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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
 [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:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 29; Journal ID: ISSN 1932-7447
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
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: