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Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon
Author(s) -
Hu Bin,
Warczinski Lisa,
Li Xiaoyu,
Lu Mohong,
Bitzer Johannes,
Heidelmann Markus,
Eckhard Till,
Fu Qi,
Schulwitz Jonas,
Merko Mariia,
Li Mingshi,
Kleist Wolfgang,
Hättig Christof,
Muhler Martin,
Peng Baoxiang
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202012816
Subject(s) - hydrogenolysis , chemistry , bifunctional , formic acid , catalysis , bond cleavage , mesoporous material , organic chemistry
Biomass‐derived 5‐hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5‐dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N‐containing and N‐free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H 2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR‐IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C‐OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd 2+ species interacting with pyridine‐like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H − .