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

Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; Connell, Justin G.; Stamenkovic, Vojislav; Markovic, Nenad

doi:10.1016/j.cattod.2015.09.010

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

Journal Article · Mon Sep 28 04:00:00 EDT 2015 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2015.09.010· OSTI ID:1245206

Lopes, Pietro P. ^[1]; Strmcnik, Dusan ^[1]; Jirkovsky, Jakub S. ^[1]; Connell, Justin G. ^[1]; Stamenkovic, Vojislav ^[1]; Markovic, Nenad ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)

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 OH_ad and alkali metal cations (AMCⁿ⁺), we were able to gain deep insights into the multiple roles that OH_ad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OH_ad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OH_ad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formation of a “true oxide” layer at higher electrode potentials. Although OH_ad 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 OH_ad—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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Materials Sciences and Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1245206

Alternate ID(s):: OSTI ID: 1396946

Journal Information:: Catalysis Today, Journal Name: Catalysis Today Journal Issue: C Vol. 262; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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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

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