a b s t r a c tThe selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO 2 , ZnO, ␥-Al 2 O 3 , CeO 2 is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 • C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO 2 and ␥-Al 2 O 3 . In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature.
Highlights High OSCs' oxide supports promote CO-enriched syngas production of Rh-catalysed DRM Low carbon deposition was revealed, increasing in the order Rh/CZ
Furfural
is a key bioderived platform chemical whose reactivity
under hydrogen atmospheres affords diverse chemical intermediates.
Here, temperature-programmed reaction spectrometry and complementary
scanning tunneling microscopy (STM) are employed to investigate furfural
adsorption and reactivity over a Pt(111) model catalyst. Furfural
decarbonylation to furan is highly sensitive to reaction conditions,
in particular, surface crowding and associated changes in the adsorption
geometry: furfural adopts a planar geometry on clean Pt(111) at low
coverage, tilting at higher coverage to form a densely packed furfural
adlayer. This switch in adsorption geometry strongly influences product
selectivity. STM reveals the formation of hydrogen-bonded networks
for planar furfural, which favor decarbonylation on clean Pt(111)
and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed
hydrogen promotes furfural hydrogenation to furfuryl alcohol and its
subsequent hydrogenolysis to methyl furan, while suppressing residual
surface carbon. Furfural chemistry over Pt is markedly different from
that over Pd, with weaker adsorption over the former affording a simpler
product distribution than the latter; Pd catalyzes a wider range of
chemistry, including ring-opening to form propene. Insight into the
role of molecular orientation in controlling product selectivity will
guide the design and operation of more selective and stable Pt catalysts
for furfural hydrogenation.
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