CO2 Electroreduction to Long‐Chain Hydrocarbons on Cobalt Catalysts

• Published in: Advanced energy materials 2024-12, Vol.14 (47), p.n/a
• Main Authors: Preikschas, Phil, Zhang, Jie, Seemakurthi, Ranga Rohit, Lian, Zan, Martín, Antonio José, Xi, Shibo, Krumeich, Frank, Ma, Haibin, Zhou, Yansong, López, Núria, Yeo, Boon Siang, Pérez‐Ramírez, Javier
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Catalysts; CO2 reduction; cobalt; Cobalt oxides; Electrocatalysts; Electrolysis; heterogeneous catalysis; Hydrocarbons; Metal oxides; metal‐metal oxide interface; Molecular chains; multicarbon products
• ISSN: 1614-6832; 1614-6840
• DOI: 10.1002/aenm.202401447

Renewable‐powered electrocatalytic CO2 conversion to long‐chain hydrocarbons represents a sustainable path to produce chemicals and fuels. However, recently discovered systems still lack C–C coupling capabilities required to yield longer, more valuable carbon chains. This study reports cobalt catalysts with a focus on a Co3O4‐derived material for the selective conversion of CO2 to C1–C7 hydrocarbons, following an Anderson–Schulz–Flory distribution. The obtained chain growth probability (α) of 0.54 substantially exceeds that of any other known electrocatalyst, which ranged from 0.2 to 0.4. Detailed in situ characterization and simulations indicated that Co‐Co3O4 interfaces, formed in situ during CO2 electrolysis, are the active sites that promote enhanced chain growth. To prevent overreduction that causes the deactivation of these interfacial sites, the electrode is exposed to intermittent short reoxidation cycles during CO2 electrolysis. Consequently, the catalyst regained its oxidic phase and ability to form hydrocarbons. Overall, this study opens new frontiers in the one‐step conversion of CO2 into multi‐carbon products and suggests the exploration of metal–metal oxide interfaces as a promising strategy for further progress. Catalysts derived from oxygen‐containing cobalt precursors facilitate the formation of long‐chain hydrocarbons in electrocatalytic CO2 reduction. In situ characterization and simulations reveal Co‐Co3O4 interfaces as pivotal for C–C coupling. These interfacial sites are selective, yielding a chain growth probability higher than that of any other known electrocatalyst.