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Inverse kinetic isotope effects in the oxygen reduction reaction at platinum single crystals

Nature Chemistry volume 15, pages 271–277 (2023)Cite this article

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Abstract

Although the oxygen reduction reaction (ORR) involves multiple proton-coupled electron transfer processes, early studies reported the absence of kinetic isotope effects (KIEs) on polycrystalline platinum, probably due to the use of unpurified D2O. Here we developed a methodology to prepare ultra-pure D2O, which is indispensable for reliably investigating extremely surface-sensitive platinum single crystals. We find that Pt(111) exhibits much higher ORR activity in D2O than in H2O, with potential-dependent inverse KIEs of ~0.5, whereas Pt(100) and Pt(110) exhibit potential-independent inverse KIEs of ~0.8. Such inverse KIEs are closely correlated to the lower *OD coverage and weakened *OD binding strength relative to *OH, which, based on theoretical calculations, are attributed to the differences in their zero-point energies. This study suggests that the competing adsorption between *OH/*OD and *O2 probably plays an important role in the ORR rate-determining steps that involve a chemical step preceding an electrochemical step (CE mechanism).

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Fig. 1: Cyclic voltammetric profiles of platinum single crystals in acidic ultra-high-purity H2O and D2O.
Fig. 2: Oxygen reduction reaction kinetics on platinum single crystals in acidic ultra-high-purity H2O and D2O.
Fig. 3: Carbon monoxide electrooxidation kinetics on platinum single crystals in acidic ultra-high-purity H2O and D2O.
Fig. 4: Cyclic voltammetric profiles of Pt(111) in alkaline media and theoretical calculations of OH and OD adsorption.

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Acknowledgements

This work was primarily supported by the Center for Alkaline-Based Energy Solutions (CABES), part of the Energy Frontier Research Center (EFRC) program supported by the US Department of Energy, under grant no. DE-SC-0019445. R.G.A. and J.M.M. acknowledge funding from the Molecular Electrochemistry Multi-University Research Initiative (MURI) supported by the US Air Force Office of Scientific Research, under grant nos. FA9550-18-1-0420; the US National Science Foundation award no. CHE-1904813 for support; and a supplement that supported R.G.A’s visit to the Koper laboratory in Leiden. P.H. and R.G. A acknowledge support from National Science Foundation Graduate Research Fellowships. R.R, E.H and J.M.F. acknowledge funding from Ministerio de Ciencia e Innovación (Spain) under grant no. PID2019-105653GB-I00. R.G.A. would also like to thank M. Koper and the members of his laboratory for their hospitality during his short stay in Leiden, and for introducing him to the challenges of preparing high-purity D2O.

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  1. These authors contributed equally: Yao Yang, Rishi G. Agarwal, Phillips Hutchison, Rubén Rizo.

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    Yao Yang, Xinyao Lu & Héctor D. Abruña

  2. Department of Chemistry, Yale University, New Haven, CT, USA

    Rishi G. Agarwal, Phillips Hutchison, Alexander V. Soudackov, Sharon Hammes-Schiffer & James M. Mayer

  3. Instituto de Electroquímica, Universidad de Alicante, Alicante, Spain

    Rubén Rizo, Enrique Herrero & Juan M. Feliu

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  1. Yao Yang
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Contributions

Y.Y. and H.D.A. conceived the project. Y.Y. performed electrochemical measurements with help from X.L. R.R. independently verified the experimental results under the guidance of E.H. and J.M.F. R.G.A. developed the D2O purification method under the guidance of J.M.M. P.H. and A.V.S performed DFT simulations under the guidance of S.H.-S. All of the authors discussed the results and approved the manuscript.

Corresponding authors

Correspondence to Enrique Herrero, Juan M. Feliu, Sharon Hammes-Schiffer, James M. Mayer or Héctor D. Abruña.

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Extended data

Extended Data Fig. 1 A simplified mechanisms proposed for the oxygen reduction reaction (ORR) in acid.

Reaction pathways have been established based on extensive studies on Pt surfaces and may be applicable to other types of catalysts. A superscript * by an intermediate indicates a reaction intermediate adsorbed on the electrocatalytic surface. The CE mechanism in acid, marked in green, represents a fast surface chemical reaction preceding an irreversible one−electron transfer process. PCET stands for proton-coupled electron transfer process. H2O serves as the proton donor in alkaline media. Solution species were not included for simplicity. Complete ORR mechanisms in acid and base can be found in Supplementary Fig. 5.

Extended Data Fig. 2 Comparisons of ORR polarization profiles of three low-index Pt single crystals in acidic H2O and D2O.

Comparisons of ORR polarization profiles of three low-index Pt single crystals in O2-saturated 0.1 M HClO4 in H2O (A) and D2O (B).

Source data

Extended Data Fig. 3 Potential axis.

Potential axis showing that the RDeE is equal to the RHE in acid (for example 0.1 M HClO4, pH = 1) but is more negative than the RHE by 51 mV in base (for example 0.1 M NaOH, pH = 13) due to due to the difference in pKa in H2O (14) and D2O (14.87).

Extended Data Fig. 4 Tafel plots of Pt(111) and *OD/*OH adsorption coverage in base.

(A) Tafel plots of Pt(111) in O2-sat. 0.1 M NaOH in H2O and D2O at 1600 rpm based ORR polarization profiles in Supplementary Fig. 6. (B) *OD and *OH adsorption coverage on Pt(111) in alkaline D2O and H2O as a function of potentials extracted from Fig. 4A.

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Supplementary Notes, Figs. 1–6, Tables 1–11, equations 1–3 and refs. 73–77.

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Yang, Y., Agarwal, R.G., Hutchison, P. et al. Inverse kinetic isotope effects in the oxygen reduction reaction at platinum single crystals. Nat. Chem. 15, 271–277 (2023). https://doi.org/10.1038/s41557-022-01084-y

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