Transient IR spectroscopy as a tool for studying photocatalytic materials.

Over the years, a considerable amount of attention has been given to the thermodynamics of photocatalysts, i.e. to the location of their valence and conduction bands on the energy scale. The kinetics of the photoinduced charge carriers at short times (i.e. prior to their surface redox reactions) is no less important. While significant work on the transient electronic spectra of photocatalysts has been performed, the transient vibrational spectra of this class of materials was hardly studied. This manuscript aims to increase the scientific awareness to the potential of transient IR spectroscopy (TRIR) as a complementary tool for understanding the first, crucial, steps of photocatalytic processes in solid photocatalysts. This was done herein first by describing the various techniques currently in use for measuring transient IR signals of photo-excited systems and discussing their pros and cons. Then, a variety of examples is given, representing different types of photocatalysts such as oxides (TiO, NaTaO, BiOCl, BiVO), photosensitized oxides (dye-sensitized TiO), organic polymers (graphitic carbon nitride) and organo-metalic photocatalysts (rhenium bipyridyl complexes). These examples span from materials with no IR fingerprint signals (TiO) to materials having a distinct spectrum showing well-defined, localized, relatively narrow, vibrational bands (carbon nitride). In choosing the given-above examples, care was made to represent the several pump & probe techniques that are applied when studying transient IR spectroscopy, namely dispersive, transient 2D-IR spectroscopy and step-scan IR spectroscopy. It is hoped that this short review will contribute to expanding the use of TRIR as a viable and important technique among the arsenal of tools struggling to solve the mysteries behind photocatalysis.