Dye-sensitized solar cells (DSCs) are celebrating their 30 ^th birthday and they are attracting a wealth of research efforts aimed at unleashing their full potential. Righteous font designed by Astigmatic and licensed under the Open Font License.

Photocatalysis based technologies have a key role in addressing important challenges of the ecological transition, such as environment remediation and conversion of renewable energies. Photocatalysts can in fact be used in hydrogen (H₂) production (e.g., via water splitting or photo-reforming of organic substrates), CO₂ reduction, pollution mitigation and water or air remediation via oxidation (photodegradation) of pollutants. Titanium dioxide (TiO₂) is a “benchmark” photocatalyst, thanks to many favorable characteristics. We here review the basic knowledge on the charge carrier processes that define the optical and photophysical properties of intrinsic TiO₂. We describe the main characteristics and advantages of TiO₂ as photocatalyst, followed by a summary of historical facts about its application. Next, the dynamics of photogenerated electrons and holes is reviewed, including energy levels and trapping states, charge separation and charge recombination. A section on optical absorption and optical properties follows, including a discussion on TiO₂ photoluminescence and on the effect of molecular oxygen (O₂) on radiative recombination. We next summarize the elementary photocatalytic processes in aqueous solution, including the photogeneration of reactive oxygen species (ROS) and the hydrogen evolution reaction. We pinpoint the TiO₂ limitations and possible ways to overcome them by discussing some of the “hottest” research trends toward solar hydrogen production, which are classified in two categories: (1) approaches based on the use of engineered TiO₂ without any cocatalysts. Discussed topics are highly-reduced “black TiO₂”, grey and colored TiO₂, surface-engineered anatase nanocrystals; (2) strategies based on heterojunction photocatalysts, where TiO₂ is electronically coupled with a different material acting as cocatalyst or as sensitizer. Examples discussed include TiO₂ composites or heterostructures with metals (e.g., Pt-TiO₂, Au-TiO₂), with other metal oxides (e.g., Cu₂O, NiO, etc.), direct Z-scheme heterojunctions with g-C₃N₄ (graphitic carbon nitride) and dye-sensitized TiO₂.

We remove the nonuniqueness of the embedding potential that exists in most previous quantum mechanical embedding schemes by letting the environment and embedded region share a common embedding (interaction) potential. To efficiently solve for the embedding potential, an optimized effective potential method is derived. This embedding potential, which eschews use of approximate kinetic energy density functionals, is then used to describe the environment while a correlated wavefunction (CW) treatment of the embedded region is employed. We first demonstrate the accuracy of this new embedded CW (ECW) method by calculating the van der Waals binding energy curve between a hydrogen molecule and a hydrogen chain. We then examine the prototypical adsorption of CO on a metal surface, here the Cu(111) surface. In addition to obtaining proper site ordering (top site most stable) and binding energies within this theory, the ECW exhibits dramatic changes in the p-character of the CO 4σ and 5σ orbitals upon adsorption that agree very well with x-ray emission spectra, providing further validation of the theory. Finally, we generalize our embedding theory to spin-polarized quantum systems and discuss the connection between our theory and partition density functional theory.