In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces

Developing an understanding of structure–activity relationships and reaction mechanisms of catalytic processes is critical to the successful design of highly efficient catalysts. As a fundamental reaction in fuel cells, elucidation of the oxygen reduction reaction (ORR) mechanism at Pt(hkl) surfaces has remained a significant challenge for researchers. Here, we employ in situ electrochemical surface-enhanced Raman spectroscopy (SERS) and density functional theory (DFT) calculation techniques to examine the ORR process at Pt(hkl) surfaces. Direct spectroscopic evidence for ORR intermediates indicates that, under acidic conditions, the pathway of ORR at Pt(111) occurs through the formation of HO2*, whereas at Pt(110) and Pt(100) it occurs via the generation of OH*. However, we propose that the pathway of the ORR under alkaline conditions at Pt(hkl) surfaces mainly occurs through the formation of O2−. Notably, these results demonstrate that the SERS technique offers an effective and reliable way for real-time investigation of catalytic processes at atomically flat surfaces not normally amenable to study with Raman spectroscopy. The oxygen reduction reaction, catalysed by platinum, is a crucial process in the operation of fuel cells, but the mechanistic pathways through which it occurs remain a matter for debate. Here, the authors use in situ Raman spectroscopy to identify key intermediates for this reaction at different atomically flat platinum surfaces, shedding light on the mechanism.