Abstract: The increasing demand for sustainable energy solutions has intensified the focus on technologies that can efficiently convert renewable resources into usable energy while simultaneously addressing CO2 emissions. Photoelectrochemical (PEC) water splitting emerges as a promising approach, utilizing solar energy to produce renewable H2. This study investigates PEC-driven water splitting using a multi-layered BiVO4/WO3 photoanode in combination with an ionic liquid-based anolyte under visible light, including [EMIM][OTf] and [EMIM][Ac]. The research aims to explain the effects of ionic liquid-based electrolytes on the structural integrity of the photoanode, particularly concerning morphological changes and catalyst degradation. Furthermore, the stability of the ionic liquids and their susceptibility to photodegradation are evaluated to determine their viability for PEC applications. This work reveals that the incorporation of the studied ionic liquids does not compromise the structural integrity of BiVO4/WO3 and maintains PEC functionality. Notably, the ionic liquid [EMIM][OTf] offers enhanced photostability and better operational stability (stable current and low photodegradation) compared to [EMIM][Ac]. Additionally, 1H NMR spectra indicate minimal photodegradation levels of 1 % for [EMIM][OTf] and 4 % for [EMIM][Ac], showing up the stability of these ionic liquids after use. Overall, the integration of ionic liquids into the anolyte of PEC technologies presents a promising path for enhancing the stability of systems designed for photo-assisted renewable energy applications.

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