RESUMEN
Transient absorption spectroscopy is a powerful technique to study the photoinduced phenomena in a wide range of states from solutions to solid film samples. It was designed and developed based on photoinduced absorption changes or that photoexcitation triggers a chain of reactions with intermediate states or reaction steps with presumably different absorption spectra. However, according to general electromagnetic theory, any change in the absorption properties of a medium is accompanied by a change in the refractive properties. Although this photoinduced change in refractive index has a negligible effect on solution measurements, it may significantly affect the measured response of thin films. In this Perspective paper, we examine why and how the measured responses of films differ from their expected "pure" absorption responses. The effect of photoinduced refractive index change can be concluded and studied by comparing the transmitted and reflected probe light responses. Another discussed aspect is the effect of light interference on thin films. Finally, new opportunities of monitoring the photocarrier migration in films and studying nontransparent samples using the reflected probe light response are discussed. Most of the examples provided in this article focus on studies involving perovskite, TiO2, and graphene-based films, but the general discussion and conclusions can be applicable to a wide range of semiconductor and thin metallic films.
RESUMEN
New insights into the mechanism of the improved photo(electro)catalytic activity of graphene by heteroatom doping were explored by transient transmittance and reflectance spectroscopy of multi-layer N-doped graphene-based samples on a quartz substrate prepared by chitosan pyrolysis in the temperature range 900-1200 °C compared to an undoped graphene control. All samples had an expected photo-response: fast relaxation (within 1 ps) due to decreased plasmon damping and increased conductivity. However, the N-doped graphenes had an additional transient absorption signal of roughly 10 times lower intensity, with 10-50 ps formation time and the lifetime extending into the nanosecond domain. These photo-induced responses were recalculated as (complex) dielectric function changes and decomposed into Drude-Lorentz parameters to derive the origin of the opto(electronic) responses. Consequently, the long-lived responses were revealed to have different dielectric function spectra from those of the short-lived responses, which was ultimately attributed to electron trapping at doping centers. These trapped electrons are presumed to be responsible for the improved catalytic activity of multi-layer N-doped graphene-based films compared to that of multi-layer undoped graphene-based films.
RESUMEN
Graphitic carbon nitride (g-CN) is a transition metal free semiconductor that mediates a variety of photocatalytic reactions. Although photoinduced electron transfer is often postulated in the mechanism, proton-coupled electron transfer (PCET) is a more favorable pathway for substrates possessing X-H bonds. Upon excitation of an (sp2 )N-rich structure of g-CN with visible light, it behaves as a photobase-it undergoes reductive quenching accompanied by abstraction of a proton from a substrate. The results of modeling allowed us to identify active sites for PCET-the 'triangular pockets' on the edge facets of g-CN. We employ excited state PCET from the substrate to g-CN to selectively cleavethe endo-(sp3 )C-H bond in oxazolidine-2-ones followed by trapping the radical with O2 . This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pKa value and modeling suggest that g-CN excited state can cleave X-H bonds that are characterized by bond dissociation free energy (BDFE) ≈100â kcal mol-1 .
