CO Adsorbates Induced Framework-Associated Low-Valence Co[delta]+ Sites in Co-ZSM-5 for Ethane Dehydrogenation
[EN] The dynamic structural evolution of heterogeneous catalysts is a ubiquitous phenomenon that has attracted a lot of interest. Catalyst reconstruction can occur after appropriate pretreatment, resulting in more efficient active catalysts, which is an attractive but challenging issue. Here, we rev...
| Autores: | , , , , , , , , , , , |
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| Formato: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Recursos: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:riunet.upv.es:10251/228462 |
| Acesso em linha: | https://riunet.upv.es/handle/10251/228462 |
| Access Level: | acceso abierto |
| Palavra-chave: | Heterogeneous catalysts CO activation Co-ZSM-5 Ethane dehydrogenation In situ spectroscopy Catalyst reconstruction |
| Resumo: | [EN] The dynamic structural evolution of heterogeneous catalysts is a ubiquitous phenomenon that has attracted a lot of interest. Catalyst reconstruction can occur after appropriate pretreatment, resulting in more efficient active catalysts, which is an attractive but challenging issue. Here, we reveal a CO activation strategy that controls the microenvironment of the Co sites in the high-silica Co-ZSM-5 catalyst (denoted as 0.50Co-Z5(340)), resulting in three times higher initial conversion and superior regeneration durability in the ethane dehydrogenation reaction compared to the same catalyst without CO pretreatment. In situ spectroscopy and metadynamics simulations reveal that the Co2+ sites in 0.50Co-Z5(340) dislodge from the framework and move toward the nearby Br & oslash;nsted acid sites, forming framework-associated low-valence Co delta+ species. Mechanistic studies indicate that the Co delta+ species catalyze ethane C-H bond cleavage via an oxidative addition mechanism, and ethylene is produced simultaneously with H* coupling (direct pathway). The promoted C-H bond activation and facile ethylene desorption explain the superior ethane dehydrogenation performance of the herein CO preactivated 0.50Co-Z5(340) catalyst. |
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