Photoelectrochemical (PEC) water splitting promises a solution to the problem of large-scale solar energy storage. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. Here we show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversible hydrogen electrode) is achieved. This result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.

Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-FeO is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-FeO anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward HO photooxidation.

Probing the surface kinetics of different hematite electrodes with and without surface passivations.

The performance of Ta 3 N 5 as a photoelectrode for solar water splitting is compromised by the low photovoltage and poor stability. Wang and colleagues reveal that these issues are caused by the growth of a thin oxide layer on the surface. Although self-limiting in nature, this layer pins the Fermi level and leads to almost complete suppression of the photoactivity. The effect is quantitatively measured via X-ray spectroscopy and photoelectrochemical studies. The information sheds light on strategies for improving photoelectrode performance. SUMMARYTantalum nitride (Ta 3 N 5 ) is a promising photoelectrode for solar water splitting. Although near-theoretical-limit photocurrent has already been reported on Ta 3 N 5 , its low photovoltage and poor stability remain critical challenges. In this study, we used Ta 3 N 5 nanotubes as a platform to understand the origins of these issues. Through a combination of photoelectrochemical and high-resolution electron microscope measurements, we found that the self-limiting surface oxidation of Ta 3 N 5 resulted in a thin amorphous layer (ca. 3 nm), which proved to be effective in pinning the surface Fermi levels and thus fully suppressed the photoactivity of Ta 3 N 5 . X-ray core-level spectroscopy characterization not only confirmed the surface composition change resulting from the oxidation but also revealed a Fermi-level shift toward the positive direction by up to 0.5 V. The photoactivity degradation mechanism reported here is likely to find applications in other solar-to-chemical energy-conversion systems.

Photoelectrochemistry (PEC) holds potential as a direct route for solar energy storage. Its performance is governed by how efficiently photoexcited charges are separated and how fast the charges are transferred to the solution, both of which are highly sensitive to the photoelectrode surfaces near the electrolyte. While other aspects of a PEC system, such as the light-absorbing materials and the catalysts that facilitate charge transfer, have been extensively examined in the past, an underwhelming amount of attention has been paid to the energetics at the photoelectrode/electrolyte interface. The lack of understanding of this interface is an important reason why many photoelectrode materials fail to deliver the expected performance in harvesting solar energy in a PEC system. Using hematite (α-Fe2O3) as a material platform, we present in this Perspective how surface modifications can alter the energetics and the resulting consequences on the overall PEC performance. It has been shown that a detailed understanding of the photoelectrode/eletrolyte interfaces can contribute significantly to improving the performance of hematite, which enabled unassisted solar water splitting when combined with an amorphous Si photocathode.