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

Bostjan Genorio, Jakub Staszak-Jirkovský, Rajeev S. Assary, Justin G. Connell, Dusan Strmcnik, Charles E. Diesendruck, Pietro P. Lopes, Vojislav R. Stamenkovic, Jeffrey S. Moore, Larry A. Curtiss, Nenad M. Markovic

Research output: Contribution to journalArticlepeer-review


Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O2-) electrochemistry at atomic and molecular levels. Here, 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. 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.

Original languageEnglish (US)
Pages (from-to)15909-15914
Number of pages6
JournalJournal of Physical Chemistry C
Issue number29
StatePublished - Jul 28 2016

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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