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Title: Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments

The development of alternative energy systems for clean production, storage and conversion of energy is strongly dependent on our ability to understand, at atomic-molecular-levels, functional links between activity and stability of electrochemical interfaces. Whereas structure-activity relationships are rapidly evolving, the corresponding structure-stability relationships are still missing. Primarily, this is because there is no adequate experimental approach capable of monitoring in situ stability of well-defined single crystals. Here, by blending the power of Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) connected to a stationary probe to measure in situ and real time dissolution rates of surface atoms (at above 0.4 pg cm-2s-1 levels) and a rotating disk electrode method for monitoring simultaneously the kinetic rates of electrochemical reactions in a single unite, it was possible to establish almost “atom-by-atom” the structure-stability-activity relationships for platinum single crystals in both acidic and alkaline environments. Furthermore, we found that the degree of stability is strongly dependent on the coordination of surface atoms (less coordinated yields less stable), the nature of covalent (adsorption of hydroxyl, oxygen atoms and halides species), and non-covalent interactions (interactions between hydrated Li cations and surface oxide), the thermodynamic driving force for Pt complexation (Pt ion speciation in solution) and the nature ofmore » the electrochemical reaction (the oxygen reduction/evolution and CO oxidation reactions). Consequently, these findings are opening new opportunities for elucidating key fundamental descriptors that govern both activity and stability trends, that ultimately, will assist to develop real energy conversion and storage systems.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1352658

Lopes, Pietro P., Strmcnik, Dusan, Tripkovic, Dusan, Connell, Justin G., Stamenkovic, Vojislav, and Markovic, Nenad M.. Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments. United States: N. p., Web. doi:10.1021/acscatal.5b02920.
Lopes, Pietro P., Strmcnik, Dusan, Tripkovic, Dusan, Connell, Justin G., Stamenkovic, Vojislav, & Markovic, Nenad M.. Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments. United States. doi:10.1021/acscatal.5b02920.
Lopes, Pietro P., Strmcnik, Dusan, Tripkovic, Dusan, Connell, Justin G., Stamenkovic, Vojislav, and Markovic, Nenad M.. 2016. "Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments". United States. doi:10.1021/acscatal.5b02920. https://www.osti.gov/servlets/purl/1352658.
@article{osti_1352658,
title = {Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments},
author = {Lopes, Pietro P. and Strmcnik, Dusan and Tripkovic, Dusan and Connell, Justin G. and Stamenkovic, Vojislav and Markovic, Nenad M.},
abstractNote = {The development of alternative energy systems for clean production, storage and conversion of energy is strongly dependent on our ability to understand, at atomic-molecular-levels, functional links between activity and stability of electrochemical interfaces. Whereas structure-activity relationships are rapidly evolving, the corresponding structure-stability relationships are still missing. Primarily, this is because there is no adequate experimental approach capable of monitoring in situ stability of well-defined single crystals. Here, by blending the power of Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) connected to a stationary probe to measure in situ and real time dissolution rates of surface atoms (at above 0.4 pg cm-2s-1 levels) and a rotating disk electrode method for monitoring simultaneously the kinetic rates of electrochemical reactions in a single unite, it was possible to establish almost “atom-by-atom” the structure-stability-activity relationships for platinum single crystals in both acidic and alkaline environments. Furthermore, we found that the degree of stability is strongly dependent on the coordination of surface atoms (less coordinated yields less stable), the nature of covalent (adsorption of hydroxyl, oxygen atoms and halides species), and non-covalent interactions (interactions between hydrated Li cations and surface oxide), the thermodynamic driving force for Pt complexation (Pt ion speciation in solution) and the nature of the electrochemical reaction (the oxygen reduction/evolution and CO oxidation reactions). Consequently, these findings are opening new opportunities for elucidating key fundamental descriptors that govern both activity and stability trends, that ultimately, will assist to develop real energy conversion and storage systems.},
doi = {10.1021/acscatal.5b02920},
journal = {ACS Catalysis},
number = 4,
volume = 6,
place = {United States},
year = {2016},
month = {3}
}