Computational demystification of iron carbonyls formation under syngas environment
<p dir="ltr">Iron pentacarbonyl (IPC) gas forms upon the reaction of carbon monoxide with Fe containing metallic surfaces under gas reforming conditions. IPC formation can sometimes reach alarming levels that cause metal loss, pipeline thinning corrosion, catalyst poisoning, and cont...
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| مؤلفون آخرون: | , , , , , |
| منشور في: |
2024
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إضافة وسم
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| _version_ | 1864513509345198080 |
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| author | El Tayeb Bentria (9904024) |
| author2 | Prathamesh Mahesh Shenai (17978848) Stefano Sanvito (1294110) Heesoo Park (1604989) Laurent Karim Béland (19326088) Nicholas Laycock (17150956) Fedwa El Mellouhi (18513243) |
| author2_role | author author author author author author |
| author_facet | El Tayeb Bentria (9904024) Prathamesh Mahesh Shenai (17978848) Stefano Sanvito (1294110) Heesoo Park (1604989) Laurent Karim Béland (19326088) Nicholas Laycock (17150956) Fedwa El Mellouhi (18513243) |
| author_role | author |
| dc.creator.none.fl_str_mv | El Tayeb Bentria (9904024) Prathamesh Mahesh Shenai (17978848) Stefano Sanvito (1294110) Heesoo Park (1604989) Laurent Karim Béland (19326088) Nicholas Laycock (17150956) Fedwa El Mellouhi (18513243) |
| dc.date.none.fl_str_mv | 2024-02-16T12:00:00Z |
| dc.identifier.none.fl_str_mv | 10.1038/s41529-024-00429-x |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/journal_contribution/Computational_demystification_of_iron_carbonyls_formation_under_syngas_environment/26491198 |
| dc.rights.none.fl_str_mv | CC BY 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Engineering Chemical engineering Materials engineering Iron Pentacarbonyl (IPC) Carbon Monoxide (CO) Fe Containing Metallic Surfaces Gas Reforming Conditions Catalytic Reactions Density Functional Theory (DFT) Computational Modeling |
| dc.title.none.fl_str_mv | Computational demystification of iron carbonyls formation under syngas environment |
| dc.type.none.fl_str_mv | Text Journal contribution info:eu-repo/semantics/publishedVersion text contribution to journal |
| description | <p dir="ltr">Iron pentacarbonyl (IPC) gas forms upon the reaction of carbon monoxide with Fe containing metallic surfaces under gas reforming conditions. IPC formation can sometimes reach alarming levels that cause metal loss, pipeline thinning corrosion, catalyst poisoning, and contamination of sensitive industrial equipment. In this work, we demystify using multiscale computational modeling the mechanism of Iron pentacarbonyl formation: Density functional theory (DFT) is used to explore various catalytic reactions that involve a Fe adatom reacting with adsorbed carbon monoxide. Our calculated carbonyls desorption barriers on a perfect and clean Fe surface are too high to allow the carbonyls to form then desorb at temperatures <500 K at the rates reported experimentally. Most importantly, our calculations indicate that a high CO surface coverage, in addition to the presence of Fe adatoms, favors carbonyl formation and its desorption towards the flowing gas medium. Using insights extracted from ab initio molecular dynamics simulations, we propose that the most plausible IPC formation mechanism consists of: (1) on surface reactions of adsorbed CO molecules with an Fe adatom to form iron tricarbonyl (Fe(CO)<sub>3</sub>*) molecules; (2) an adsorbate assisted movement of iron tricarbonyl on top of the CO adlayer; and (3) the interaction of iron tricarbonyl with CO molecules from the gaseous medium eventually leading to iron adatom removal as Fe(CO)<sub>5</sub> gas.</p><h2>Other Information</h2><p dir="ltr">Published in: npj Materials Degradation<br>License: <a href="https://creativecommons.org/licenses/by/4.0" target="_blank">https://creativecommons.org/licenses/by/4.0</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1038/s41529-024-00429-x" target="_blank">https://dx.doi.org/10.1038/s41529-024-00429-x</a></p> |
| eu_rights_str_mv | openAccess |
| id | Manara2_a336a16a6f362365d409f95d5b6b7170 |
| identifier_str_mv | 10.1038/s41529-024-00429-x |
| network_acronym_str | Manara2 |
| network_name_str | Manara2 |
| oai_identifier_str | oai:figshare.com:article/26491198 |
| publishDate | 2024 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY 4.0 |
| spelling | Computational demystification of iron carbonyls formation under syngas environmentEl Tayeb Bentria (9904024)Prathamesh Mahesh Shenai (17978848)Stefano Sanvito (1294110)Heesoo Park (1604989)Laurent Karim Béland (19326088)Nicholas Laycock (17150956)Fedwa El Mellouhi (18513243)EngineeringChemical engineeringMaterials engineeringIron Pentacarbonyl (IPC)Carbon Monoxide (CO)Fe Containing Metallic SurfacesGas Reforming ConditionsCatalytic ReactionsDensity Functional Theory (DFT)Computational Modeling<p dir="ltr">Iron pentacarbonyl (IPC) gas forms upon the reaction of carbon monoxide with Fe containing metallic surfaces under gas reforming conditions. IPC formation can sometimes reach alarming levels that cause metal loss, pipeline thinning corrosion, catalyst poisoning, and contamination of sensitive industrial equipment. In this work, we demystify using multiscale computational modeling the mechanism of Iron pentacarbonyl formation: Density functional theory (DFT) is used to explore various catalytic reactions that involve a Fe adatom reacting with adsorbed carbon monoxide. Our calculated carbonyls desorption barriers on a perfect and clean Fe surface are too high to allow the carbonyls to form then desorb at temperatures <500 K at the rates reported experimentally. Most importantly, our calculations indicate that a high CO surface coverage, in addition to the presence of Fe adatoms, favors carbonyl formation and its desorption towards the flowing gas medium. Using insights extracted from ab initio molecular dynamics simulations, we propose that the most plausible IPC formation mechanism consists of: (1) on surface reactions of adsorbed CO molecules with an Fe adatom to form iron tricarbonyl (Fe(CO)<sub>3</sub>*) molecules; (2) an adsorbate assisted movement of iron tricarbonyl on top of the CO adlayer; and (3) the interaction of iron tricarbonyl with CO molecules from the gaseous medium eventually leading to iron adatom removal as Fe(CO)<sub>5</sub> gas.</p><h2>Other Information</h2><p dir="ltr">Published in: npj Materials Degradation<br>License: <a href="https://creativecommons.org/licenses/by/4.0" target="_blank">https://creativecommons.org/licenses/by/4.0</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1038/s41529-024-00429-x" target="_blank">https://dx.doi.org/10.1038/s41529-024-00429-x</a></p>2024-02-16T12:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1038/s41529-024-00429-xhttps://figshare.com/articles/journal_contribution/Computational_demystification_of_iron_carbonyls_formation_under_syngas_environment/26491198CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/264911982024-02-16T12:00:00Z |
| spellingShingle | Computational demystification of iron carbonyls formation under syngas environment El Tayeb Bentria (9904024) Engineering Chemical engineering Materials engineering Iron Pentacarbonyl (IPC) Carbon Monoxide (CO) Fe Containing Metallic Surfaces Gas Reforming Conditions Catalytic Reactions Density Functional Theory (DFT) Computational Modeling |
| status_str | publishedVersion |
| title | Computational demystification of iron carbonyls formation under syngas environment |
| title_full | Computational demystification of iron carbonyls formation under syngas environment |
| title_fullStr | Computational demystification of iron carbonyls formation under syngas environment |
| title_full_unstemmed | Computational demystification of iron carbonyls formation under syngas environment |
| title_short | Computational demystification of iron carbonyls formation under syngas environment |
| title_sort | Computational demystification of iron carbonyls formation under syngas environment |
| topic | Engineering Chemical engineering Materials engineering Iron Pentacarbonyl (IPC) Carbon Monoxide (CO) Fe Containing Metallic Surfaces Gas Reforming Conditions Catalytic Reactions Density Functional Theory (DFT) Computational Modeling |