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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The effect of the morphology of Ir particles supported on γ-Al2O3, 8mol%Y2O3-stabilized ZrO2 (YSZ), 10mol%Gd2O3-doped CeO2 (GDC) and 80wt%Al2O3-10wt%CeO2-10wt%ZrO2 (ACZ) on their stability on oxidative conditions, the associated metal-support interactions and activity for catalytic decomposition of N2O has been studied. Supports with intermediate or high oxygen ion lability (GDC and ACZ) effectively stabilized Ir nanoparticles against sintering, in striking contrast to supports offering negligible or low oxygen ion lability (γ-Al2O3 and YSZ). Turnover frequency studies using size-controlled Ir particles showed strong structure sensitivity, de-N2O catalysis being favoured on large catalyst particles. Although metallic Ir showed some de-N2O activity, IrO2 was more active, possibly present as a superficial overlayer on the iridium particles under reaction conditions. Support-induced turnover rate modifications, resulted from an effective double layer [O δ-δ + ](Ir) on the surface of iridium nanoparticles, via O 2backspillover from the support, were significant in the case of GDC and ACZ.

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Various methods of physical, chemical and combined physicochemical pre-treatments for lignocellulosic biomass waste valorisation to value-added feedstock/solid fuels for downstream processes in chemical industries have been reviewed. The relevant literature was scrutinized for lignocellulosic waste applicability in advanced thermochemical treatments for either energy or liquid fuels. By altering the overall naturally occurring bio-polymeric matrix of lignocellulosic biomass waste, individual components such as cellulose, hemicellulose and lignin can be accessed for numerous downstream processes such as pyrolysis, gasification and catalytic upgrading to value-added products such as low carbon energy. Assessing the appropriate lignocellulosic pre-treatment technology is critical to suit the downstream process of both small- and large-scale operations. The cost to operate the process (temperature, pressure or energy constraints), the physical and chemical structure of the feedstock after pre-treatment (decomposition/degradation, removal of inorganic components or organic solubilization) or the ability to scale up the pre-treating process must be considered so that the true value in the use of bio-renewable waste can be revealed.