Shape-Controlled Pathways in the Hydrogen Production from Ethanol Steam Reforming over Ceria Nanoparticles

[Image: see text] The ethanol surface reaction over CeO(2) nanooctahedra (NO) and nanocubes (NC), which mainly expose (111) and (100) surfaces, respectively, was studied by means of infrared spectroscopy (TPSR-IR), mass spectrometry (TPSR-MS), and density functional theory (DFT) calculations. TPSR-MS results show that the production of H(2) is 2.4 times higher on CeO(2)-NC than on CeO(2)-NO, which is rationalized starting from the different types of adsorbed ethoxy species controlled by the shape of the ceria particles. Over the CeO(2)(111) surface, monodentate type I and II ethoxy species with the alkyl chain perpendicular or parallel to the surface, respectively, were identified. Meanwhile, on the CeO(2)(100) surface, bidentate and monodentate type III ethoxy species on the checkerboard O-terminated surface and on a pyramid of the reconstructed (100) surface, respectively, are found. The more labile surface ethoxy species on each ceria nanoshape, which are the monodentate type I or III ethoxy on CeO(2)-NO and CeO(2)-NC, respectively, react on the surface to give acetate species that decompose to CO(2) and CH(4), while H(2) is formed via the recombination of hydroxyl species. In addition, the more stable monodentate type II and bidentate ethoxy species on CeO(2)-NO and CeO(2)-NC, respectively, give an ethylenedioxy intermediate, the binding of which is facet-dependent. On the (111) facet, the less strongly bound ethylenedioxy desorbs as ethylene, whereas on the (100) facet, the more strongly bound intermediate also produces CO(2) and H(2) via formate species. Thus, on the (100) facet, an additional pathway toward H(2) formation is found. ESR activity measurements show an enhanced H(2) production on the nanocubes.