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Abstract: We have made high surface area catalysts for the selective oxidation of methanol to formaldehyde. This is done in two ways – (i) by doping haematite with Al ions, to increase the surface area of the material, but which itself is unselective and (ii) by surface coating with Mo which induces high selectivity. Temperature programmed desorption (TPD) of methanol shows little difference in surface chemistry of the doped haematite from the undoped material, with the main products being CO2 and CO, but shifted to somewhat higher desorption temperature. However, when Mo is dosed onto the haematite surface, the chemistry changes completely to show mainly the selective product, formaldehyde, with no CO2 production, and this is little changed up to 10% Al loading. But at 15 wt% Al, the chemistry changes to indicate the presence of a strongly acidic function at the surface, with additional dimethyl ether and CO/CO2 production characteristic of the presence of alumina. Structurally, X-ray diffraction (XRD) shows little change over the range 0–20% Al doping, except for some small lattice contraction, while the surface area increases from around 20 to 100 m2 g−1. Using X-ray absorption spectroscopy (XAS) it is clear that, at 5% loading, the Al is incorporated into the Fe2O3 corundum lattice, which has the same structure as α-alumina. By 10% loading then it appears that the alumina starts to nano-crystallise within the haematite lattice into the γ form. At higher loadings, there is evidence of phase separation into separate Al-doped haematite and γ-alumina. If we add 1 monolayer equivalent of Mo to the surface there is already high selectivity to formaldehyde, but little change in structure, because that monolayer is isolated at the surface. However, when three monolayers equivalent of Mo is added, we then see aluminium molybdate type signatures in the XANES spectra at 5% Al loading and above. These appear to be in a sub-surface layer with Fe molybdate, which we interpret as due to Al substitution into ferric molybdate layers immediately beneath the topmost surface layer of molybdena. It seems like the separate γ-alumina phase is not covered by molybdena and is responsible for the appearance of the acid function products in the TPD.

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Abstract: The catalytic performance of a series of 1 wt % Pd/C catalysts prepared by the sol-immobilization method has been studied in the liquid-phase hydrogenation of furfural. The temperature range studied was 25–75 °C, keeping the H2 pressure constant at 5 bar. The effect of the catalyst preparation using different capping agents containing oxygen or nitrogen groups was assessed. Polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and poly (diallyldimethylammonium chloride) (PDDA) were chosen. The catalysts were characterized by ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The characterization data suggest that the different capping agents affected the initial activity of the catalysts by adjusting the available Pd surface sites, without producing a significant change in the Pd particle size. The different activity of the three catalysts followed the trend: PdPVA/C > PdPDDA/C > PdPVP/C. In terms of selectivity to furfuryl alcohol, the opposite trend has been observed: PdPVP/C > PdPDDA/C > PdPVA/C. The different reactivity has been ascribed to the different shielding effect of the three ligands used; they influence the adsorption of the reactant on Pd active sites.

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Abstract: Multicomponent oxide shell@core catalysts have been prepared, affording overlayers of MoOx on Fe2O3. This design approach allows bulk characterization techniques, such as X-ray Absorption Fine Structure (XAFS), to provide surface sensitive information. Coupling this approach with in situ methodologies provides insights during crucial catalytic processes. Calcination studies were followed by a combination of XAFS and Raman, and demonstrate that amorphous multi-layers of MoOx are first converted to MoO3 before formation of Fe2(MoO4)3. However, a single overlayer of Oh Mo units remains at the surface at all times. In situ catalysis studies during formaldehyde production identified that Mo6+ was present throughout, confirming that gas phase oxygen transfer to molybdenum is rapid under reaction conditions. Reduction studies in the presence of MeOH resulted in the formation of reduced Mo-Mo clusters with a bonding distance of 2.6 Å. It is proposed that the presence of the clusters indicates that the selective conversion of MeOH to formaldehyde requires multiple Mo sites.