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

Abstract

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.

Authors:
 [1];  [1];  [2];  [1];  [3];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Univ. of Sao Paulo (Brazil). Inst. de Quimica de Sao Carlos
  3. Univ. of Sao Paulo (Brazil). Inst. de Quimica de Sao Carlos
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
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
OSTI Identifier:
1459887
Alternate Identifier(s):
OSTI ID: 1549313
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Electroanalytical Chemistry
Additional Journal Information:
Journal Volume: 819; Journal Issue: C; Journal ID: ISSN 1572-6657
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dissolution mechanism; Dynamics of dissolution; Oxide formation/reduction; Pt redeposition kinetics; Pt single-crystals; Structure-Stability relationships

Citation Formats

Lopes, Pietro P., Tripkovic, Dusan, Martins, Pedro F. B. D., Strmcnik, Dusan, Ticianelli, Edson A., Stamenkovic, Vojislav R., and Markovic, Nenad M. Dynamics of electrochemical Pt dissolution at atomic and molecular levels. United States: N. p., 2017. Web. doi:10.1016/j.jelechem.2017.09.047.
Lopes, Pietro P., Tripkovic, Dusan, Martins, Pedro F. B. D., Strmcnik, Dusan, Ticianelli, Edson A., Stamenkovic, Vojislav R., & Markovic, Nenad M. Dynamics of electrochemical Pt dissolution at atomic and molecular levels. United States. https://doi.org/10.1016/j.jelechem.2017.09.047
Lopes, Pietro P., Tripkovic, Dusan, Martins, Pedro F. B. D., Strmcnik, Dusan, Ticianelli, Edson A., Stamenkovic, Vojislav R., and Markovic, Nenad M. Sat . "Dynamics of electrochemical Pt dissolution at atomic and molecular levels". United States. https://doi.org/10.1016/j.jelechem.2017.09.047. https://www.osti.gov/servlets/purl/1459887.
@article{osti_1459887,
title = {Dynamics of electrochemical Pt dissolution at atomic and molecular levels},
author = {Lopes, Pietro P. and Tripkovic, Dusan and Martins, Pedro F. B. D. and Strmcnik, Dusan and Ticianelli, Edson A. and Stamenkovic, Vojislav R. and Markovic, Nenad M.},
abstractNote = {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.},
doi = {10.1016/j.jelechem.2017.09.047},
journal = {Journal of Electroanalytical Chemistry},
number = C,
volume = 819,
place = {United States},
year = {Sat Sep 23 00:00:00 EDT 2017},
month = {Sat Sep 23 00:00:00 EDT 2017}
}

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Works referenced in this record:

Energy and fuels from electrochemical interfaces
journal, December 2016

  • Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4738

Sustainability and in situ monitoring in battery development
journal, December 2016

  • Grey, C. P.; Tarascon, J. M.
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4777

Materials for solar fuels and chemicals
journal, December 2016

  • Montoya, Joseph H.; Seitz, Linsey C.; Chakthranont, Pongkarn
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4778

Glucose oxidase: an ideal enzyme
journal, January 1992


Electrochemical biosensors: Towards point-of-care cancer diagnostics
journal, April 2006


Additive Manufacturing of Metal Structures at the Micrometer Scale
journal, January 2017

  • Hirt, Luca; Reiser, Alain; Spolenak, Ralph
  • Advanced Materials, Vol. 29, Issue 17
  • DOI: 10.1002/adma.201604211

Electroactive conducting polymers for corrosion control: Part 1. General introduction and a review of non-ferrous metals
journal, July 2001

  • Tallman, Dennis E.; Spinks, Geoff; Dominis, Anton
  • Journal of Solid State Electrochemistry, Vol. 6, Issue 2
  • DOI: 10.1007/s100080100212

Electroactive conducting polymers for corrosion control: Part 2. Ferrous metals
journal, July 2001

  • Spinks, Geoffrey M.; Dominis, Anton J.; Wallace, Gordon G.
  • Journal of Solid State Electrochemistry, Vol. 6, Issue 2
  • DOI: 10.1007/s100080100211

Preparation of monocrystalline Pt microelectrodes and electrochemical study of the plane surfaces cut in the direction of the {111} and {110} planes
journal, February 1980

  • Clavilier, J.; Faure, R.; Guinet, G.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 107, Issue 1
  • DOI: 10.1016/S0022-0728(79)80022-4

The role of anion on the electrochemical behaviour of a {111} platinum surface; an unusual splitting of the voltammogram in the hydrogen region
journal, February 1980


Interfaces in Electrochemistry
journal, April 1980

  • Parsons, Roger
  • Journal of The Electrochemical Society, Vol. 127, Issue 4
  • DOI: 10.1149/1.2129755

The Interface between Mercury and Aqueous Perchloric Acid
journal, December 1975


The electrical double layer at solid/liquid interfaces
journal, February 1981


Structural effects on adsorption at the solid metal/electrolyte interface
journal, July 1983


Adsorption phenomena in electrochemistry
journal, December 1980


Formic acid oxidation on single crystal platinum electrodes. Comparison with polycrystalline platinum
journal, July 1981

  • Clavilier, J.; Parsons, R.; Durand, R.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 124, Issue 1-2
  • DOI: 10.1016/S0022-0728(81)80311-7

Structural effects in electrocatalysis
journal, July 1983

  • Lamy, C.; Leger, J. M.; Clavilier, J.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2
  • DOI: 10.1016/S0022-0728(83)80191-0

Anisotropic electroreflectance of single crystal gold electrodes
journal, September 1978

  • Nguyen Van Huong, C.; Hinnen, C.; Lecoeur, J.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 92, Issue 2
  • DOI: 10.1016/S0022-0728(78)80183-1

The behaviour of water at stepped surfaces of single crystal gold electrodes
journal, January 1982


Mechanismus der Elektrolytischen Wasserstoffabscheidung und Adsorptionsenergie von Atomarem Wasserstoff
journal, January 1958


The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen
journal, January 1958

  • Parsons, Roger
  • Transactions of the Faraday Society, Vol. 54, p. 1053-1063
  • DOI: 10.1039/tf9585401053

Oxygen Reduction on Platinum Low-Index Single-Crystal Surfaces in Sulfuric Acid Solution: Rotating Ring-Pt(hkl) Disk Studies
journal, March 1995

  • Markovic, Nenad M.; Gasteiger, Hubert A.; Ross, Philip N.
  • The Journal of Physical Chemistry, Vol. 99, Issue 11, p. 3411-3415
  • DOI: 10.1021/j100011a001

Hydrogen electrochemistry on platinum low-index single-crystal surfaces in alkaline solution
journal, January 1996

  • Markovića, Nenad M.; Sarraf, Stella T.; Gasteiger, Hubert A.
  • J. Chem. Soc., Faraday Trans., Vol. 92, Issue 20
  • DOI: 10.1039/FT9969203719

Surface science studies of model fuel cell electrocatalysts
journal, April 2002


Oxide growth dynamics at Pt(111) in absence of specific adsorption: A mechanistic study
journal, August 2013


Sequential Pt(111) oxide formation in perchloric acid: An electrochemical study of surface species inter-conversion
journal, January 2013


Electrochemical oxide film formation at noble metals as a surface-chemical process
journal, August 1995


When Small is Big: The Role of Impurities in Electrocatalysis
journal, September 2015


Structure-relationships in electrocatalysis: oxygen reduction and hydrogen oxidation reactions on Pt(111) and Pt(100) in solutions containing chloride ions
journal, March 2001


Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review
journal, July 2001


Surface orientation dependence of oxide film growth at platinum single crystals
journal, November 1992


I n s i t u scanning tunneling microscopy of platinum (111) surface with the observation of monatomic steps
journal, January 1990

  • Itaya, K.; Sugawara, S.; Sashikata, K.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 8, Issue 1
  • DOI: 10.1116/1.576378

Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments
journal, March 2016


Comprehensive study of the growth of thin oxide layers on Pt electrodes under well-defined temperature, potential, and time conditions
journal, April 2006


Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction
journal, November 2008

  • Strmcnik, Dusan S.; Tripkovic, Dusan V.; van der Vliet, Dennis
  • Journal of the American Chemical Society, Vol. 130, Issue 46
  • DOI: 10.1021/ja8032185

The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum
journal, August 2009

  • Strmcnik, D.; Kodama, K.; van der Vliet, D.
  • Nature Chemistry, Vol. 1, Issue 6
  • DOI: 10.1038/nchem.330

Stability Limits and Defect Dynamics in Ag Nanoparticles Probed by Bragg Coherent Diffractive Imaging
journal, February 2017


Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts
journal, May 2012

  • Subbaraman, Ram; Tripkovic, Dusan; Chang, Kee-Chul
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3313

Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011


Potential dependent surface structure of the Pt(1 1 1) electrolyte interface
journal, October 1994

  • Tidswell, I. M.; Markovic, N. M.; Ross, P. N.
  • Journal of Electroanalytical Chemistry, Vol. 376, Issue 1-2
  • DOI: 10.1016/0022-0728(94)03553-9

In situ X-ray scattering study of the Pt(111)-solution interface: Ordered anion structures and their influence on copper underpotential deposition
journal, April 1996


X-ray Crystal Truncation Rod Studies of Surface Oxidation and Reduction on Pt(111)
journal, March 2016

  • Liu, Yihua; Barbour, Andi; Komanicky, Vladimir
  • The Journal of Physical Chemistry C, Vol. 120, Issue 29
  • DOI: 10.1021/acs.jpcc.6b00492

In‐situ x‐ray reflectivity study of incipient oxidation of Pt(111) surface in electrolyte solutions
journal, March 1994

  • You, H.; Zurawski, D. J.; Nagy, Z.
  • The Journal of Chemical Physics, Vol. 100, Issue 6
  • DOI: 10.1063/1.466254

Structural effects on the surface oxidation processes at Pt single-crystal electrodes studied by X-ray photoelectron spectroscopy
journal, January 2011

  • Wakisaka, Mitsuru; Udagawa, Yu; Suzuki, Hirokazu
  • Energy & Environmental Science, Vol. 4, Issue 5
  • DOI: 10.1039/c0ee00756k

A surface‐electrochemical basis for the direct logarithmic growth law for initial stages of extension of anodic oxide films formed at noble metals
journal, December 1990

  • Conway, B. E.; Barnett, B.; Angerstein‐Kozlowska, H.
  • The Journal of Chemical Physics, Vol. 93, Issue 11
  • DOI: 10.1063/1.459319

Towards a comprehensive understanding of platinum dissolution in acidic media
journal, January 2014

  • Topalov, Angel A.; Cherevko, Serhiy; Zeradjanin, Aleksandar R.
  • Chem. Sci., Vol. 5, Issue 2
  • DOI: 10.1039/C3SC52411F

Oxygen reduction on stepped platinum surfaces in acidic media
journal, January 2007


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Identical-location TEM investigations of Pt/C electrocatalyst degradation at elevated temperatures
journal, November 2011

  • Schlögl, Katrin; Mayrhofer, Karl J. J.; Hanzlik, Marianne
  • Journal of Electroanalytical Chemistry, Vol. 662, Issue 2
  • DOI: 10.1016/j.jelechem.2011.09.003

Accelerated degradation of Pt3Co/C and Pt/C electrocatalysts studied by identical-location transmission electron microscopy in polymer electrolyte environment
journal, October 2015

  • Nikkuni, Flávio R.; Dubau, Laetitia; Ticianelli, Edson A.
  • Applied Catalysis B: Environmental, Vol. 176-177
  • DOI: 10.1016/j.apcatb.2015.04.035

Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation
journal, October 2007

  • Borup, Rod; Meyers, Jeremy; Pivovar, Bryan
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr050182l

Works referencing / citing this record:

Electrochemical On‐line ICP‐MS in Electrocatalysis Research
journal, December 2018

  • Kasian, Olga; Geiger, Simon; Mayrhofer, Karl J. J.
  • The Chemical Record, Vol. 19, Issue 10
  • DOI: 10.1002/tcr.201800162

Platinum Dissolution and Redeposition from Pt/C Fuel Cell Electrocatalyst at Potential Cycling
journal, January 2018

  • Pavlišič, Andraž; Jovanovič, Primož; Šelih, Vid Simon
  • Journal of The Electrochemical Society, Vol. 165, Issue 6
  • DOI: 10.1149/2.0191806jes

Dissolution of Platinum Single Crystals in Acidic Medium
journal, November 2019

  • Sandbeck, Daniel J. S.; Brummel, Olaf; Mayrhofer, Karl J. J.
  • ChemPhysChem, Vol. 20, Issue 22
  • DOI: 10.1002/cphc.201900866

Effect of Dwell Time and Scan Rate during Voltage Cycling on Catalyst Degradation in PEM Fuel Cells
journal, January 2018

  • Kneer, Alexander; Wagner, Nadja; Sadeler, Christian
  • Journal of The Electrochemical Society, Vol. 165, Issue 10
  • DOI: 10.1149/2.0651810jes

3D PtAu nanoframe superstructure as a high-performance carbon-free electrocatalyst
journal, January 2019

  • Yoo, Sungjae; Cho, Sanghyun; Kim, Dajeong
  • Nanoscale, Vol. 11, Issue 6
  • DOI: 10.1039/c8nr08231f

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation
journal, August 2019

  • Abdelrahman, Areeg; Hermann, Johannes M.; Jacob, Timo
  • ChemPhysChem, Vol. 20, Issue 22
  • DOI: 10.1002/cphc.201900560

Thermodynamics of the formation of surface PtO 2 stripes on Pt(111) in the absence of subsurface oxygen
journal, January 2020

  • Hanselman, Selwyn; McCrum, Ian T.; Rost, Marcel J.
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 19
  • DOI: 10.1039/c9cp05107d