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Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Nature Materials volume 21, pages 88–94 (2022)Cite this article

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Abstract

Theoretical descriptors differentiate the catalytic activity of materials for the oxygen evolution reaction by the strength of oxygen binding in the reactive intermediate created upon electron transfer. Recently, time-resolved spectroscopy of a photo-electrochemically driven oxygen evolution reaction followed the vibrational and optical spectra of this intermediate, denoted M-OH*. However, these inherently kinetic experiments have not been connected to the relevant thermodynamic quantities. Here we discover that picosecond optical spectra of the Ti-OH* population on lightly doped SrTiO3 are ordered by the surface hydroxylation. A Langmuir isotherm as a function of pH extracts an effective equilibrium constant relatable to the free energy difference of the first oxygen evolution reaction step. Thus, time-resolved spectroscopy of the catalytic surface reveals both kinetic and energetic information of elementary reaction steps, which provides a critical new connection between theory and experiment by which to tailor the pathway of water oxidation and other surface reactions.

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Fig. 1: Photo-electrochemical configuration and optical spectra.
Fig. 2: SVD and rotation analysis.
Fig. 3: Constrained SVD analysis and extraction of 2 ps Ti-OH* population.
Fig. 4: Langmuir isotherm model and the effective equilibrium constant (K).

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Data availability

The representative data and all of the analyses from the extended dataset that support the findings of this paper are available in the paper and the Supplementary Information. The extended dataset that supports the findings in this paper is available from the corresponding authors on reasonable request.

Change history

  • 25 November 2021

    In the version of this article now appearing online, various notation errors have been corrected to improve readability. No data or conclusions are affected.

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Acknowledgements

The experimental work was supported by the Director, Office of Science, Office of Basic Energy Sciences and by the Division of Chemical Sciences, Geosciences and Biosciences of the US Department of Energy at the Renewable and Sustainable Energy Institute (RASEI; Boulder, CO) under contract no. DE-SC0018939 awarded to T.C. This included full support for one postdoctoral fellow and one graduate student, and partial support for another graduate student. We thank C. D. Pemmaraju and H. Frei for helpful discussions.

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Authors and Affiliations

  1. Renewable and Sustainable Energy Institute (RASEI), University of Colorado, Boulder, Boulder, CO, USA

    Ilya Vinogradov, Suryansh Singh, Hanna Lyle, Michael Paolino, Aritra Mandal & Tanja Cuk

  2. Materials Science and Engineering Program, University of Colorado, Boulder, Boulder, CO, USA

    Suryansh Singh, Hanna Lyle & Tanja Cuk

  3. Department of Physics, University of Colorado, Boulder, Boulder, CO, USA

    Michael Paolino

  4. Department of Chemistry, University of Copenhagen, Copenhagen, Denmark

    Jan Rossmeisl

  5. Department of Chemistry, University of Colorado, Boulder, Boulder, CO, USA

    Tanja Cuk

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Contributions

T.C. conceived of the project, managed the data collection process and wrote the manuscript with the input of all authors. I.V., S.S. and H.L. constructed the transient set-up and collected the transient data. M.P. helped collect the transient data on the highly doped samples. I.V. and A.M. processed the results and analysed the data using principal component analyses. T.C., with input from J.R., developed the theoretical model. J.R. placed the results in the context of previous theoretical models.

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Correspondence to Aritra Mandal or Tanja Cuk.

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Peer review information Nature Materials thanks Bert Weckhuysen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–18 and Sections I–X.

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Vinogradov, I., Singh, S., Lyle, H. et al. Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy. Nat. Mater. 21, 88–94 (2022). https://doi.org/10.1038/s41563-021-01118-9

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