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

Nature Energy volume 4, pages 60–67 (2019)Cite this article

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Abstract

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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Fig. 1: Schematic illustration of the SHINERS study of the ORR process and correlated characterization and 3D-FDTD results at Pt(hkl) surfaces.
Fig. 2: Electrochemical results of the ORR process at Pt(hkl) surfaces in acidic conditions and correlated EC-SHINERS and DFT results of the ORR at a Pt(111) surface.
Fig. 3: In situ EC-SHINERS results of the ORR at Pt(100) and Pt(110) surfaces in acidic conditions and DFT result of OH* at a Pt(110) surface.
Fig. 4: EC-SHINERS study of the ORR at Pt(hkl) surfaces in alkaline conditions.
Fig. 5: The proposed mechanism of the ORR at Pt(hkl) surfaces in a 0.1 M HClO4 solution and relevant Gibbs free energy (eV) of different intermediates at Pt(hkl) surfaces.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

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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Authors and Affiliations

  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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Contributions

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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Correspondence to Juan Miguel Feliu or Jian-Feng Li.

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Supplementary Notes 1–14, Supplementary Figures 1–25, Supplementary Tables 1–6, Supplementary References

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Dong, JC., Zhang, XG., Briega-Martos, V. et al. In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces. Nat Energy 4, 60–67 (2019). https://doi.org/10.1038/s41560-018-0292-z

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