The selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) represents a crucial catalytic approach for obtaining high-performance, next-generation biofuels from renewable biomass resources. This conversion is of particular significance as DMF possesses excellent fuel properties, such as high energy density and low solubility in water, rendering it a promising alternative to gasoline. In this study, an innovative Pd2+-Pd0/activated carbon (AC) bifunctional catalyst, containing synergistic coexistence of Pd2+ and Pd0 species, was successfully fabricated via a customized adsorption-precipitation-in situ partial reduction strategy. This synthetic methodology allows for precise control over the oxidation states and spatial distribution of Pd species on the AC support. The effects of key reaction parameters, specifically reaction temperature, hydrogen pressure, reaction time as well as catalyst pre-reduction time, on the hydrogenation reaction pathways, product selectivity and overall catalytic performance for HMF conversion were comprehensively investigated in an n-butanol solvent system. Under the meticulously optimized conditions, exceptional catalytic results were attained: the HMF conversion achieved 99.6%, and the yield of the target molecule DMF reached as high as 90.4%, demonstrating outstanding selectivity. To unravel the intrinsic structure-activity relationships and the source of the high DMF yield, the catalysts were subjected to a suite of advanced characterization techniques. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (H2-TPR) were employed in tandem. These analyses provided compelling evidence for a synergistic catalytic mechanism between the two types of Pd species: the metallic Pd0 sites primarily account for the efficient activation and dissociation of H2, generating active hydrogen species; concurrently, an appropriate amount of Lewis-acidic Pd2+ sites facilitates the critical activation of the C=O group in HMF and its intermediate, and promote the subsequent hydrogenolysis of the hydroxymethyl group. This collaborative action between the two functionalities creates an optimized reaction pathway that minimizes side reactions, thereby directing the selectivity decisively toward DMF formation. This work not only presents a highly efficient catalytic system for DMF production but also offers fundamental insights into the rational design of bifunctional metal catalysts for the selective hydrogenation of biomass-derived platform molecules.
Jia Xiangyu
,
Xue Yuxiang
,
Yuan Kai
,
Zhu Shanhui
. The selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran catalyzed by Pd2+-Pd0/AC[J]. Acta Chimica Sinica, 2026
: 26070248
.
DOI: 10.6023/A26070248
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