Chiral organic–inorganic hybrid perovskites exhibiting circular dichroism were prepared as a new class of chiral semiconductors.

In this review, we survey recent strategies for photoelectrode optimization and advanced characterization methods towards efficient water splitting cells via feedback from these characterization methods.

Hydrogen evolution electrocatalysts can achieve sustainable hydrogen production via electrocatalytic water splitting; however, designing highly active and stable noble‐metal‐free hydrogen evolution electrocatalysts that perform as efficiently as Pt catalysts over a wide pH range is a challenging task. Herein, a new 2D cobalt phosphide/nickelcobalt phosphide (CoP/NiCoP) hybrid nanosheet network is proposed, supported on an N‐doped carbon (NC) matrix as a highly efficient and durable pH‐universal hydrogen evolution reaction (HER) electrocatalyst. It is derived from topological transformation of corresponding layer double hydroxides and graphitic carbon nitride. This 2D CoP/NiCoP/NC catalyst exhibits versatile HER electroactivity with very low overpotentials of 75, 60, and 123 mV in 1 m KOH, 0.5 m H2SO4, and 1 m PBS electrolytes, respectively, delivering a current density of 10 mA cm−2 for HER. Such impressive HER performance of the hybrid electrocatalyst is mainly attributed to the collective effects of electronic structure engineering, strong interfacial coupling between CoP and NiCoP in heterojunction, an enlarged surface area/exposed catalytic active sites due to the 2D morphology, and conductive NC support. This method is believed to provide a basis for the development of efficient 2D electrode materials with various electrochemical applications.

Determining cost-effective semiconductors exhibiting desirable properties for commercial photoelectrochemical water splitting remains a challenge. Herein, we report a Sb 2 Se 3 semiconductor that satisfies most requirements for an ideal high-performance photoelectrode, including a small band gap and favourable cost, optoelectronic properties, processability, and photocorrosion stability. Strong anisotropy, a major issue for Sb 2 Se 3 , is resolved by suppressing growth kinetics via close space sublimation to obtain high-quality compact thin films with favourable crystallographic orientation. The Sb 2 Se 3 photocathode exhibits a high photocurrent density of almost 30 mA cm −2 at 0 V against the reversible hydrogen electrode, the highest value so far. We demonstrate unassisted solar overall water splitting by combining the optimised Sb 2 Se 3 photocathode with a BiVO 4 photoanode, achieving a solar-tohydrogen efficiency of 1.5% with stability over 10 h under simulated 1 sun conditions employing a broad range of solar fluxes. Low-cost Sb 2 Se 3 can thus be an attractive breakthrough material for commercial solar fuel production.

Sb2Se3 has recently spurred great interest as a promising light‐absorbing material for solar energy conversion. Sb2Se3 consists of 1D covalently linked nanoribbons stacked via van der Waals forces and its properties strongly depend on the crystallographic orientation. However, strategies for adjusting the anisotropy of 1D Sb2Se3 nanostructures are rarely investigated. Here, a novel approach is presented to fabricate 1D Sb2Se3 nanostructure arrays with different aspect ratios on conductive substrates by simply spin‐coating Sb‐Se solutions with different molar ratios of thioglycolic acid and ethanolamine. A relatively small proportion of thioglycolic acid induces the growth of short Sb2Se3 nanorod arrays with preferred orientation, leading to fast carrier transport and enhanced photocurrent. After the deposition of TiO2 and Pt, an appropriately oriented Sb2Se3 nanostructure array exhibits a significantly enhanced photoelectrochemical performance; the photocurrent reaches 12.5 mA cm−2 at 0 V versus reversible hydrogen electrode under air mass 1.5 global illumination.

Solar-energy conversion by photoelectrochemical (PEC) devices is driven by the separation and transfer of photogenerated charge carriers. Thus, understanding carrier dynamics in a PEC device is essential to realizing efficient solar-energy conversion. Here, we investigate time-resolved carrier dynamics in emerging low-cost Sb 2 Se 3 nanostructure photocathodes for PEC water splitting. Using terahertz spectroscopy, we observed an initial mobility loss within tens of picoseconds due to carrier localization and attributed the origin of carrier localization to the rich surface of Sb 2 Se 3 nanostructures. In addition, a possible recombination at the interface between Sb 2 Se 3 and the back contact is elucidated by time-resolved photoluminescence analysis. We also demonstrated the dual role of the RuO x co-catalyst in reducing surface recombination and enhancing charge transfer in full devices using intensity-modulated spectroscopy. The relatively low onset potential of the Sb 2 Se 3 photocathode is attributed to the sluggish charge transfer at a low applied bias rather than to fast surface recombination. We believe that our insights on carrier dynamics would be an important step toward achieving highly efficient Sb 2 Se 3 photocathodes.

Although antimony triselenide (Sb2Se3) has been intensively investigated as a low-cost p-type semiconductor for photoelectrochemical (PEC) water splitting, most previous studies focused on only the top interface of Sb2Se3 photocathodes. Herein, a solution-processed Cu-doped NiO x (Cu:NiO x ) thin film is proposed as an effective bottom contact layer for the Sb2Se3 photocathode. The photocurrent density of the Sb2Se3 photocathode is improved to a record-high level of 17.5 mA cm–2 upon the insertion of Cu:NiO x capable of blocking the recombination at the back interface, while facilitating hole extraction. Electrochemical impedance spectroscopy and intensity-modulated photocurrent spectroscopy, in conjunction with other observations, indicate that the enhanced photocurrent is due to the improved quality of the bottom contact without a noticeable change in the top interface. This study not only provides new insight into the role of the bottom contact layer in photocathodes, but also is an important step toward efficient PEC H2 production via a solution-processable Earth-abundant photoelectrode.

We present a novel solution-based synthesis method enabling the morphology variation of Sb2Se3 light absorbers. The morphology of Sb2Se3 films varies from dense particulate planar films to one-dimensional nanowire-stacked films upon modulating the Sb and Se molar ratio in the precursor ink. The effect of morphology and crystallographic orientation on the electrical and consequently the PEC properties of Sb2Se3-based photocathodes is investigated. Sequential deposition of CdS as a buffer layer with TiO2 and Pt enables us to build a favorable band structure. An onset potential of 0.47 V versus a reversible hydrogen electrode (RHE) is observed with 13.5 mA cm–2 at 0 V versus a RHE under air mass 1.5 global illumination in a pH 1 electrolyte. In addition, the surface-modified photocathode stably produces hydrogen with a photocurrent of 11 mA cm–2 at 0 V versus RHE in a neutral electrolyte, thus demonstrating the promising potential of the proposed Sb2Se3 photocathodes as efficient PEC water-splitting devices.