Highly efficient heterogeneous photooxidation of 2-propanol to acetone with amorphous manganese oxide catalysts

Abstract

Amorphous manganese oxides, potassium oxalatomanganate complexes, and crystalline tunnel structure manganese oxides (hollandite, todorokite, pyrolusite) have been prepared and used as photocatalysts for the oxidation of 2-propanol to acetone. Amorphous mixed valent manganese oxides, a new class of photocatalytic materials, were the most active catalysts studied at room temperature under visible light illumination. High activities correlate with higher oxidation state manganese (Mn[sup 3+], Mn[sup 4+]) oxides, large surface oxygen concentrations, and the presence of hydroxyl groups on surfaces of these catalysts. BET (surface area analysis), XRD (X-ray diffraction), EDX (energy dispersive X-ray analysis), SEM (scanning electron microscopy), XPS (X-ray photoelectron spectroscopy), and FTIR (Fourier transform infrared) data support these correlations. A mechanism for these photooxidation flow reactions involving manganese oxide catalysts has been proposed. Photochemical and characterization data suggest that the design of active photocatalysts may rely on preparation of mixed valent amorphous oxides that release oxygen more readily than crystalline materials. Conversions as high as 8% and 100% selectivity to acetone have been realized with such systems. 45 refs., 9 figs., 1 tab.