In situ and operando Raman spectroscopy of semiconducting photoelectrodes and devices for photoelectrochemistry

Marco Favaro, Heejung Kong, Ronen Gottesman

Research output: Contribution to journalReview articlepeer-review

3 Scopus citations


Future alternative and promising energy sources involve photoelectrochemical (PEC) devices that can convert sunlight and abundant resources such as water and CO2 into chemical fuels and value-added products. However, identifying suitable photoabsorber semiconductor materials that fulfill all the stringent requirements of photoelectrodes in PEC devices remains a significant challenge. A key factor for tailoring and optimizing existing and novel photoabsorbers is understanding the processes occurring at the semiconductor/liquid electrolyte interface under working conditions. This perspective focuses on the application of operando Raman spectroscopy (RS) in synergy with (photo)electrochemical techniques. Despite being a relatively new field of application, when applied to photoelectrochemistry, operando RS offers insights into the evolution of photoelectrode structure (i.e. phase purity and degree of crystallinity) and surface defects under working conditions. The challenges associated with operando RS for (photo)electrochemical applications, including the low quantum efficiency of inelastic scattering and fluorescence, and possible mitigation strategies are discussed. Furthermore, practical aspects such as sample/reactor geometry requirements and the surrounding environment of the photoelectrode sample during operando RS under PEC conditions are reviewed. We demonstrate that operando RS can be used to perform product analysis of solar-driven biomass reforming reactions, showing the approach’s limitations and discussing possible solutions to overcome them. This work concludes with a discussion on the current state of operando RS of semiconducting photoelectrodes and devices for photoelectrochemistry. We show a new methodology for performing operando RS with illumination resembling AM1.5 conditions and with time resolution spanning from tens to hundreds of milliseconds, suitable timescales for real-time monitoring of chemical reactions and degradation mechanisms occurring at the photoelectrode under investigation.

Original languageEnglish
Article number103002
JournalJournal Physics D: Applied Physics
Issue number10
StatePublished - 8 Mar 2024
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2023 The Author(s). Published by IOP Publishing Ltd.


Operando RS activities at the Institute for Solar Fuels of the Helmholtz Zentrum Berlin are supported by the Helmholtz Energy Materials Foundry (HEMF, GZ 714-48172-21/1) and by the German Federal Ministry of Education and Research (BMBF) through the CatLab project (Förderkennzeichen 03EW0015A). M F acknowledges Senapati Sri Krishnamurti for supporting the finite element analysis investigation. M F also acknowledges Katrin Tietz and Marvin Bruns for fabricating the PEC cell described in this work and Daniel Bieg and Dr Dieter Bingemann (Wasatch Photonics) for their technical support. H K kindly acknowledges the European Innovation Council (EIC) via OHPERA project (Grant Agreement 101071010) for support. R G thanks the Azrieli Foundation for financial support within the Azrieli Fellows program and the construction of a similar operando RS system at the Hebrew University, Israel, as described here for the development of novel semiconducting photoelectrode materials for photoelectrochemistry applications.

FundersFunder number
HORIZON EUROPE European Innovation Council101071010
Bundesministerium für Bildung und Forschung03EW0015A
Hebrew University of Jerusalem
Azrieli Foundation
Helmholtz Energy Materials FoundryGZ 714-48172-21/1


    • operando Raman spectroscopy
    • photoelectrochemical conversion
    • photoelectrochemical devices
    • photoelectrochemical techniques
    • renewable energy
    • semiconducting photoelectrodes


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