Dynamics of electrochemical Pt dissolution at atomic and molecular levels

Lopes, Pietro P.; Tripkovic, Dusan; Martins, Pedro F. B. D.; Strmcnik, Dusan; Ticianelli, Edson A.; Stamenkovic, Vojislav R.; Markovic, Nenad M.

doi:10.1016/j.jelechem.2017.09.047

Title: Dynamics of electrochemical Pt dissolution at atomic and molecular levels

Journal Article · Sat Sep 23 00:00:00 EDT 2017 · Journal of Electroanalytical Chemistry

DOI:https://doi.org/10.1016/j.jelechem.2017.09.047· OSTI ID:1459887

Lopes, Pietro P. ^[1]; Tripkovic, Dusan ^[1]; Martins, Pedro F. B. D. ^[2]; Strmcnik, Dusan ^[1]; Ticianelli, Edson A. ^[3]; Stamenkovic, Vojislav R. ^[1]; Markovic, Nenad M. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Univ. of Sao Paulo (Brazil). Inst. de Quimica de Sao Carlos
Univ. of Sao Paulo (Brazil). Inst. de Quimica de Sao Carlos

Understanding and controlling electrochemical interfaces at atomic and molecular levels have transformed electrochemistry into a science with clearly defined fundamental principles leading to significant impact on various electrochemical systems and devices. Although the principles guiding the activity of electrochemical reactions are quite well established, the driving forces that control stability are still poorly understood. Here we utilize in situ monitoring of the early stages of Pt dissolution using the stationary probe rotating disk electrode technique coupled to inductively coupled plasma mass spectrometry (SPRDE-ICPMS). Our unique SPRDE-ICPMS method provides picogram sensitivity levels that, in combination with STM, provide otherwise inaccessible information about the dissolution and redeposition of Pt(111) in acidic environments. We propose two distinct dissolution mechanisms that are active during oxide formation and subsequent oxide reduction. Whereas an electrochemical dissolution mechanism is observed during anodic Pt dissolution (Pt→Pt²⁺+2e^-), a combination of electrochemical (PtO*+2H⁺+2e^-→Pt⁰+H₂O) and chemical (PtO*+2H⁺→Pt²⁺+H₂O) steps control the dissolution of Pt during the cathodic scan. The redeposition of Pt (Pt²⁺+2e^-→Pt) observed on the cathodic scan is controlled by a delicate balance between the diffusion of Pt²⁺ from the double layer and redeposition of Pt²⁺ on Pt oxide-free sites.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1459887

Alternate ID(s):: OSTI ID: 1549313

Journal Information:: Journal of Electroanalytical Chemistry, Vol. 819, Issue C; ISSN 1572-6657

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 57 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dissolution mechanism
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Title: Dynamics of electrochemical Pt dissolution at atomic and molecular levels

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