https://ogma.newcastle.edu.au/vital/access/ /manager/Index en-au 5 Structural and activity investigation into Al<sup>3+</sup>, La<sup>3+</sup> and Ce<sup>3+</sup> addition to the phosphomolybdate heteropolyanion for isobutane selective oxidation https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:12410 xH3–3x[PMo12O40] (M = Al, La or Ce; 0 ≤ x ≤ 1). These compounds were analyzed by XRD and adsorption isotherm. Aluminum addition causes a primitive cubic phase, while lanthanum and cerium yield body-centered structures. La and Ce addition reduces surface area of phosphomolybdate structure. Temperature-programmed experiments for the selective oxidation of isobutane yielded methacrolein, 3-methyl-2-oxetanone (lactone), acetic acid (not with aluminous compounds), propene (only with aluminous compounds), carbon dioxide and water. The preference for propene rather than acetic acid formation with Al3+ may be due to the smaller cation size, or primitive cubic structure. These products form via two distinct reaction processes, labeled categories 1 and 2. Category 1 formation is associated with isobutane forming products on the surface, but reaction rate determined by bulk migration of charged particles. Category 2 formation is concerned with isobutane penetrating deep within the bulk of the substrate and forming products which subsequently desorb in a series of bell-shaped humps. Methacrolein forms via both category 1 and 2, whilst all other products form via category 2 exclusively. Kinetic analysis showed apparent activation barriers for category 1 methacrolein formation range from 67 ± 2 kJ mol-1to[350 kJ mol-1, and occur in groups with small, medium and large activation barriers. The addition of +3 metal cations to the phosphomolybdate anion increase thermal stability, significantly decreasing deactivation; IR spectroscopy shows that the Keggin structure remains intact during temperature-programmed experiments with the Al, La and Ce salts.]]> Sat 24 Mar 2018 08:14:51 AEDT ]]> Accurate low-pressure kinetics for isobutane oxidation over phosphomolybdic acid and copper(II) phosphomolybdates https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:5049 Sat 24 Mar 2018 07:48:44 AEDT ]]>