Photoelectrochemical (PEC) water splitting is an attractive approach to capturing and storing the earth's abundant solar energy influx. The challenging four-electron water-oxidation half-cell reaction has hindered this technology, giving rise to slow wateroxidation kinetics at the photoanode surfaces relative to competitive loss processes. In this perspective, we review recent efforts to improve PEC efficiencies by modification of semiconductor photoanode surfaces with water-oxidationcatalysts that can operate at low overpotentials. This approach allows separation of the tasks of photon absorption, charge separation, and surface catalysis, allowing each to be optimized independently. In particular, composite photoanodes marrying nanocrystalline and molecular/non-crystalline components provide flexibility in adjusting the properties of each component, but raise new challenges in interfacial chemistries.
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