO[subscript 2] hydrogenation to formic acid on Ni(111) |
| title_full | CO[subscript 2] hydrogenation to formic acid on Ni(111) |
| title_fullStr | CO[subscript 2] hydrogenation to formic acid on Ni(111) |
| title_full_unstemmed | CO[subscript 2] hydrogenation to formic acid on Ni(111) |
| title_short | CO[subscript 2] hydrogenation to formic acid on Ni(111) |
| title_sort | co subscript 2 hydrogenation to formic acid on ni 111 |
| url | http://hdl.handle.net/1721.1/95962 https://orcid.org/0000-0002-9989-6622 |
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