Controlled selectivity for ethanol steam reforming reaction over doped CeO2 surfaces: The role of gallium

[Display omitted] •Novel promotion of CeO2 with gallium enhances both H2 yield and H2:CO2 ratio.•Gallium plays a role in avoiding coke formation by suppressing ethylene production.•LD ethoxy species on pure CeO2 are responsible for ethylene formation.•Ga addition to ceria shifts the decomposition pathway of LD ethoxy to acetate.•CeOGa interface assists the acetate decomposition to CO2 and CH4 at lower T. The ethanol steam reforming reaction, together with the adsorption and decomposition of ethanol was studied on CeO2 and gallium-doped ceria (CeGaOx) by a combined experimental and theoretical approach using infrared spectroscopy (IR), mass spectrometry (MS) and density functional theory (DFT) calculations. At 100 °C, different types of monodentate ethoxy species were identified as standing-up (SU) on Ce4+ and lying-down (LD) on Ce4+ and Ga3+, with the alkyl chain more perpendicular or parallel to the surface, respectively. It is suggested that the incorporation of Ga into the ceria lattice changes the decomposition pathway of LD species, which converts to acetate instead of ethylene, attributed to the increased lattice oxygen lability in the CeOGa interface upon doping and the propensity to form GaH surface species. Under ethanol steam reforming conditions, Ga doping of ceria-based materials has a drastic effect by improving the H2:CO2 ratio, changing the product distribution and reducing coke formation.