Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction
Abstract Dual active sites with synergistic valence state regulation under oxidizing and reducing conditions are essential for catalytic reactions with step-wise mechanisms to modulate the complex adsorption sites of reactant molecules on the surfaces of heterogeneous catalysts with maximized cataly...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56161-w |
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| author | Xing-Chi Li Jun-Hao Wang Tao-Tao Huang Yang Hu Xin Li De-Jiu Wang Wei-Wei Wang Kai Xu Chun-Jiang Jia Hao Dong Guangshe Li Chen Li Ya-Wen Zhang |
| author_facet | Xing-Chi Li Jun-Hao Wang Tao-Tao Huang Yang Hu Xin Li De-Jiu Wang Wei-Wei Wang Kai Xu Chun-Jiang Jia Hao Dong Guangshe Li Chen Li Ya-Wen Zhang |
| author_sort | Xing-Chi Li |
| collection | DOAJ |
| description | Abstract Dual active sites with synergistic valence state regulation under oxidizing and reducing conditions are essential for catalytic reactions with step-wise mechanisms to modulate the complex adsorption sites of reactant molecules on the surfaces of heterogeneous catalysts with maximized catalytic performances, but it has been rarely explored. In this work, uniformly dispersed CuCo alloy and CoO nanosheet composite catalysts with dual active sites are constructed, which shows huge boost in activity for catalyzing water-gas shift reaction (WGSR), with a record high reaction rate reaching 204.2 μmolCO gcat. −1 s−1 at 300 °C for Cu1Co9Ox amongst the reported Cu-based and Co-based catalysts. A synergistic mechanism is proposed that Coδ+ species can be easily reduced by CO adsorbed on Cu and Co0 can be oxidized by H2O. Systematic in situ characterization results reveal that the addition of Cu can regulate the redox properties of Co species and thus modulate the adsorption properties of catalysts. Particularly, doping of Cu0 sites weakens the affinity of the surface to CO or CO2 to a moderate level. Moreover, it also promotes the oxidation of *CO to *COOH and the desorption of the product CO2, reducing the carbon poisoning of the catalyst and thus increasing the reactivity. The results would provide guidance for the construction of novel heterogeneous catalyst with dual active sites and clarify its underlying reactivity enhancement mechanism induced by the tunning of valence state of metal centers for heterogeneous catalytic reactions. |
| format | Article |
| id | doaj-art-2267d1bb4774404c95ea57df8802ca2e |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-2267d1bb4774404c95ea57df8802ca2e2025-01-19T12:31:15ZengNature PortfolioNature Communications2041-17232025-01-0116111110.1038/s41467-025-56161-wTunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reactionXing-Chi Li0Jun-Hao Wang1Tao-Tao Huang2Yang Hu3Xin Li4De-Jiu Wang5Wei-Wei Wang6Kai Xu7Chun-Jiang Jia8Hao Dong9Guangshe Li10Chen Li11Ya-Wen Zhang12Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking UniversityState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin UniversitySchool of Materials and Energy, Lanzhou UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking UniversityKey Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong UniversityKey Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong UniversityKey Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking UniversityState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking UniversityAbstract Dual active sites with synergistic valence state regulation under oxidizing and reducing conditions are essential for catalytic reactions with step-wise mechanisms to modulate the complex adsorption sites of reactant molecules on the surfaces of heterogeneous catalysts with maximized catalytic performances, but it has been rarely explored. In this work, uniformly dispersed CuCo alloy and CoO nanosheet composite catalysts with dual active sites are constructed, which shows huge boost in activity for catalyzing water-gas shift reaction (WGSR), with a record high reaction rate reaching 204.2 μmolCO gcat. −1 s−1 at 300 °C for Cu1Co9Ox amongst the reported Cu-based and Co-based catalysts. A synergistic mechanism is proposed that Coδ+ species can be easily reduced by CO adsorbed on Cu and Co0 can be oxidized by H2O. Systematic in situ characterization results reveal that the addition of Cu can regulate the redox properties of Co species and thus modulate the adsorption properties of catalysts. Particularly, doping of Cu0 sites weakens the affinity of the surface to CO or CO2 to a moderate level. Moreover, it also promotes the oxidation of *CO to *COOH and the desorption of the product CO2, reducing the carbon poisoning of the catalyst and thus increasing the reactivity. The results would provide guidance for the construction of novel heterogeneous catalyst with dual active sites and clarify its underlying reactivity enhancement mechanism induced by the tunning of valence state of metal centers for heterogeneous catalytic reactions.https://doi.org/10.1038/s41467-025-56161-w |
| spellingShingle | Xing-Chi Li Jun-Hao Wang Tao-Tao Huang Yang Hu Xin Li De-Jiu Wang Wei-Wei Wang Kai Xu Chun-Jiang Jia Hao Dong Guangshe Li Chen Li Ya-Wen Zhang Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction Nature Communications |
| title | Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction |
| title_full | Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction |
| title_fullStr | Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction |
| title_full_unstemmed | Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction |
| title_short | Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction |
| title_sort | tunning valence state of cobalt centers in cu co coo1 x for significantly boosting water gas shift reaction |
| url | https://doi.org/10.1038/s41467-025-56161-w |
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