H+−H− Pairs in Partially Oxidized MAX Phases for Bifunctional Catalytic Conversion of Furfurals into Linear Ketones

Currently, less favorable C=O hydrogenation and weak concerted acid catalysis cause unsatisfactory catalytic performance in the upgrading of biomass‐derived furfurals (i.e., furfural, 5‐methyl furfural, and 5‐hydroxymethyl furfural) to ketones (i.e., cyclopentanone, 2,5‐hexanedione, and 1‐hydroxyl‐2...

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Published in:Angewandte Chemie International Edition 2023-02, Vol.62 (9), p.e202211461-n/a
Main Authors: Deng, Qiang, Zhou, Rong, Zhang, Yong‐Chao, Li, Xiang, Li, Jiahui, Tu, Shaobo, Sheng, Guan, Wang, Jun, Zeng, Zheling, Yoskamtorn, Tatchamapan, Edman Tsang, Shik Chi
Format: Article
Language:English
Subjects:
Acidity
Catalysis
Catalysts
Catalytic activity
Catalytic converters
Conversion
Frustrated Lewis Pairs
Furfural
Hydrogen
Hydrogenation
Ketones
MAX Phases
Palladium
Ring opening
Synergistic Reactions
Titanium silicon carbide
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Summary:Currently, less favorable C=O hydrogenation and weak concerted acid catalysis cause unsatisfactory catalytic performance in the upgrading of biomass‐derived furfurals (i.e., furfural, 5‐methyl furfural, and 5‐hydroxymethyl furfural) to ketones (i.e., cyclopentanone, 2,5‐hexanedione, and 1‐hydroxyl‐2,5‐hexanedione). A series of partially oxidized MAX phase (i.e., Ti3AlC2, Ti2AlC, Ti3SiC2) supporting Pd catalysts were fabricated, which showed high catalytic activity; Pd/Ti3AlC2 in particular displayed high performance for conversion of furfurals into targeted ketones. Detailed studies of the catalytic mechanism confirm that in situ hydrogen spillover generates Frustrated Lewis H+−H− pairs, which not only act as the hydrogenation sites for selective C=O hydrogenation but also provide acid sites for ring opening. The close intimate hydrogenation and acid sites promote bifunctional catalytic reactions, substantially reducing the reported minimum reaction temperature of various furfurals by at least 30–60 °C. Frustrated Lewis H+−H− pairs, generated in situ by hydrogen spillover on partially oxidized MAX phases, act as the hydrogenation sites for C=O hydrogenation and provide acid sites for ring opening. The close intimate hydrogenation and acid sites demonstrate unprecedented bifunctional catalytic performance for the conversion of furfurals.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202211461