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Crystal Phase Engineering of Cobalt‐Based Catalyst for Switching CO2 Hydrogenation Selectivity From CH4 to CO.

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Title: Crystal Phase Engineering of Cobalt‐Based Catalyst for Switching CO2 Hydrogenation Selectivity From CH4 to CO.
Authors: Jin, Shuo1,2 (AUTHOR), Li, Jingru1,2 (AUTHOR), Shang, Longmei1,2 (AUTHOR) shanglm@hqu.edu.cn, Cai, Dongren1 (AUTHOR) 15506@hqu.edu.cn, Zhan, Guowu1,2 (AUTHOR) gwzhan@hqu.edu.cn
Source: ChemCatChem. 4/14/2026, Vol. 18 Issue 7, p1-9. 9p.
Subjects: Cobalt catalysts, Catalyst selectivity, Water gas shift reactions, Catalytic hydrogenation, Catalysts, Oxygen vacancy, Crystal lattices
Abstract: Altering the inherent selectivity of catalysts toward the C1 product is of great significance for enriching the selection of CO2 directional conversion. Herein, we demonstrate that regulating the crystal phase of cobalt (Co)‐based catalysts enables a dramatic shift from methane (CH4) to carbon monoxide (CO). At 320°C and ambient pressure, the Co with a face‐centered cubic structure (FCC‐Co) predominantly yields CH4 in CO2 hydrogenation, achieving 94% of CH4 selectivity and 53% of CO2 conversion, while the hexagonal close‐packed structure (HCP‐Co) exhibits exceptional selectivity toward CO, with 96% of CO selectivity and 21% of CO2 conversion. Multimodal characterizations reveal that compared to FCC‐Co, the lower content of oxygen vacancies and metallic Co0 over HCP‐Co results in the weak CO2/CO adsorption and insufficient hydrogen dissociation, which suppresses the CO→CH4 step in the CO2 hydrogenation, thereby redirecting product selectivity toward CO rather than CH4. This work highlights crystal phase tailoring of Co‐based catalysts as a viable strategy to regulate product selectivity in CO2 hydrogenation, offering insights for rational catalyst design in RWGS reactions. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:Altering the inherent selectivity of catalysts toward the C1 product is of great significance for enriching the selection of CO2 directional conversion. Herein, we demonstrate that regulating the crystal phase of cobalt (Co)‐based catalysts enables a dramatic shift from methane (CH4) to carbon monoxide (CO). At 320°C and ambient pressure, the Co with a face‐centered cubic structure (FCC‐Co) predominantly yields CH4 in CO2 hydrogenation, achieving 94% of CH4 selectivity and 53% of CO2 conversion, while the hexagonal close‐packed structure (HCP‐Co) exhibits exceptional selectivity toward CO, with 96% of CO selectivity and 21% of CO2 conversion. Multimodal characterizations reveal that compared to FCC‐Co, the lower content of oxygen vacancies and metallic Co0 over HCP‐Co results in the weak CO2/CO adsorption and insufficient hydrogen dissociation, which suppresses the CO→CH4 step in the CO2 hydrogenation, thereby redirecting product selectivity toward CO rather than CH4. This work highlights crystal phase tailoring of Co‐based catalysts as a viable strategy to regulate product selectivity in CO2 hydrogenation, offering insights for rational catalyst design in RWGS reactions. [ABSTRACT FROM AUTHOR]
ISSN:18673880
DOI:10.1002/cctc.202501850