The effects of sulphur adsorbates and other typical solid oxide fuel cell (SOFC) poisons on the electronic and ionic properties of an SrO-terminated (La,Sr)CoO3 (LSC) surface and on its oxygen exchange kinetics have been investigated experimentally with near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), low energy ion scattering (LEIS) and impedance spectroscopy as well as computationally with density functional theory (DFT). The experiment shows that trace amounts of sulphur in measurement atmospheres form SO2- 4 adsorbates and strongly deactivate a pristine LSC surface. They induce a work function increase, indicating a changing surface potential and a surface dipole. DFT calculations reveal that the main participants in these charge transfer processes are not sub-surface transition metals, but surface oxygen atoms. The study further shows that sulphate adsorbates strongly affect oxygen vacancy formation energies in the LSC (sub-)surface, thus affecting defect concentrations and oxygen transport properties. To generalize these results, the investigation was extended to other acidic oxides which are technologically relevant as SOFC cathode poisons, such as CO2 and CrO3. The results unveil a clear correlation of work function changes and redistributed charge with the Smith acidity of the adsorbed oxide and clarify fundamental mechanistic details of atomic surface modifications. The impact of acidic adsorbates on various aspects of the oxygen exchange reaction rate is discussed in detail.
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