Correlative Operando Characterization of Dynamic (Photo)electrochemical Interfaces
Francesca M. Toma a
a Helmholtz-Zentrum Hereon, Institute of Functional Materials for Sustainability, 14153, Teltow, Germany
Proceedings of MATSUS Fall 2026 Conference (MATSUSFall26)
C1 Multiscale Insights into Solid–Liquid Interfaces for Sustainable Energy Technologies
Palma, Spain, 2026 October 26th - 30th
Organizers: Marco Fontana, Elena Magnano, Silvia Nappini and Francesca Risplendi
Invited Speaker, Francesca M. Toma, presentation 278
Publication date: 22nd July 2026

The efficiency and durability of photoelectrodes for solar fuel production are largely determined by the dynamic processes that take place at the solid–liquid interface. Resolving these processes calls for correlative characterization across length and time scales, from operating devices down to the nanoscale. We present such a multiscale approach to elucidate performance-limiting mechanisms and to identify pathways toward improved photoelectrode design. 

To probe degradation processes more broadly, we recently introduced operando spectroscopic ellipsometry as a quantitative tool for real-time monitoring of photocorrosion, revealing strong dependencies on crystallinity, illumination, and electrolyte conditions in TiO₂ model systems. Complementary nanoscale analysis using time-resolved Kelvin probe force microscopy further establishes direct correlations between local morphology and charge carrier dynamics, highlighting superior charge separation and transport in crystalline regions. Extending this correlative approach to other photocathodes, we uncover competing redox-driven degradation pathways and implement a protection strategy based on catalyst integration and heterojunction design, enabling stable CO₂ reduction with high selectivity.

Taken together, these results provide a multiscale framework linking interfacial chemistry, microstructure, and charge transport to photoelectrode performance and stability, offering actionable design principles for next-generation materials in sustainable energy technologies.

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