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.

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This work was supported by the NSFC (21522508, 21427813, 21521004, 21533006, 21621091 and 21775127), “111” Project (B17027), Natural Science Foundation of Guangdong Province (2016A030308012), the Fundamental Research Funds for the Central Universities (20720180037), and the Thousand Youth Talents Plan of China. Support from MINECO and Generalitat Valenciana (Spain), through projects CTQ2016–76221-P (AEI/FEDER, UE) and PROMETEOII/2014/013, respectively, is greatly acknowledged. V.B.-M. acknowledges MINECO for the award of a pre-doctoral grant (BES-2014–068176, project CTQ2013–44803-P). We thank H. Zhang, M. Su, Y. H. Wang, J. Cheng, G. Attard, B. Ren, Z.Y. Zou, B.A. Lu and X.D. Yang for discussions.

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  1. MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    • Jin-Chao Dong
    • , Xia-Guang Zhang
    • , Xi Jin
    • , Ji Yang
    • , De-Yin Wu
    • , Zhong-Qun Tian
    •  & Jian-Feng Li
  2. Instituto de Electroquímica, Universidad de Alicante, Alicante, Spain

    • Valentín Briega-Martos
    •  & Juan Miguel Feliu
  3. Department of Physics, Research Institute for Biomimetics and Soft Matter, Xiamen University, Xiamen, China

    • Shu Chen
    • , Zhi-Lin Yang
    •  & Jian-Feng Li
  4. Department of Chemical Engineering, University of South Carolina, Columbia, SC, USA

    • Christopher T. Williams
  5. Shenzhen Research Institute of Xiamen University, Shenzhen, China

    • Jian-Feng Li


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J.-C.D., V.B.-M. and J.Y. carried out the experiments. X.-G.Z., X.J. and D.-Y.W. conducted the DFT calculations. S.C. and Z.-L.Y. conducted the FDTD simulations. J.M.F, C.T.W, J.-F.L. and Z.-Q.T. designed the experiments. All authors contributed to the preparation of the manuscript.

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The authors declare no competing interests.

Corresponding authors

Correspondence to Juan Miguel Feliu or Jian-Feng Li.

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