Synthesis of mesoporous ceria using metal- and halogen-free ordered mesoporous carbon as a hard template†
Ordered mesoporous cerias were synthesised by employing metal- and halogen-free ordered mesoporous carbons (OMCs) as the hard templates in a ‘nanocasting’ procedure. TEM, small angle (SA) and wide angle (WA) XRD, and N2 physisorption analyses were used to characterise the templates, intermediates and ceria products and electron tomography (STEM-HAADF) was used to explore the 3D morphology of the ceria nanostructures grown within the carbon templates. This allowed the relationships between the structures of the OMC templates and the products to be considered in detail as two parameters were varied. These were: the method of impregnation of the ceria precursor; and the temperature of calcination of the OMC template. Of the four impregnation methods tested, the solid–liquid method was found to be the most successful. This gave a high quality product with the highest yield of uniform mesopores, and crystalline nanorods of ceria arrayed in clear long-range order, as viewed by TEM and determined in SA and WAXRD. The specific surface area and pore volume exhibited by this sample were 111 m2 g−1 and 0.39 cm3 g−1, respectively. 3D electron tomography reconstructions revealed the presence of a network of ordered, nanoscale, rod-like structures interlinked in a complex fashion. The effect of calcination temperature of the template on uptake of the ceria precursor during impregnation was studied by calcining OMCs at temperatures from 350 to 800 °C and using these as hard templates for the nanocasting of ceria. Of these, the carbon template calcined at 400 °C gave the highest quality product.