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Potential-Dependent Competitive Electroreduction of CO2 into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
journal contribution
posted on 2020-05-28, 00:13 authored by Lihui Ou, Zixi HeAn improved density functional theory-based
H coverage-dependent
electrochemical model with explicit solvent effect is proposed for
Cu(111), which is used to identify potential-dependent initial competitive
CO2 electroreduction pathways considering HER. We find
that a chemisorbed CO2 molecule at the present electrode/aqueous
interface can be spontaneously formed and the overpotentials can affect
its coordination pattern. The Eley–Rideal mechanism may be
more favorable during the initial CO2 electroreduction
into CO, whereas chemisorbed CO2 reacting with adsorbed
H into HCOO– via the Langmuir–Hinshelwood
mechanism is more facile to occur. The analyses of energetics suggest
that the low overpotentials have a negligible influence on CO and
HCOO– formation, and HCOO– species
with monodentate and bidentate configurations may also parallelly
form with the surmountable barriers at room temperature. However,
the high potentials have an interruptive effect on initial CO2 electroreduction because of the significantly increased barriers,
indicating that the chemisorbed CO2 can be stabilized by
imposing more negative potentials and thus going against initial CO2 electroreduction. By analyzing the competing HER with initial
CO2 electroreduction into CO, we find that HER is competitive
with initial CO formation because of the required lower overpotentials.
Simultaneously, the present study shows that the blocked Cu surface
by adsorbed H and CO can explain why the initial CO formation pathway
is unfavorable at the high overpotentials. Our present conclusions
can also confirm the previous experimental report on initial formation
of CO and HCOO–.
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bidentate configurationsparallelly formchemisorbed CO 2 moleculeCO 2 electroreduction pathwaysinterruptive effectCO formation pathwayCO 2 electroreductionExplicit Solvent Effectcoordination patternHERCu surfaceroom temperatureHCOOtheory-based H coverage-dependent electrochemical modelsurmountable barriersCO 2H Coverage-Dependent Electrochemical ModelCO formationchemisorbed CO 2
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