Abstract
Nanostructured composite materials based on noble mono-(Pd) or bi-metallic (Ag/Pd) particles supported on mixed iron oxides (II/III) with bulk magnetite structure (Fe(3)O(4)) have been developed in order to assess their potential for heterogeneous catalysis applications in methane partial oxidation. Advancing the direct transformation of methane into value-added chemicals is consensually accepted as the key to ensuring sustainable development in the forthcoming future. On the one hand, nanosized Fe(3)O(4) particles with spherical morphology were synthesized by an aqueous-based reflux method employing different Fe (II)/Fe (III) molar ratios (2 or 4) and reflux temperatures (80, 95 or 110 °C). The solids obtained from a Fe (II)/Fe (III) nominal molar ratio of 4 showed higher specific surface areas which were also found to increase on lowering the reflux temperature. The starting 80 m(2) g(-1) was enhanced up to 140 m(2) g(-1) for the resulting optimized Fe(3)O(4)-based solid consisting of nanoparticles with a 15 nm average diameter. On the other hand, Pd or Pd-Ag were incorporated post-synthesis, by impregnation on the highest surface Fe(3)O(4) nanostructured substrate, using 1-3 wt.% metal load range and maintaining a constant Pd:Ag ratio of 8:2 in the bimetallic sample. The prepared nanocomposite materials were investigated by different physicochemical techniques, such as X-ray diffraction, thermogravimetry (TG) in air or H(2), as well as several compositions and structural aspects using field emission scanning and scanning transmission electron microscopy techniques coupled to energy-dispersive X-ray spectroscopy (EDS). Finally, the catalytic results from a preliminary reactivity study confirmed the potential of magnetite-supported (Ag)Pd catalysts for CH(4) partial oxidation into formaldehyde, with low reaction rates, methane conversion starting at 200 °C, far below temperatures reported in the literature up to now; and very high selectivity to formaldehyde, above 95%, for Fe(3)O(4) samples with 3 wt.% metal, either Pd or Pd-Ag.