On the Limits of Photocatalytic Water Splitting

The major drawbacks on the limited H2 and O2 evolution activities of one-step photocatalytic water splitting systems are given here with the emphasis on charge recombination, back-oxidation reactions, and mass transfer limitations. Suppression of these unwanted phenomena is shown to be possible with the usage of small crystal-sized photocatalysts with low defect concentrations, presence of phase junctions, selection of co-catalyst that would be active for H2 evolution but inactive for O2 reduction, coating of the co-catalyst or the whole photocatalyst with selectively permeable nanolayers, and usage of photocatalytic systems with high solid–liquid and liquid–gas surface areas. The mass transfer limitations are shown to be important especially in the liquid–gas interfaces for agitated and suspended systems with estimated H2 transfer rates in the range of ∼200–8000 μmol/h.