• catalysis;
  • composite materials;
  • electrodes;
  • electronic structures/processes/mechanisms;
  • fuel cells


Solid oxide fuel cells (SOFCs) have grown in recognition as a viable technology able to convert chemical energy directly into electricity, with higher efficiencies than conventional thermal engines. Direct feeding of the SOFCs anode with hydrocarbons from fossil or renewable sources, appears more attractive compared to the use of hydrogen as a fuel. The addition of mixed oxide-ion/electron conductors, like gadolinium-doped ceria (GDC), to commonly used nickel-based anodes is a well–known strategy that significantly enhances the performance of the SOFCs. Here we provide in situ experimental evidence of the active surface oxidation state and composition of Ni/GDC anodes during methane electroxidation using realistic solid oxide electrode assemblies. Ambient pressure X-ray photoelectron and near edge X-ray absorption fine structure spectroscopies (APPES and NEXAFS respectively) combined with on line electrical and gas phase measurements, were used to directly associate the surface state and the electrocatalytic performance of Ni/GDC anodes working at intermediate temperatures (700°C). A reduced anode surface (Ce3+ and Ni), with an optimum Ni to Ce surface composition, were found to be the most favorable configuration for maximum cell currents. Experimental results are rationalized on the basis of first principles calculations, proposing a detailed mechanism of the cell function.