Ordered versus Non-Ordered Mesoporous CeO2-Based Systems for the Direct Synthesis of Dimethyl Carbonate from CO2

In this work, non-ordered and ordered CeO2-based catalysts are proposed for CO2 conversion to dimethyl carbonate (DMC). Particularly, non-ordered mesoporous CeO2, consisting of small nanoparticles of about 8 nm, is compared with two highly porous (635–722 m2/g) ordered CeO2@SBA-15 nanocomposites obtained by two different impregnation strategies (a two-solvent impregnation method (TS) and a self-combustion (SC) method), with a final CeO2 loading of 10 wt%. Rietveld analyses on XRD data combined with TEM imaging evidence the influence of the impregnation strategy on the dispersion of the active phase as follows: nanoparticles of 8 nm for the TS composite vs. 3 nm for the SC composite. The catalytic results show comparable activities for the mesoporous ceria and the CeO2@SBA-15_SC nanocomposite, while a lower DMC yield is found for the CeO2@SBA-15_TS nanocomposite. This finding can presumably be ascribed to a partial obstruction of the pores by the CeO2 nanoparticles in the case of the TS composite, leading to a reduced accessibility of the active phase. On the other hand, in the case of the SC composite, where the CeO2 particle size is much lower than the pore size, there is an improved accessibility of the active phase to the molecules of the reactants