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Title: Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments

Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O 2 ) electrochemistry at atomic and molecular levels. Here, in this work, a combination of experimental and theoretical techniques are used for rationalizing, and ultimately understanding, the complexity of superoxide anion (electro)chemistry in organic environments. By exploring the O 2 + e ↔ O 2 reaction on well-characterized metal single crystals (Au, Pt, Ir), Pt single crystal modified with a single layer of graphene (Graphene@Pt(111)), and glassy carbon (GC) in 1,2 dimethoxyethane (DME) electrolytes, we demonstrate that (i) the reaction is an outer-sphere process; (ii) the reaction product O 2 can “attack” any part of the DME molecule, i.e., the C–O bond via nucleophilic reaction and the C–H bond via radical hydrogen abstraction; (iii) the adsorption of carbon-based decomposition products and the extent of formation of a “solid electrolyte interface” (“SEI”) increases in the same order as the reactivity of the substrate, i.e., Pt(hkl)/Ir(hkl) » Au(hkl)/GC > Gaphene@Pt(111); and (iv) the formation of the “SEI” layer leads to irreversible superoxide electrochemistry on Pt(hkl) and Ir(hkl) surfaces. In conclusion, we believe this fundamental insight provides a pathway for the rational design of stablemore » organic solvents that are urgently needed for the development of a new generation of reliable and affordable battery systems.« less
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [3] ;  [2] ;  [2] ;  [3] ;  [2] ;  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; University of Ljubljana, Faculty of Chemistry and Chemical Technology (Slovenia)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  3. Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States). Department of Chemistry
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 29; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
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; 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; nucleophilic attack; outer-sphere reaction; radical hydrogen abstraction; solid electrolyte interface; solvent decomposition; superoxide anion; well-characterized interfaces
OSTI Identifier:
1352586

Genorio, Bostjan, Staszak-Jirkovský, Jakub, Assary, Rajeev S., Connell, Justin G., Strmcnik, Dusan, Diesendruck, Charles E., Lopes, Pietro P., Stamenkovic, Vojislav R., Moore, Jeffrey S., Curtiss, Larry A., and Markovic, Nenad M.. Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments. United States: N. p., Web. doi:10.1021/acs.jpcc.5b12230.
Genorio, Bostjan, Staszak-Jirkovský, Jakub, Assary, Rajeev S., Connell, Justin G., Strmcnik, Dusan, Diesendruck, Charles E., Lopes, Pietro P., Stamenkovic, Vojislav R., Moore, Jeffrey S., Curtiss, Larry A., & Markovic, Nenad M.. Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments. United States. doi:10.1021/acs.jpcc.5b12230.
Genorio, Bostjan, Staszak-Jirkovský, Jakub, Assary, Rajeev S., Connell, Justin G., Strmcnik, Dusan, Diesendruck, Charles E., Lopes, Pietro P., Stamenkovic, Vojislav R., Moore, Jeffrey S., Curtiss, Larry A., and Markovic, Nenad M.. 2016. "Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments". United States. doi:10.1021/acs.jpcc.5b12230. https://www.osti.gov/servlets/purl/1352586.
@article{osti_1352586,
title = {Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments},
author = {Genorio, Bostjan and Staszak-Jirkovský, Jakub and Assary, Rajeev S. and Connell, Justin G. and Strmcnik, Dusan and Diesendruck, Charles E. and Lopes, Pietro P. and Stamenkovic, Vojislav R. and Moore, Jeffrey S. and Curtiss, Larry A. and Markovic, Nenad M.},
abstractNote = {Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O2–) electrochemistry at atomic and molecular levels. Here, in this work, a combination of experimental and theoretical techniques are used for rationalizing, and ultimately understanding, the complexity of superoxide anion (electro)chemistry in organic environments. By exploring the O2 + e– ↔ O2– reaction on well-characterized metal single crystals (Au, Pt, Ir), Pt single crystal modified with a single layer of graphene (Graphene@Pt(111)), and glassy carbon (GC) in 1,2 dimethoxyethane (DME) electrolytes, we demonstrate that (i) the reaction is an outer-sphere process; (ii) the reaction product O2– can “attack” any part of the DME molecule, i.e., the C–O bond via nucleophilic reaction and the C–H bond via radical hydrogen abstraction; (iii) the adsorption of carbon-based decomposition products and the extent of formation of a “solid electrolyte interface” (“SEI”) increases in the same order as the reactivity of the substrate, i.e., Pt(hkl)/Ir(hkl) » Au(hkl)/GC > Gaphene@Pt(111); and (iv) the formation of the “SEI” layer leads to irreversible superoxide electrochemistry on Pt(hkl) and Ir(hkl) surfaces. In conclusion, we believe this fundamental insight provides a pathway for the rational design of stable organic solvents that are urgently needed for the development of a new generation of reliable and affordable battery systems.},
doi = {10.1021/acs.jpcc.5b12230},
journal = {Journal of Physical Chemistry. C},
number = 29,
volume = 120,
place = {United States},
year = {2016},
month = {2}
}