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@ARTICLE{Schatz:1016716,
author = {Schatz, Michael and Kochs, Johannes Florian and Jovanovic,
Sven and Eichel, Rüdiger-A. and Granwehr, Josef},
title = {{I}nterplay of {L}ocal p{H} and {C}ation {H}ydrolysis
during {E}lectrochemical {CO} 2 {R}eduction {V}isualized by
{I}n {O}perando {C}hemical {S}hift-{R}esolved {M}agnetic
{R}esonance {I}maging},
journal = {The journal of physical chemistry / C},
volume = {127},
number = {38},
issn = {1932-7447},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2023-03708},
pages = {18986 - 18996},
year = {2023},
abstract = {The Cu-catalyzed electrochemical CO2 reduction enables the
conversion of greenhouse gas emissions to fuels or platform
chemicals with prospects of storing intermittent energy from
renewable sources. While current research in tuning catalyst
activity and product selectivity is often mired in finding
electrode engineering solutions, the importance of
electrolyte engineering is mostly overlooked. This study
presents a method for measuring local pH profiles in
electrode proximity and correlating them to cation-induced
buffering effects. Magnetic resonance imaging (MRI)
techniques were applied to evaluate the local pH values
using spatially resolved 13C resonances of the
CO2/HCO3–/CO32– equilibrium. The buffering effect of
cation hydrolysis is substantiated by local shifts of the
23Na resonance of Na+ in the NaHCO3 electrolytes. Steeper
local pH gradients, compared to experiments with KHCO3,
account for increased selectivity for acetate formation from
the solution-based reaction. Proven itself capable of
elucidating the effect of cations on local pH values, our
presented method supports tailoring the
electrode–electrolyte interface to selectively generate
value-added products.},
cin = {IEK-9},
ddc = {530},
cid = {I:(DE-Juel1)IEK-9-20110218},
pnm = {1232 - Power-based Fuels and Chemicals (POF4-123) / HITEC -
Helmholtz Interdisciplinary Doctoral Training in Energy and
Climate Research (HITEC) (HITEC-20170406)},
pid = {G:(DE-HGF)POF4-1232 / G:(DE-Juel1)HITEC-20170406},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001122214700001},
doi = {10.1021/acs.jpcc.3c03563},
url = {https://juser.fz-juelich.de/record/1016716},
}