Co-CoO
x
-containing N-doped porous carbon-supported
palladium catalysts were prepared via a ZIF precursor calcination
and a simple impregnation route. The material was employed for the
hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran
(DMF). The Co-CoO
x
-containing N-doped
porous carbon provides a high dispersion and anchoring effect on active
metal as well as abundant surface defects with strong adsorption ability
to the oxygenated groups and enhanced electron transfer capability,
which could promote the activation and H2 spillover and
the cascade reaction of HMF hydrogenolysis to DMF. As-obtained palladium-based
nanocatalysts exhibited excellent catalytic hydrogenolysis performance,
and there is no apparent change in activity in six runs. The reasonable
synergism between surface defects and active metallic species is the
primary reason for such excellent catalytic effects. Most importantly,
the strategy proposed enables us to adjust the physicochemical properties
of the catalyst surface to design new bifunctional catalysts with
significantly improved performance.
Pd‐based catalysts supported on porous zinc oxide nanoparticles derived from nanoscale zeolitic imidazolate framework‐8 (ZIF‐8) are prepared and used for the selective hydrogenation of 5‐hydroxymethylfurfural (HMF). The X‐ray photoelectron spectroscopy and transmission electron microscopy results suggest that PdZn nanoalloy was formed during the calcination process of the catalyst precursor with the in situ reduction effect of carbon. The experiments and the density functional theory calculation results suggest that the exposed PdZn(111) and PdZn(200) faces on the prepared PdZn catalysts show lower activation energies and dissociative adsorption energies for H2 compared with Pd(111), which favors the migration of H atom and the hydrogenation reaction. Furthermore, PdZn(111) and PdZn(200) faces also display weaker adsorption ability for BHMF and the furan ring of HMF, which could efficiently inhibit the excessive hydrogenation of CC in furan ring and the hydrogenolysis of BHMF. Alloying Pd with Zn alters the reaction routes of HMF hydrogenation to BHMF. The first step of HMF hydrogenation more likely starts with the CH2O intermediate on the PdZn(111) and PdZn(200) faces, while the CHOH intermediate is preferentially formed on the Pd(111) face.
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