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Optical method for quantifying the potential of zero charge at the platinum–water electrochemical interface

Nature Materials volume 22, pages 503–510 (2023)Cite this article

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Abstract

When an electrode contacts an electrolyte, an interfacial electric field forms. This interfacial field can polarize the electrode’s surface and nearby molecules, but its effect can be countered by an applied potential. Quantifying the value of this countering potential (‘potential of zero charge’ (pzc)) is, however, not straightforward. Here we present an optical method for determining the pzc at an electrochemical interface. Our approach uses phase-sensitive second-harmonic generation to determine the electrochemical potential where the interfacial electric field vanishes at an electrode–electrolyte interface with Pt–water as a model experiment. Our method reveals that the pzc of the Pt–water interface is 0.23 ± 0.08 V versus standard hydrogen electrode (SHE) and is pH independent from pH 1 to pH 13. First-principles calculations with a hybrid explicit–implicit solvent model predict the pzc of the Pt(111)–water interface to be 0.23 V versus SHE and reveal how the interfacial water structure rearranges as the electrode potential is moved above and below the pzc. We further show that pzc is sensitive to surface modification; deposition of Ni on Pt shifts the interfacial pzc in the cathodic direction by ~360 mV. Our work demonstrates a materials-agnostic approach for quantifying the interfacial electrical field and water orientation at an electrochemical interface without requiring probe molecules and confirms the long-held view that the interfacial electric field is more intense during hydrogen electrocatalysis in alkaline than in acid.

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Fig. 1: Overview of the proposed optical method for pzc determination.
Fig. 2: The potential-dependent SHG intensity and phase from the Pt surface in pH 1 solution.
Fig. 3: SHG study of the Pt surface in different pHs.
Fig. 4: Top and side views of (3 × 3) water adlayers on Pt(111) embedded in an implicit electrolyte and optimized at different surface charge densities (q).
Fig. 5: Potential-dependent SHG intensity and phase of a Pt electrode before and after Ni modification.

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The data for Figs. 2, 3 and 5 are provided in Source data. Any other data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported as part of the Center for Alkaline Based Energy Solutions, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award #DE-SC0019445. J.S. acknowledges the Sloan Research Fellowship. This work made use of the Cornell Center for Materials Research Shared Facilities which are supported through the Materials Research Science and Engineering Centers program from the National Science Foundation (DMR-1719875). The computational work was performed in part using supercomputing resources from the National Energy Research Scientific Computing Center (BES-ERCAP0019973), a DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory and operated under contract DE-AC02-05CH11231.

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Author notes

  1. These authors contributed equally: Pengtao Xu, Alexander D. von Rueden.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Cornell University, Ithaca, NY, USA

    Pengtao Xu & Jin Suntivich

  2. Department of Chemical and Biological Engineering, University of Wisconsin–Madison, Madison, WI, USA

    Alexander D. von Rueden, Roberto Schimmenti & Manos Mavrikakis

  3. Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, NY, USA

    Jin Suntivich

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Contributions

P.X. developed the phase-sensitive second-harmonic generation technique and performed the spectroscopic and electrochemical measurements and data processing. A.D.v.R. and R.S. designed and performed the theoretical modelling work. M.M. and J.S. supervised the project. All authors discussed the results and contributed to writing the manuscript. P.X. and A.D.v.R. contributed equally.

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Correspondence to Manos Mavrikakis or Jin Suntivich.

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Nature Materials thanks Xihan Chen, Jan Rossmeisl and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Xu, P., von Rueden, A.D., Schimmenti, R. et al. Optical method for quantifying the potential of zero charge at the platinum–water electrochemical interface. Nat. Mater. 22, 503–510 (2023). https://doi.org/10.1038/s41563-023-01474-8

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