Oxygen Reduction Reaction on Au Revisited at Different pH Values using in situ Surface-Enhanced Raman Spectroscopy

The mechanisms of the oxygen reduction reaction (ORR) on Au surfaces are revisited in electrolytes with different pH values by using a combination of electrochemical and in situ surface-enhanced Raman scattering spectroscopy. Surprisingly, the in situ Raman signal of the O-O stretching vibration was detected during the ORR on a Au surface by using a λ=785 nm laser. Both the intermediate products O₂ ^- and H₂ O₂ could be detected, which indicates the difficulty of the further reduction H₂ O₂ and results in a lower electron transfer number, especially in neutral and acid electrolytes. The weak absorption ability of HO₂ on the Au surface may explain the poor ORR in neutral and acid electrolytes. This work not only provides a deep insight to understand the reduction mechanisms of O₂ on Au in electrolytes with different pH values but also supplies a new idea for the selection and optimization of electrolytes and efficient electrocatalysts for oxygen reduction.