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Title: Double layer effects in electrocatalysis: The oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations

Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OHad and alkali metal cations (AMCn+), we were able to gain deep insights into the multiple roles that OHad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OHad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OHad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formation of a “true oxide” layer at higher electrode potentials. Although OHad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li+) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na+, without changing the product distribution for the reaction. This cation effect suggests that OHad—Li+(H2O)x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Finally, our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.
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  1. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
OSTI Identifier:
Grant/Contract Number:
AC02-06CH11357; AC0206CH11357
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 262; Journal Issue: C; Journal ID: ISSN 0920-5861
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Materials Sciences and Engineering Division
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; surface spectators; non-covalent interactions; cation effect; oxygen reduction; ethanol