Recent developments in complex metal oxide photoelectrodes

Photoelectrochemical (PEC) water splitting, a process that directly produces hydrogen from water and sunlight using semiconductor materials, is an attractive form of renewable energy production. The hydrogen that is produced can be easily transported, stored, and utilized as a fuel without the emission of greenhouse gasses. However, many scientific and engineering challenges need to be overcome before PEC water splitting can be implemented on a large scale. One of the biggest challenges is the identification of suitable semiconductor materials to use in the construction of photoelectrodes. This topical review highlights a promising class of materials, complex metal oxides, which can be used as photoelectrodes for PEC water splitting. The advantages and limitations of complex metal oxides are first discussed, and strategies to overcome the limitations are outlined using the model case of bismuth vanadate (BiVO₄), one of the highest performing complex metal oxide photoanodes reported to date. Building on the success story of BiVO₄, we discuss pathways towards achieving even higher water splitting performance, including bandgap engineering as well as the development of alternative complex metal oxides with more appropriate bandgaps for obtaining high solar-to-hydrogen efficiency. Several classes of complex metal oxides (e.g. delafossites, tungstates, vanadates, spinels) are presented as promising candidates for photoelectrode materials. Finally, we conclude by summarizing the key properties of these complex metal oxides and providing an outlook towards expedited discovery of new and novel complex metal oxides for use as photoelectrodes. (topical review)