Platinum hydride formation during cathodic corrosion in aqueous solutions

Thomas J P Hersbach; Angel T Garcia-Esparza; Selwyn Hanselman; Oscar A Paredes Mellone; Thijs Hoogenboom; Ian T McCrum; Dimitra Anastasiadou; Jeremy T Feaster; Thomas F Jaramillo; John Vinson; Thomas Kroll; Amanda C Garcia; Petr Krtil; Dimosthenis Sokaras; Marc T M Koper

doi:10.1038/s41563-024-02080-y

Platinum hydride formation during cathodic corrosion in aqueous solutions

Nat Mater. 2025 Jan 22. doi: 10.1038/s41563-024-02080-y. Online ahead of print.

Authors

Thomas J P Hersbach^{1

2}, Angel T Garcia-Esparza², Selwyn Hanselman¹, Oscar A Paredes Mellone², Thijs Hoogenboom^{1

3}, Ian T McCrum⁴, Dimitra Anastasiadou¹, Jeremy T Feaster^{5

6

7}, Thomas F Jaramillo^{5

6}, John Vinson⁸, Thomas Kroll², Amanda C Garcia^{1

9}, Petr Krtil¹⁰, Dimosthenis Sokaras¹¹, Marc T M Koper¹²

Affiliations

¹ Leiden Institute of Chemistry, Leiden University, Leiden, The Netherlands.
² Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
³ Leiden Institute of Physics, Leiden University, Leiden, The Netherlands.
⁴ Department of Chemical and Biomolecular Engineering, Clarkson University, Potsdam, NY, USA.
⁵ SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
⁶ Department of Chemical Engineering, Stanford University, Stanford, CA, USA.
⁷ Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, USA.
⁸ Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA.
⁹ Faculty of Science, Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, The Netherlands.
¹⁰ J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Prague, Czech Republic.
¹¹ Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. [email protected].
¹² Leiden Institute of Chemistry, Leiden University, Leiden, The Netherlands. [email protected].

PMID: 39843682
DOI: 10.1038/s41563-024-02080-y

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.