  We use photo-electrons as a non-contact probe to measure local electrical
potentials in a solid-oxide electrochemical cell. We characterize the cell in
operando at near-ambient pressure using spatially-resolved X-ray photoemission
spectroscopy. The overpotentials at the interfaces between the Ni and Pt
electrodes and the yttria-stabilized zirconia (YSZ) electrolyte are directly
measured. The method is validated using electrochemical impedance spectroscopy.
Using the overpotentials, which characterize the cell's inefficiencies, we
compare without ambiguity the electro-catalytic efficiencies of Ni and Pt,
finding that on Ni H_2O splitting proceeds more rapidly than H2 oxidation,
while on Pt, H2 oxidation proceeds more rapidly than H2O splitting.
