CO Adsorbates Induced Framework-Associated Low-Valence Co<sup>δ+</sup> Sites in Co-ZSM-5 for Ethane Dehydrogenation
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. <i>In situ</i> spectroscopy and metadynamics simulations reveal that the Co<sup>2+</sup> sites in 0.50Co-Z5(340) dislodge from the framework and move toward the nearby Brønsted acid sites, forming framework-associated low-valence Co<sup>δ+</sup> species. Mechanistic studies indicate that the Co<sup>δ+</sup> species catalyze ethane C-H bond cleavage <i>via</i> 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.
Authors
- Irene Barba-Nieto (ORCID: https://orcid.org/0000-0001-7793-685X)
- Shaojia Song (ORCID: https://orcid.org/0009-0009-0155-3727)
- Weiyu Song (ORCID: https://orcid.org/0000-0001-5720-204X)
- Riguang Zhang (ORCID: https://orcid.org/0000-0001-8956-8425)
- Yumeng Fo
- Marcos Fernández–García (ORCID: https://orcid.org/0000-0002-9987-0289)
- Patricia Concepción (ORCID: https://orcid.org/0000-0003-2058-3103)
- Zhen Zhao (ORCID: https://orcid.org/0000-0003-3650-0747)
- Jian Liu (ORCID: https://orcid.org/0000-0003-3392-9812)
- Xinyu Chen (ORCID: https://orcid.org/0000-0001-7655-7823)
- Minjie Zhao (ORCID: https://orcid.org/0009-0004-2198-1570)
- Chunming Xu (ORCID: https://orcid.org/0009-0009-6255-2090)
Institutions
- Consejo Superior de Investigaciones Científicas (ES)
- Brookhaven National Laboratory (US)
- China University of Petroleum, Beijing (CN)
- Instituto de Catálisis y Petroleoquímica (ES)
- Division of Chemistry (US)
- Instituto de Tecnología Química (ES)
- Karamay Central Hospital (CN)
- Karamay Central Hospital of Xinjiang (CN)
- Universitat Politècnica de València (ES)
- Taiyuan University of Technology (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-09-05
- DOI
- https://doi.org/10.1021/jacs.5c09290
- Citations
- 3
- Primary Topic
- Catalysis and Oxidation Reactions
- Type
- article
- Field-Weighted Citation Impact
- 1.17
Funders
- National Natural Science Foundation of China
- China Scholarship Council
- Agencia Estatal de Investigación
- National Key Research and Development Program of China
- Brookhaven National Laboratory