Publication date: 21st July 2025
Selective oxidation of biomass-derived molecules such as glycerol at the photoanode offers a compelling strategy to enhance the efficiency and value proposition of photoelectrochemical (PEC) systems [1]. In this talk, we will present our recent work on the PEC oxidation of glycerol over nanoporous BiVO4 photoanodes, which exhibit intrinsic activity without the need for co-catalysts [2, 3]. Focusing on electrolyte engineering, we demonstrate how specific anion and cation effects—interpreted through the Hofmeister series—modulate interfacial charge transfer, photocurrent response, product selectivity, and long-term stability [3]. Among various electrolytes, NaNO₃ yields the highest selectivity (~50%) toward glycolaldehyde and overall PEC performance [3], highlighting the critical role of electrolyte composition in driving complex multielectron oxidation reactions.
To complement these experimental insights, we will discuss our thermodynamic analysis of glycerol oxidation under PEC-relevant conditions [4]. Our calculations reveal how applied bias and temperature influence product distributions, energy efficiency, and reaction spontaneity [4], providing a framework for interpreting experimental trends and guiding future materials and device optimization.
Lastly, we will introduce a modular, side-by-side design for a membraneless PEC device enabling simultaneous solar-driven glycerol oxidation and hydrogen production [5]. By addressing crossover and stability challenges via flow dynamics and electrolyte symmetry, we demonstrate a scalable approach to solar-driven biomass reforming. These results underline the synergy between materials design, electrolyte selection, and device architecture in advancing PEC systems for sustainable fuel and chemical production.
The works reported in this abstract were supported by the European Innovation Council (EIC) via the OHPERA project (grant agreement 101071010) and co-funded by the European Union under grant agreement 101137889 (PH2OTOGEN).
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