| Summary: | The photoexcitation of suitable semiconducting materials in aqueous environments can lead to the production of reactive oxygen species (ROS). ROS can inactivate microorganisms and degrade a range of chemical compounds. In the case of heterogeneous photocatalysis, semiconducting materials may suffer from fast recombination of electron–hole pairs and require post-treatment to separate the photocatalyst when a suspension system is used. To reduce recombination and improve the rate of degradation, an externally applied electrical bias can be used where the semiconducting material is immobilised onto an electrically conducive support and connected to a counter electrode. These electrochemically assisted photocatalytic systems have been termed “<i>photoelectrocatalytic</i>” (PEC). This review will explain the fundamental mechanism of PECs, photoelectrodes, the different types of PEC reactors reported in the literature, the (photo)electrodes used, the contaminants degraded, the key findings and prospects in the research area.
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