Nanosecond laser flash photolysis studies for the elucidation of photoinduced processes in different TiO2 photocatalysts

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Spectroscopic and kinetic characterization of photogenerated charge carriers in photocatalysts

The catastrophic consequences of increased power consumption, such as drastically rising CO2 levels, natural disasters, environmental pollution and dependence on fossil fuels supplied by countries with totalitarian regimes, illustrate the urge to develop sustainable technologies for energy generation. Photocatalysis presents eco-friendly means for fuels production via solar-to-chemical energy conversion. The conversion efficiency of a photocatalyst critically depends on charge carrier processes taking place in the ultrafast time regime. Transient absorption spectroscopy (TAS) serves as a perfect tool to track those processes. The spectral and kinetic characterization of charge carriers is indispensable for the elucidation of photocatalytic mechanisms and for the development of new materials. Hence, in this review, we will first present the basics of TAS and subsequently discuss the procedure required for the interpretation of the transient absorption spectra and transient kinetics. The discussion will include specific examples for charge carrier processes occurring in conventional and plasmonic semiconductors

Photocatalytic activity and charge carrier dynamics of TiO2 powders with a binary particle size distribution

The effects of the particle size distribution on the charge carrier dynamics and the photocatalytic activity of mixed titanium dioxide (TiO2) powder samples were investigated in this work. Instead of the synthesis of the small semiconductor particles, the binary particle size distributions of the powders were obtained by mixing commercially available TiO2 powders with different particle sizes. The pure anatase samples (average diameters: 7, 20, and 125 nm, respectively) were created via ultrasound treatment and discreet drying. The photocatalytic activity of the powder samples was assessed by the degradation of nitric oxide (NO) and acetaldehyde in the gas phase. Furthermore, the charge carrier kinetics was determined using transient absorption spectroscopy following pulsed laser excitation. Importantly, a recently published model based on fractal dimensions was used to fit the transient signals of the photo generated charge carriers in the TiO2 powder samples. The effects of the particle size on the acetaldehyde degradation could be explained by the formation of agglomerates, which reduce the available surface area of smaller particles. The fast oxidation of acetaldehyde on the surface of TiO2 by direct hole transfer was further independent of the observed charge carrier lifetimes on the microsecond time scale. The photocatalytic NO degradation, on the other hand, increased for samples containing larger amounts of small particles. The corresponding photonic efficiencies correlated well with the charge carrier lifetimes determined by the time-resolved studies. Hence, it was concluded that a long charge carrier lifetime generally leads to higher fractional conversions of NO. The employed fractal fit function was proved to be beneficial for the kinetic analysis of charge carrier recombination in TiO2, in direct comparison with a second order fit function. © 2018 the Owner Societies

Ionic liquid-mediated microstructure regulations of layered perovskite for enhanced visible light photocatalytic activity

The presence of pollutants, e.g., pharmaceutical residues and industrial pollutants causes serious risks and irreversible damage to public health and ecological balance. Semiconductor-based photocatalysis is an attractive way to treat polluted water. Rational design and nanostructuring of semiconductors with visible light absorption and prominent surfaces could strengthen surface-interface reactions, resulting in improved photocatalytic degradation. Herein, layered structured perovskites Bi4Ti3O12 (BTO) were synthesized by an ionic liquid [1-butyl-3-methylimidazolium iodide (Bmim)I] assisted approach. The precise tuning of synthetic conditions allowed formations of various microstructures, including spherical nanoparticles, nanoplates and nanorods, respectively. The optical analyses demonstrated that samples were typically visible light absorbents with narrow band gap energies (2.96–2.73 eV), and displayed pronounced degradation for pharmaceutical residues under visible light illumination. The factors responsible for the high efficiency of BTO photocatalysts were discussed in terms of unique structure, optical alignment, dipole induced carrier separation and formation of active radicals. Among studied samples, the nanorod shaped BTO showed 1.31 and 1.46 times higher apparent rate constants for tetracycline and ibuprofen degradation than its counterparts (spherical nanoparticles and nanoplates), respectively. The better performance of nanorods was ascribed to their higher visible light harvesting ability. Importantly, BTO nanorods exhibited nonselective degradation activity for diverse pollutants of pharmaceutical residues and industrial contaminants. This work demonstrates the unique strategy of microstructure regulation and a wide range of applications of layered perovskites for environmental remediation

Understanding charge transfer processes on metal oxides - A laser-flash-photolysis study

In the focus of this study, mixtures of commercially available TiO2 powders were created and their photocatalytic activity concerning the acetaldehyde degradation in the gas phase was tested. Further, the lifetime of the photogenerated charge carriers was analyzed by Laser-Flash-Photolysis-Spectroscopy. The acetaldehyde degradation experiments of the mixed powders lead to positive and negative deviations from the expected weighted mean. Nevertheless, their photocatalytic activity could be correlated with the lifetime of the charge carriers. A longer charge carrier lifetime at ambient conditions correlated with a lower fractional conversion of acetaldehyde. The advantageous activities of the samples were associated with a charge transfer reaction between larger and smaller particles comparable to the antenna mechanism. © 2016 SPIE.BMBFKRONOS International, Inc

Laser-flash-photolysis-spectroscopy: A nondestructive method?

Herein, we report the effect of the laser illumination during the diffuse-reflectance laser-flash-photolysis measurements on the morphological and optical properties of TiO2 powders. A grey-blue coloration of the TiO2 nanoparticles has been observed after intense laser illumination. This is explained by the formation of nonreactive trapped electrons accompanied by the release of oxygen atoms from the TiO2 matrix as detected by means of UV-vis and EPR spectroscopy. Moreover, in the case of the pure anatase sample a phase transition of some TiO2 nanoparticles located in the inner region from anatase to rutile occurred. It is suggested that these structural changes in TiO2 are caused by an energy and charge transfer to the TiO2 lattice.BMBF/13N13350Government of the Russian FederationGlobal Research Laboratory (GRL)/NRF-2014K1A1A204104

Improved charge carrier separation in barium tantalate composites investigated by laser flash photolysis

Charge carrier dynamics in phase pure Ba5Ta4O15 and in a Ba5Ta4O15–Ba3Ta5O15 composite have been studied by means of diffuse reflectance laser flash photolysis spectroscopy in the presence and absence of an electron donor, in order to reveal the reason for the improved photocatalytic performance of the latter. For the first time the transient absorption of trapped electrons with a maximum at around 650 nm and of trapped holes with a transient absorption maximum at around 310 nm is reported for tantalates. The decay kinetics of the photogenerated charge carriers could be fitted by second order reaction kinetics, and the direct recombination of the trapped electrons with the trapped holes was proven. In the absence of an electron donor, no difference in the decay behavior between the phase pure material and the composite material is found. In the presence of methanol, for the pure phase Ba5Ta4O15 the recombination of the charge carriers could not be prevented and the trapped electrons also recombine with the ˙CH2OH radical formed via the methanol oxidation by the trapped holes. However, in the composite, the electron can be stored in the system, the ˙CH2OH radical injects an electron into the conduction band of the second component of the composite, i.e., Ba3Ta5O15. Thus, the electrons are available for an extended period to induce reduction reactions

The Sloan Digital Sky Survey Reverberation Mapping Project: Post-Starburst Signatures in Quasar Host Galaxies at z < 1

Quasar host galaxies are key for understanding the relation between galaxies and the supermassive black holes (SMBHs) at their centers. We present a study of 191 broad-line quasars and their host galaxies at z < 1, using high signal-to-noise ratio (SNR) spectra produced by the Sloan Digital Sky Survey Reverberation Mapping project. Clear detection of stellar absorption lines allows a reliable decomposition of the observed spectra into nuclear and host components, using spectral models of quasar and stellar radiations as well as emission lines from the interstellar medium. We estimate age, mass (M*), and velocity dispersion (sigma*) of the host stars, the star formation rate (SFR), quasar luminosity, and SMBH mass (Mbh), for each object. The quasars are preferentially hosted by massive galaxies with M* ~ 10^{11} Msun characterized by stellar ages around a billion years, which coincides with the transition phase of normal galaxies from the blue cloud to the red sequence. The host galaxies have relatively low SFRs and fall below the main sequence of star-forming galaxies at similar redshifts. These facts suggest that the hosts have experienced an episode of major star formation sometime in the past billion years, which was subsequently quenched or suppressed. The derived Mbh - sigma* and Mbh - M* relations agree with our past measurements and are consistent with no evolution from the local Universe. The present analysis demonstrates that reliable measurements of stellar properties of quasar host galaxies are possible with high-SNR fiber spectra, which will be acquired in large numbers with future powerful instruments such as the Subaru Prime Focus Spectrograph.Comment: ApJ in pres