We report an efficient molecular light-driven system to oxidize water to oxygen and a kinetic analysis of the factors determining the efficiency of the system. The system comprises a highly active molecular catalyst ([Ru^IV(tda)(py)₂(O)]), [Ru^II(bpy)(bpy-COOEt)₂]²⁺ (RuP), as sensitizer and Na₂S₂O₈ as sacrificial electron acceptor. This combination exhibits a high quantum yield (25%) and chemical yield (93%) for photodriven oxygen evolution from water. The processes underlying this performance are identified using optical techniques, including transient absorption spectroscopy and photoluminescence quenching. A high catalyst concentration is found to be required to optimize the efficiency of electron transfer between the oxidized sensitizer and the catalyst, which also has the effect of improving sensitizer stability. The main limitation of the quantum yield is the relatively low efficiency of S₂O₈^2– as an electron scavenger to oxidize the photoexcited ruthenium sensitizer RuP* to 2 RuP⁺, mainly due to competing back electron transfers to the RuP ground state. The overall rate of light-driven oxygen generation is determined primarily by the rate of photon absorption by the molecular sensitizer under the incident photon flux. As such, the performance of this efficient light-driven system is limited not by the properties of the molecular water oxidation catalyst, which exhibits both good kinetics and stability, but rather by the light absorption and quantum efficiency properties of the sensitizer and electron scavenger. We conclude by discussing the implications of these results for further optimization of molecular light-driven systems for water oxidation.

Electrocatalytic reduction of CO2 recently emerged as a viable solution in view of changing the common belief and considering carbon dioxide as a valuable reactant instead of a waste product. In this view, we herein propose the one-step synthesis of gold nanostructures of different morphologies grown on fluorine-doped tin oxide electrodes by means of pulsed-laser deposition. The resulting cathodes are able to produce syngas mixtures of different compositions at overpotentials as low as 0.31 V in CO2-presaturated aqueous media. Insights into the correlation between the structural features/morphology of the cathodes and their catalytic activity are also provided, confirming recent reports on the remarkable sensitivity toward CO production for gold electrodes exposing undercoordinated sites and facets.

The deposition of perylene diimide-based aggregates (PDI) onto wide band gap n-type Sb-doped SnO₂ (ATO) was investigated with the aim of finding efficient and versatile dye-sensitized platforms for photoelectrochemical solar fuel generation. These ATO-PDI photoanodes displayed hydrolytic stability in a wide range of pH (from 1 to 13) and revealed superior performances (up to 1 mA/cm² net photocurrent at 1 V vs SCE) compared to both WO₃-PDI and undoped SnO₂-PDI when used in a photoelectrochemical setup for HBr splitting. Although ATO, SnO₂, and WO₃ are endowed with similar conduction band edge energetics, in ATO the presence of a significant density of intrabandgap states, whose occupancy varies with the applied potential, plays a substantial role in tuning the efficiency of photoinduced charge separation and collection. Furthermore, the investigation of the charge injection kinetics confirmed that, even in the absence of applied bias, ATO and WO₃ are the best substrates for the oxidative quenching of poorly reducing PDI excited states, with at least a fraction of them injecting within <200 fs. The charge-separated states recombination occurs on longer time scales, allowing for their exploitation to drive demanding chemical reactions, as confirmed in photoelectrochemical water oxidation using IrO₂-modified ATO-PDI photoanodes.

Hematite (α-Fe₂O₃) is an earth-abundant indirect n-type semiconductor displaying a band gap of about 2.2 eV, useful for collecting a large fraction of visible photons, with frontier energy levels suitably aligned for carrying out the photoelectrochemical water oxidation reaction under basic conditions. The modification of hematite mesoporous thin-film photoanodes with Ti(IV), as well as their functionalization with an oxygen-evolving catalyst, leads to a 6-fold increase in photocurrent density with respect to the unmodified electrode. In order to provide a detailed understanding of this behavior, we report a study of Ti-containing phases within the mesoporous film structure. Using X-ray absorption fine structure and high-resolution transmission electron microscopy coupled with electron energy loss spectroscopy, we find that Ti(IV) ions are incorporated within ilmenite (FeTiO₃) near-surface layers, thus modifying the semiconductor–electrolyte interface. To the best of our knowledge, this is the first time that an FeTiO₃/α-Fe₂O₃ composite is used in a photoelectrochemical setup for water oxidation. In fact, previous studies of Ti(IV)-modified hematite photoanodes reported the formation of pseudobrookite (Fe₂TiO₅) at the surface. By means of transient absorption spectroscopy, transient photocurrent experiments, and electrochemical impedance spectroscopy, we show that the formation of the Fe₂O₃/FeTiO₃ interface passivates deep traps at the surface and induces a large density of donor levels, resulting in a strong depletion field that separates electron and holes, favoring hole injection in the electrolyte. Our results provide the identification of a phase coexistence with enhanced photoelectrochemical performance, allowing for the rational design of new photoanodes with improved kinetics.

A hybrid photoanode, made of a multilayered heterostructured WO₃/BiVO₄ semiconductor, a carbon nanotube fibre and a rugged and highly active molecular water oxidation catalyst is described.