The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis
Abstract Cobalt is an efficient catalyst for Fischer−Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H2) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental...
Saved in:
| Main Authors: | , , , , , , , , , , , , , , , , , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2024-11-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54578-3 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832585547664588800 |
|---|---|
| author | Hao Chen Zan Lian Xiao Zhao Jiawei Wan Priscilla F. Pieters Judit Oliver-Meseguer Ji Yang Elzbieta Pach Sophie Carenco Laureline Treps Nikos Liakakos Yu Shan Virginia Altoe Ed Wong Zengqing Zhuo Feipeng Yang Ji Su Jinghua Guo Monika Blum Saul H. Lapidus Adrian Hunt Iradwikanari Waluyo Hirohito Ogasawara Haimei Zheng Peidong Yang Alexis T. Bell Núria López Miquel Salmeron |
| author_facet | Hao Chen Zan Lian Xiao Zhao Jiawei Wan Priscilla F. Pieters Judit Oliver-Meseguer Ji Yang Elzbieta Pach Sophie Carenco Laureline Treps Nikos Liakakos Yu Shan Virginia Altoe Ed Wong Zengqing Zhuo Feipeng Yang Ji Su Jinghua Guo Monika Blum Saul H. Lapidus Adrian Hunt Iradwikanari Waluyo Hirohito Ogasawara Haimei Zheng Peidong Yang Alexis T. Bell Núria López Miquel Salmeron |
| author_sort | Hao Chen |
| collection | DOAJ |
| description | Abstract Cobalt is an efficient catalyst for Fischer−Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H2) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental and theoretical study using model catalysts consisting of crystalline CoMnOx nanoparticles and thin films, where Co and Mn are mixed at the sub-nm scale. Employing TEM and in-situ X-ray spectroscopies (XRD, APXPS, and XAS), we determine the catalyst’s atomic structure, chemical state, reactive species, and their evolution under FTS conditions. We show the concentration of CHx, the key intermediates, increases rapidly on CoMnOx, while no increase occurs without Mn. DFT simulations reveal that basic O sites in CoMnOx bind hydrogen atoms resulting from H2 dissociation on Co0 sites, making them less available to react with CHx intermediates, thus hindering chain termination reactions, which promotes the formation of long-chain hydrocarbons. |
| format | Article |
| id | doaj-art-14c2695ac20e4208a2185d80a69c5b4b |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-14c2695ac20e4208a2185d80a69c5b4b2025-01-26T12:40:14ZengNature PortfolioNature Communications2041-17232024-11-0115111010.1038/s41467-024-54578-3The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesisHao Chen0Zan Lian1Xiao Zhao2Jiawei Wan3Priscilla F. Pieters4Judit Oliver-Meseguer5Ji Yang6Elzbieta Pach7Sophie Carenco8Laureline Treps9Nikos Liakakos10Yu Shan11Virginia Altoe12Ed Wong13Zengqing Zhuo14Feipeng Yang15Ji Su16Jinghua Guo17Monika Blum18Saul H. Lapidus19Adrian Hunt20Iradwikanari Waluyo21Hirohito Ogasawara22Haimei Zheng23Peidong Yang24Alexis T. Bell25Núria López26Miquel Salmeron27Chemical Sciences Division, Lawrence Berkeley National LaboratoryInstitute of Chemical Research of Catalonia (ICIQ-CERCA), Barcelona Institute of Science and Technology (BIST)Materials Science Division, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryDepartment of Chemistry, University of CaliforniaChemical Sciences Division, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryChemical Sciences Division, Lawrence Berkeley National LaboratoryMolecular Foundry, Lawrence Berkeley National LaboratoryMolecular Foundry, Lawrence Berkeley National LaboratoryAdvanced Light Source, Lawrence Berkeley National LaboratoryAdvanced Light Source, Lawrence Berkeley National LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryAdvanced Light Source, Lawrence Berkeley National LaboratoryAdvanced Light Source, Lawrence Berkeley National LaboratoryAdvanced Photon Source, Argonne National LaboratoryNational Synchrotron Light Source II, Brookhaven National LaboratoryNational Synchrotron Light Source II, Brookhaven National LaboratorySLAC National Accelerator LaboratoryMaterials Science Division, Lawrence Berkeley National LaboratoryChemical Sciences Division, Lawrence Berkeley National LaboratoryChemical Sciences Division, Lawrence Berkeley National LaboratoryInstitute of Chemical Research of Catalonia (ICIQ-CERCA), Barcelona Institute of Science and Technology (BIST)Chemical Sciences Division, Lawrence Berkeley National LaboratoryAbstract Cobalt is an efficient catalyst for Fischer−Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H2) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental and theoretical study using model catalysts consisting of crystalline CoMnOx nanoparticles and thin films, where Co and Mn are mixed at the sub-nm scale. Employing TEM and in-situ X-ray spectroscopies (XRD, APXPS, and XAS), we determine the catalyst’s atomic structure, chemical state, reactive species, and their evolution under FTS conditions. We show the concentration of CHx, the key intermediates, increases rapidly on CoMnOx, while no increase occurs without Mn. DFT simulations reveal that basic O sites in CoMnOx bind hydrogen atoms resulting from H2 dissociation on Co0 sites, making them less available to react with CHx intermediates, thus hindering chain termination reactions, which promotes the formation of long-chain hydrocarbons.https://doi.org/10.1038/s41467-024-54578-3 |
| spellingShingle | Hao Chen Zan Lian Xiao Zhao Jiawei Wan Priscilla F. Pieters Judit Oliver-Meseguer Ji Yang Elzbieta Pach Sophie Carenco Laureline Treps Nikos Liakakos Yu Shan Virginia Altoe Ed Wong Zengqing Zhuo Feipeng Yang Ji Su Jinghua Guo Monika Blum Saul H. Lapidus Adrian Hunt Iradwikanari Waluyo Hirohito Ogasawara Haimei Zheng Peidong Yang Alexis T. Bell Núria López Miquel Salmeron The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis Nature Communications |
| title | The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis |
| title_full | The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis |
| title_fullStr | The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis |
| title_full_unstemmed | The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis |
| title_short | The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis |
| title_sort | role of manganese in comnox catalysts for selective long chain hydrocarbon production via fischer tropsch synthesis |
| url | https://doi.org/10.1038/s41467-024-54578-3 |
| work_keys_str_mv | AT haochen theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT zanlian theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT xiaozhao theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jiaweiwan theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT priscillafpieters theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT juditolivermeseguer theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jiyang theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT elzbietapach theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT sophiecarenco theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT laurelinetreps theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT nikosliakakos theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT yushan theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT virginiaaltoe theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT edwong theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT zengqingzhuo theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT feipengyang theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jisu theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jinghuaguo theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT monikablum theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT saulhlapidus theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT adrianhunt theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT iradwikanariwaluyo theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT hirohitoogasawara theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT haimeizheng theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT peidongyang theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT alexistbell theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT nurialopez theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT miquelsalmeron theroleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT haochen roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT zanlian roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT xiaozhao roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jiaweiwan roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT priscillafpieters roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT juditolivermeseguer roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jiyang roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT elzbietapach roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT sophiecarenco roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT laurelinetreps roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT nikosliakakos roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT yushan roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT virginiaaltoe roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT edwong roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT zengqingzhuo roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT feipengyang roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jisu roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT jinghuaguo roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT monikablum roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT saulhlapidus roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT adrianhunt roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT iradwikanariwaluyo roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT hirohitoogasawara roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT haimeizheng roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT peidongyang roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT alexistbell roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT nurialopez roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis AT miquelsalmeron roleofmanganeseincomnoxcatalystsforselectivelongchainhydrocarbonproductionviafischertropschsynthesis |