Platinum dissolution and restructuring due to surface oxidation are primary degradation mechanisms that limit the lifetime of platinum-based electrocatalysts for electrochemical energy conversion. Here, we have studied well-defined Pt(100) and Pt(111) electrode surfaces by in situ high-energy surface X-ray diffraction, online inductively coupled plasma mass spectrometry and density functional theory calculations to elucidate the atomic-scale mechanisms of these processes. The locations of the extracted platinum atoms after Pt(100) oxidation reveal distinct differences from the Pt(111) case, which explains the different surface stability. The evolution of a specific oxide stripe structure on Pt(100) produces unstable surface atoms that are prone to dissolution and restructuring, leading to one order of magnitude higher dissolution rates.
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Communications Chemistry Open Access 13 October 2022
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The raw X-ray data as well as the atomic coordinates of the optimized computational models have been deposited in the repository https://doi.org/10.5281/zenodo.3937672. All other data supporting the findings of this study are available within the article and its Supplementary Information, or from the corresponding author upon reasonable request. Source data are provided with this paper.
The custom software for the analysis of the CTR data and the custom BINoculars backend for HESXRD structure factor determination are deposited in the repository https://doi.org/10.5281/zenodo.3941003. All other software used for this study is publicly available or can be obtained from the corresponding author upon reasonable request.
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We acknowledge the European Synchrotron Radiation Facility for provision of SXRD facilities, and H. Isern and T. Dufrane for their help with the SXRD experiments. Funding is acknowledged from the NSERC (grant no. RGPIN-2017-04045) and Deutsche Forschungsgemeinschaft (grant nos. MA 1618/23 and CH 1763/5-1). F.C.-V acknowledges funding from Spanish MICIUN RTI2018-095460-B-I00 and María de Maeztu MDM-2017-0767 grants, and thanks RES for supercomputing time at SCAYLE (projects QS-2019-3-0018, QS-2019-2-0023, and QCM-2019-1-0034) and MareNostrum (project QS-2020-1-0012). The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended Data Fig. 1 Cyclic voltammograms measured in the electrochemical cell used for the Surface X-ray Diffraction measurements.
Cyclic voltammograms of (a) Pt(100) and (b) Pt(111) in 0.1 M HClO4 with a scan rate of 50 mV/s.
Extended Data Fig. 2 Crystal truncation rods of Pt(100) at 0.12 V prior to surface oxidation and after oxide reduction.
Crystal truncation rods (CTR) of the pristine Pt(100) surface after sample preparation and the CTRs of the roughened Pt(100) surface after oxide formation at 1.17 V and subsequent oxide reduction at 0.12 V. The grey lines indicate the CTRs of a bulk terminated Pt(100) surface. The decrease of the CTR structure factor after surface oxidation can be attributed to the formation of adatoms Ptad and vacancies in the Pt1 layer. Best fits with a quantitative model (solid blue line) that includes these surface defects result in a Ptad coverage of 0.07 ML.
Extended Data Fig. 3 Crystal truncation rods (CTR) and corresponding CTR fits of Pt(100) close to and in the region of oxide formation.
CTRs of Pt(100) at a potential slightly negative (0.95 V) and three potentials positive (1.07, 1.12 and 1.17 V) of the Oads peak in the cyclic voltammogram (Fig. 1b, Extended Data Fig. 1). Solid lines are the corresponding CTR fits. The CTRs for the different potentials are offset to each other by a factor 10 and shown together with the CTR fits of the smooth surface at 0.95 V (grey lines). Details on the CTR fits are given in the Supplementary Note 3 and the corresponding structural parameters are given in Supplementary Table 4.
(a) Oxygen coverage θO dependent Gibbs energy ΔG for the extraction of the first atom on Pt(111) and Pt(100). (b) ΔG for the dissolution of the extracted atom after first extraction on Pt(111) and first, second and third extraction on Pt(100). The correspondence between the oxygen coverage θO and potential U is in the inset of (b).
Pourbaix diagram of (a) Pt(111) and (b) Pt(100). The dashed line represents the oxygen reduction reaction (O2 + 4(H+ + e−) → 2H2O).
Extended Data Fig. 6 Additional views of the lowest-energy structures in the process of Pt extraction.
(a) Top view of the Pt extraction process on Pt(111). (b) Side view of the Pt extraction process on Pt(100).
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Fuchs, T., Drnec, J., Calle-Vallejo, F. et al. Structure dependency of the atomic-scale mechanisms of platinum electro-oxidation and dissolution. Nat Catal 3, 754–761 (2020). https://doi.org/10.1038/s41929-020-0497-y
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