TY - JOUR
T1 - MnOx/IrOx as Selective Oxygen Evolution Electrocatalyst in Acidic Chloride Solution
AU - Vos, Johannes G.
AU - Wezendonk, Tim A.
AU - Jeremiasse, Adriaan W.
AU - Koper, Marc T.M.
PY - 2018
Y1 - 2018
N2 - The oxygen evolution reaction (OER) and chlorine evolution reaction (CER) are electrochemical processes with high relevance to water splitting for (solar) energy conversion and industrial production of commodity chemicals, respectively. Carrying out the two reactions separately is challenging, since the catalytic intermediates are linked by scaling relations. Optimizing the efficiency of OER over CER in acidic media has proven especially difficult. In this regard, we have investigated the OER versus CER selectivity of manganese oxide (MnOx), a known OER catalyst. Thin films (∼5-20 nm) of MnOx were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrOx/GC) in aqueous chloride solutions of pH ∼0.9. Using rotating ring-disk electrode voltammetry and online electrochemical mass spectrometry, it was found that deposition of MnOx onto IrOx decreases the CER selectivity of the system in the presence of 30 mM Cl- from 86% to less than 7%, making it a highly OER-selective catalyst. Detailed studies of the CER mechanism and ex-situ structure studies using SEM, TEM, and XPS suggest that the MnOx film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions.
AB - The oxygen evolution reaction (OER) and chlorine evolution reaction (CER) are electrochemical processes with high relevance to water splitting for (solar) energy conversion and industrial production of commodity chemicals, respectively. Carrying out the two reactions separately is challenging, since the catalytic intermediates are linked by scaling relations. Optimizing the efficiency of OER over CER in acidic media has proven especially difficult. In this regard, we have investigated the OER versus CER selectivity of manganese oxide (MnOx), a known OER catalyst. Thin films (∼5-20 nm) of MnOx were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrOx/GC) in aqueous chloride solutions of pH ∼0.9. Using rotating ring-disk electrode voltammetry and online electrochemical mass spectrometry, it was found that deposition of MnOx onto IrOx decreases the CER selectivity of the system in the presence of 30 mM Cl- from 86% to less than 7%, making it a highly OER-selective catalyst. Detailed studies of the CER mechanism and ex-situ structure studies using SEM, TEM, and XPS suggest that the MnOx film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions.
UR - http://www.scopus.com/inward/record.url?scp=85050646640&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b05382
DO - 10.1021/jacs.8b05382
M3 - Article
AN - SCOPUS:85050646640
SN - 0002-7863
VL - 140
SP - 10270
EP - 10281
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 32
ER -