Abstract
Cathodic corrosion is an electrochemical phenomenon that etches metals at moderately negative potentials. Although cathodic corrosion probably occurs by forming a metal-containing anion, such intermediate species have not yet been observed. Here, aiming to resolve this long-standing debate, our work provides such evidence through X-ray absorption spectroscopy. High-energy-resolution X-ray absorption near-edge structure experiments are used to characterize platinum nanoparticles during cathodic corrosion in 10 mol l−1 NaOH. These experiments detect minute chemical changes in the Pt during corrosion that match first-principles simulations of X-ray absorption spectra of surface platinum multilayer hydrides. Thus, this work supports the existence of hydride-like platinum during cathodic corrosion. Notably, these results provide a direct observation of these species under conditions where they are highly unstable and where prominent hydrogen bubble formation interferes with most spectroscopy methods. Therefore, this work identifies the elusive intermediate that underlies cathodic corrosion.
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Data availability
All data used for this study are available within the Article and its Supplementary Information. Source data are provided with this paper. The data files are also available from the corresponding authors upon request.
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Acknowledgements
We acknowledge M.-Y. Wu from MYAnalysis for assisting with transmission electron microscopy measurements. Certain equipment, instruments, software or materials, commercial or non-commercial, are identified in this Article to specify the experimental procedure adequately. Such identification is not intended to imply recommendation or endorsement of any product or service by NIST, nor is it intended to imply that the materials or equipment identified are necessarily the best available for the purpose. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. This work was supported in part by the Netherlands Organization for Scientific Research (NWO) in the framework of the Solar Fuels Graduate Program. The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO. OCEAN simulations were performed using resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility operated under contract no. DE-AC02-05CH11231.
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T.J.P.H., D.S. and M.T.M.K. designed the experimental study. T.J.P.H. conducted and coordinated most of the experimental work, data analysis and data reduction. A.T.G.-E., O.A.P.M. and J.V. performed the OCEAN simulations activities. S.H. and I.T.M. generated the platinum surfaces for first-principles calculations. A.T.G.-E., D.A., J.T.F., T.F.J., A.C.G., P.K., T.K. and D.S. participated in the experimental work. T.H. designed the operando grazing incidence cell. T.J.P.H. led the drafting of the manuscript, with contributions from A.T.G.-E., S.H., J.V., D.S. and M.T.M.K. for editing. D.S. and M.T.M.K. supervised the work and obtained funding and resources. All authors discussed the results and the manuscript.
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Supplementary information
Supplementary Information
Supplementary Figs. 1–20, discussion and Table 1.
Supplementary Data 1
DFT coordinates used as OCEAN input structure files for Fig. 1a,c.
Supplementary Data 2
DFT coordinates used as OCEAN input structure files for Fig. 1b,d and Supplementary Figs. 8 and 12.
Supplementary Data 3
DFT coordinates used as OCEAN input structure files for Supplementary Fig. 10.
Source data
Source Data Fig. 1
OCEAN spectra and difference spectra for hydrogen-covered platinum surfaces and bulk platinides.
Source Data Fig. 2
Experimental HERFD-XANES spectra, smoothed experimental HERFD-XANES spectra and unsmoothed experimental HERFD-XANES spectra.
Source Data Fig. 3
Smoothed experimental HERFD-XANES difference spectra and rescaled OCEAN difference spectra for hydrogen-covered platinum surfaces and bulk platinides.
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Hersbach, T.J.P., Garcia-Esparza, A.T., Hanselman, S. et al. Platinum hydride formation during cathodic corrosion in aqueous solutions. Nat. Mater. 24, 574–580 (2025). https://doi.org/10.1038/s41563-024-02080-y
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DOI: https://doi.org/10.1038/s41563-024-02080-y
