Influence of electrode potential on the electrochemical behavior of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF₄) solution containing 5 wt % 1-ethyl-3-methylimidazolium bromide (EMImBr) has been investigated using electrochemical and synchrotron-initiated high-resolution in situ X-ray photoelectron spectroscopy (XPS) methods. Observation of the Br 3d5/2 in situ XPS signal, collected in a 5 wt % EMImBr solution at an EMImBF₄⁻vacuum interface, enabled the detection of the start of the electrooxidation process of the Br⁻ anion to Br₃⁻ anion and thereafter to the Br₂ at the micro-mesoporous carbon electrode, polarized continuously at the high fixed positive potentials. A new photoelectron peak, corresponding to B⁻O bond formation in the B 1s in situ XPS spectra at E ≤ ⁻1.17 V, parallel to the start of the electroreduction of the residual water at the micro-mesoporous carbon electrode, was observed and is discussed. The electroreduction of the residual water caused a reduction in the absolute value of binding energy vs. potential plot slope twice to ca. dBE dE-1 = ⁻0.5 eV V-1 at E ≤ ⁻1.17 V for C 1s, N 1s, B 1s, F 1s, and Br 3d5/2 photoelectrons.
Keywords: binding energies; cyclic voltammetry; electrochemical impedance spectroscopy; in situ X-ray photoelectron spectroscopy; micro-mesoporous carbon electrode; room temperature ionic liquids; supercapacitor materials.