Semiconductor-Based Photoelectrocatalysts in Water Splitting: From the Basics to Mechanistic Insights—A Brief Review

Hydrogen and oxygen serve as energy carriers that can ease the transition of energy due to their high energy densities. Nonetheless, their production processes entail the development of efficient and low-cost storage and conversion technologies. In this regard, photoelectrocatalysts are materials based on the photoelectronic effect where electrons and holes interact with H₂O, producing H₂ and O_2, and in some cases, this is achieved with acceptable efficiency. Although there are several reviews on this topic, most of them focus on traditional semiconductors, such as TiO₂ and ZnO, neglecting others, such as those based on non-noble metals and organic ones. Herein, semiconductors like CdSe, NiWO₄, Fe₂O₃, and others have been investigated and compared in terms of photocurrent density, band gap, and charge transfer resistance. In addition, this brief review aims to discuss the mechanisms of overall water-splitting reactions from a photonic point of view and subsequently discusses the engineering of material synthesis. Advanced composites are also addressed, such as WO₃/BiVO₄/Cu₂O and CN-FeNiOOH-CoOOH, which demonstrate high efficiency by delivering photocurrent densities of 5 mAcm⁻² and 3.5 mA cm⁻² at 1.23 vs. RHE, respectively. Finally, the authors offer their perspectives and list the main challenges based on their experience in developing semiconductor-based materials applied in several fields. In this manner, this brief review provides the main advances in these topics, used as references for new directions in designing active materials for photoelectrocatalytic water splitting.