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CeO2 nanoshapes, cubes with dominant (1 0 0) facets and octahedra with dominant (1 1 1) facets, were synthesized to investigate the influence of surface structure on acid-base properties. An optimization of calcination temperatures, coupled with Raman and TEM, was employed to minimize the intrinsic (Frenkel-type) defect sites and their potential complications on the facet studies involved in this work. The acid-base properties of these CeO2 nanoshapes were characterized with in situ pyridine and CO2 adsorption using infrared spectroscopy and quantified using pyridine, ammonia, and CO2 temperature-programmed desorption (TPD). The (1 0 0) facet displayed weaker acid sites with lower site density than the (1 1 1) facet which had a similar density of base sites but those on the (1 0 0) facet were stronger. A strong correlation was observed between 2-propanol conversion and each facet’s acid-base properties. CeO2 cubes exhibited greater base-site catalyzed dehydrogenation to acetone while the more acidic CeO2 octahedra were more active in dehydration to propene.

In the present study, we investigate the surface acid–base properties of anatase TiO2 nanomaterials with dominant {101} and {001} facets via methanol titrations. Two anatase nanoparticles, TiO2(101...

Hydrodeoxygenation of lignin-derived phenols could be achieved generally with three reaction pathways: tautomerization, direct ring hydrogenation and direct C–O bond cleavage. The former pathway has been extensively studied over Pd/Fe catalyst in liquid-phase reaction, however, the contribution of the latter two is yet subject to further investigations. In this report, a comparative study of direct C–O bond cleavage and direct ring hydrogenation reaction pathways is presented on Pd/Fe, Fe and Pd/C catalysts using diphenyl ether as modelling compound. Despite its much higher activation energy than direct ring hydrogenation, direct C–O bond cleavage is dominant over Pd/Fe with much higher rates than the monometallic analogues due to the synergic catalysis of Pd–Fe. Based on this study and our previous results, the detailed reaction network for HDO of diphenyl ether is proposed.

Alkanol dehydration on Lewis acid–base pairs of transition metal oxide catalysts is a reaction of importance in oxygen removal from biomass-derived feedstocks and their conversion to chemicals in g...

Tailoring the graphene-covered Fe with Cs modifies the surface electronic properties of the catalysts such that selective C–O bond cleavage of phenol is achieved in liquid phase by inhibiting the facile tautomerization followed by ring saturation., Development of inexpensive sulfur-free catalysts for selective hydrogenolysis of the C–O bond in phenolics (i.e., selective removal of oxygen without aromatic ring saturation) under liquid-phase conditions is highly challenging. Here, we report an efficient approach to engineer earth-abundant Fe catalysts with a graphene overlayer and alkali metal (i.e., Cs), which produces arenes with 100% selectivity from liquid-phase hydrodeoxygenation (HDO) of phenolics with high durability. In particular, we report that a thin (a few layers) surface graphene overlayer can be engineered on metallic Fe particles (G@Fe) by a controlled surface reaction of a carbonaceous compound, which prevents the iron surface from oxidation by hydroxyls or water produced during HDO reaction. More importantly, further tailoring the surface electronic properties of G@Fe with the addition of cesium, creating a Cs-G@Fe composite catalyst in contrast to a deactivated Cs@Fe one, promotes the selective C–O bond cleavage by inhibiting the tautomerization, a pathway that is very facile under liquid-phase conditions. The current study could open a general approach to rational design of highly efficient catalysts for HDO of phenolics.

Although Pd/Fe bimetallic catalysts have been extensively studied in vapor-phase hydrodeoxygenation of phenolics (i.e., guaiacol, cresol), little is yet known about their performance in liquid-phase reactions. In this work, we present a mechanistic study on the Pd/Fe bimetallic catalysts in liquid-phase hydrodeoxygenation of phenolics. The role of tautomerization in hydrodeoxygenation of the lignin-derived phenolics, particularly for ring saturation, is systematically studied by employing two representative modeling compounds: phenol (a molecule that is keto-enol tautomeric) and diphenyl ether (a molecule that does not allow ketol-enol tautomerization). It was found that although the addition of oxyphilic Fe inhibits the direct aromatic ring saturation reaction typically occurring on Pd, tautomerization opens another reaction pathway toward ring saturation products (i.e. cyclohexanone, cyclohexanol, cyclohexane et al.), where both tautomerization and the hydrogenation of keto isomers are significantly enhanced to produce cyclohexanol followed by direct hydrogenolysis of the cyclohexanol to cyclohexane.

Iron-carbide-based catalysts have been explored in the selective hydrodeoxygenation (HDO) of phenol, aiming at elucidating the role of active site and alkali metal. Complementary characterization such as X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and scanning transmission electron microscopy coupled with electron energy loss spectroscopy, together with catalytic evaluations revealed a rapid structural reconstruction of iron carbide (Fe3 C) catalysts, leading to a stable defective graphene-covered metallic Fe active phase (G@Fe) under reaction conditions. Further studies using different alkali metals (i. e., Na, K, and Cs) revealed that alkali metals showed negligible effect on the phase transformation of Fe3 C. However, the reconstructed G@Fe doped with alkali metals inhibited the tautomerization, a facile reaction pathway to saturation of the aromatic ring, leading to enhanced selectivity to arene. The extent of inhibition of tautomerization or selectivity to arene was closely related to the degree of electron donation of alkali metal to Fe.