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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

Journal Article · · Catalysis Today
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  1. Argonne National Lab. (ANL), Lemont, IL (United States)
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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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1245206
Alternate ID(s):
OSTI ID: 1396946
Journal Information:
Catalysis Today, Vol. 262, Issue C; ISSN 0920-5861
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 62 works
Citation information provided by
Web of Science

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Cited By (9)

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Unravelling the electrochemical double layer by direct probing of the solid/liquid interface journal August 2016
How cations affect the electric double layer and the rates and selectivity of electrocatalytic processes journal October 2019
Plasma-modified C-doped Co 3 O 4 nanosheets for the oxygen evolution reaction designed by Butler–Volmer and first-principle calculations journal January 2019
Effect of hydrophobic cations on the oxygen reduction reaction on single‒crystal platinum electrodes journal November 2018
Emergence of high ORR activity through controlling local density-of-states by alloying immiscible Au and Ir journal January 2019
Carbon‐Free Cathode Materials for Li−O 2 Batteries journal February 2019
Ab Initio Cyclic Voltammetry on Cu(111), Cu(100) and Cu(110) in Acidic, Neutral and Alkaline Solutions journal September 2019
Pyrrolidone Modifying Gold Nanocatalysts for Enhanced Catalytic Activities in Aerobic Oxidation of Alcohols and Carbon Monoxide journal January 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalysis
surface spectators
non-covalent interactions
cation effect
oxygen reduction
ethanol