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Shedding light on overpotentials and underpotentials in (photo)electrochemical reactions.

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Title: Shedding light on overpotentials and underpotentials in (photo)electrochemical reactions.
Authors: Nishiori, Daiki1 (AUTHOR), Reyes Cruz, Edgar A.1 (AUTHOR), Hensleigh, Lillian K.1 (AUTHOR), Nguyen, Nghi P.1 (AUTHOR), Moore, Gary F.1 (AUTHOR) gfmoore@asu.edu
Source: Chemical Society Reviews. 4/14/2026, Vol. 55 Issue 7, p3737-3765. 29p.
Subjects: Overpotential, Photoelectrochemistry, Surface photovoltage, Photoelectrochemical cells, Catalysts, Electrode reactions, Fermi level
Abstract: The concept of overpotential is central to evaluating the performance of catalysts for electrochemical and photoelectrochemical transformations. This thermodynamic metric is well defined in the context of electrochemical reactions involving conducting electrodes, where the overpotential is the difference between an applied bias potential (which sets the energetics/potential of the electrode's Fermi level) and the equilibrium potential (which is set by the mixture of oxidized and reduced chemical species in the bulk solution and establishes the applied bias potential at which no net current flows, i.e., the open-circuit potential). Nonetheless, there are at least two ways the term overpotential—or in some cases "underpotential"—has been used to describe photoelectrochemical reactions involving semiconducting electrodes, where illumination results in a splitting of the photoelectrode's Fermi level into majority- and minority-carrier quasi-Fermi levels. In one approach, the overpotential/underpotential remains defined as the difference between an applied bias potential and the equilibrium potential. In the alternative approach, the overpotential is defined as the difference between the minority-carrier quasi-Fermi-level potential at the semiconductor surface and the equilibrium potential, thereby accounting for the surface photovoltage generated upon illumination of a semiconductor electrode. This article provides an overview of conceptual differences involving overpotentials and underpotentials in (photo)electrochemical reactions and considers applied electrode potentials in terms of their enthalpic versus entropic contributions. [ABSTRACT FROM AUTHOR]
Copyright of Chemical Society Reviews is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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DbLabel: Engineering Source
An: 193088461
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
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  Data: Shedding light on overpotentials and underpotentials in (photo)electrochemical reactions.
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  Data: <searchLink fieldCode="AR" term="%22Nishiori%2C+Daiki%22">Nishiori, Daiki</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Reyes+Cruz%2C+Edgar+A%2E%22">Reyes Cruz, Edgar A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Hensleigh%2C+Lillian+K%2E%22">Hensleigh, Lillian K.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Nguyen%2C+Nghi+P%2E%22">Nguyen, Nghi P.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Moore%2C+Gary+F%2E%22">Moore, Gary F.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> gfmoore@asu.edu</i>
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  Data: <searchLink fieldCode="JN" term="%22Chemical+Society+Reviews%22">Chemical Society Reviews</searchLink>. 4/14/2026, Vol. 55 Issue 7, p3737-3765. 29p.
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  Data: <searchLink fieldCode="DE" term="%22Overpotential%22">Overpotential</searchLink><br /><searchLink fieldCode="DE" term="%22Photoelectrochemistry%22">Photoelectrochemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Surface+photovoltage%22">Surface photovoltage</searchLink><br /><searchLink fieldCode="DE" term="%22Photoelectrochemical+cells%22">Photoelectrochemical cells</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Electrode+reactions%22">Electrode reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Fermi+level%22">Fermi level</searchLink>
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  Data: The concept of overpotential is central to evaluating the performance of catalysts for electrochemical and photoelectrochemical transformations. This thermodynamic metric is well defined in the context of electrochemical reactions involving conducting electrodes, where the overpotential is the difference between an applied bias potential (which sets the energetics/potential of the electrode's Fermi level) and the equilibrium potential (which is set by the mixture of oxidized and reduced chemical species in the bulk solution and establishes the applied bias potential at which no net current flows, i.e., the open-circuit potential). Nonetheless, there are at least two ways the term overpotential—or in some cases "underpotential"—has been used to describe photoelectrochemical reactions involving semiconducting electrodes, where illumination results in a splitting of the photoelectrode's Fermi level into majority- and minority-carrier quasi-Fermi levels. In one approach, the overpotential/underpotential remains defined as the difference between an applied bias potential and the equilibrium potential. In the alternative approach, the overpotential is defined as the difference between the minority-carrier quasi-Fermi-level potential at the semiconductor surface and the equilibrium potential, thereby accounting for the surface photovoltage generated upon illumination of a semiconductor electrode. This article provides an overview of conceptual differences involving overpotentials and underpotentials in (photo)electrochemical reactions and considers applied electrode potentials in terms of their enthalpic versus entropic contributions. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Chemical Society Reviews is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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        Value: 10.1039/d4cs00695j
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        Text: English
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        PageCount: 29
        StartPage: 3737
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        Type: general
      – SubjectFull: Photoelectrochemistry
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      – SubjectFull: Surface photovoltage
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      – SubjectFull: Photoelectrochemical cells
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      – SubjectFull: Catalysts
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      – SubjectFull: Electrode reactions
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      – SubjectFull: Fermi level
        Type: general
    Titles:
      – TitleFull: Shedding light on overpotentials and underpotentials in (photo)electrochemical reactions.
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              Text: 4/14/2026
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              Y: 2026
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