Abstract: Green hydrogen -a carbon-free renewable fuel- has the capability to decarbonise a variety of sectors. The generation of green hydrogen is currently restricted to water electrolysers. The use of freshwater resources and critical raw materials, however, limits their use. Alternative water splitting methods for green hydrogen generation via photocatalysis and photoelectrocatalysis (PEC) have been explored in the past few decades; however, their commercial potential still remains unexploited due to the high hydrogen generation costs. Novel PEC-based simultaneous generation of green hydrogen and wastewater treatment/high-value product production is therefore seen as an alternative to conventional water splitting. Interestingly, the organic/inorganic pollutants in wastewater and biomass favourably act as electron donors and facilitate the dual-functional process of recovering green hydrogen while oxidising the organic matter. The generation of green hydrogen through the dual-functional PEC process opens up opportunities for a "circular economy". It further enables the end-of-life commodities to be reused, recycled and resourced for a better life-cycle design while being economically viable for commercialisation. This review brings together and critically analyses the recent trends towards simultaneous wastewater treatment/biomass reforming while generating hydrogen gas by employing the PEC technology. We have briefly discussed the technical challenges associated with the tandem PEC process, new avenues, techno-economic feasibility and future directions towards achieving net neutrality.

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