Diffuse Reflectance Transient Absorption Research Articles

Regarding the Nature of Charge Carriers Formed by UV or Visible Light Excitation of Carbon-Modified Titanium Dioxide

Although titanium dioxide gathers many of the required properties for its application in photocatalytic processes, its lack of activity in the visible range is a major hurdle yet to be overcome. Among different strategies, the post-synthesis modification of TiO2 powders with organic compounds has already led to commercially available materials, such as KRONOClean 7000. In this work, we apply diffuse reflectance transient absorption spectroscopy on this visible-light active photocatalyst and study the dynamics of the charge carriers alternatively induced by UV or visible light laser irradiation, under inert or reactive atmospheres. Our results can be interpreted by considering the material as TiO2 sensitized by an organic-based layer, in agreement with previous studies on it, and show that the oxidative power of the material is considerably diminished under visible light irradiation. By complementarily performing continuous visible light irradiation photocatalysis experiments in aerated aqueous suspensions, we show that, although the oxidation of methanol proceeds at a very slow rate, the oxidation of chlorpromazine occurs much faster thanks to its better suited redox potential.

Time-Resolved Studies of Charge Recombination in the Pyrene/TCNQ Charge-Transfer Crystal: Evidence for Tunneling

Previous studies of solid-state tetracyanobenzene-based donor-acceptor complexes showed that these materials were highly susceptible to both laser and mechanical damage that complicated the analysis of their electron-transfer kinetics. In this paper, we characterize the optical properties of a pyrene/tetracyanoquinodimethane charge-transfer crystal that is much more robust than the tetracyanobenzene compounds. This donor-acceptor complex has a charge-transfer absorption that extends into the near-infrared, rendering the crystal black. We use time-resolved fluorescence and diffuse reflectance transient absorption to study its dynamics after photoexcitation. We show that the initially excited charge-transfer state undergoes a rapid, monoexponential decay with a lifetime of 290 ps at room temperature. There is no evidence for any long-lived intermediate or dark states; therefore, this decay is attributed to charge recombination back to the ground state. Fluorescence lifetime measurements demonstrate that this process becomes temperature-independent below 60 K, indicative of a thermally activated tunneling mechanism. The subnanosecond charge recombination makes this low-band-gap donor-acceptor material a poor candidate for generating long-lived electron-hole pairs.

Optical Spectroscopy and Microscopy Studies on the Spatial Distribution and Reaction Dynamics in Zeolites

This Perspective describes current research into the photochemistry of zeolites, pointing out issues yet to be resolved and suggesting future directions of investigation. The fascinating host materials are known to act as a support for guest ions, molecules, or clusters both within their large interior cage/channel networks and on their exterior surfaces, together providing rich chemistry. Two techniques have proven particularly successful for their study, diffuse reflectance transient absorption spectroscopy and optical microscopy. The various properties revealed by these techniques include intracrystalline and intercrystalline migration, migration-assisted photochemical reactions, and heterogeneous distribution of guest molecules among and within crystals.

Femtosecond Diffuse Reflectance Transient Absorption for Dye-Sensitized Solar Cells under Operational Conditions: Effect of Electrolyte on Electron Injection

By applying diffuse reflectance transient absorption spectroscopy to dye-sensitized solar cells under operational conditions, we were able to directly correlate interfacial electron injection kinetics from a Ru complex sensitizer to a TiO(2) nanocrystalline electrode with the incident photon to current efficiency values. It was revealed that ionic liquid electrolytes reduced the initial electron injection efficiency by suppression of the approximately 100 ps process.

(Invited) Femtosecond Diffuse Reflectance Transient Absorption to Measure Dye-Sensitized Solar Cells under Operational Conditions

not Available.

Surface Photochemistry: Organic Molecules within Nanocavities of Calixarenes

In order to gain more information regarding photochemical processes in heterogeneous environments (opaque or powdered samples) laser induced time resolved luminescence and diffuse reflectance transient absorption spectroscopies were used for the study of benzophenone (and other neutral organic molecules) as guests and p-tert-butylcalix[n]arenes with n = 4, 6 and 8 (H(n)CLX[n]) and partially or totally O-propylated p-tert-butylcalix[4]arenes (H(n)Pr(m)CLX[4], n = 2, 1 and 0; m = 2, 3 and 4, respectively) were used as hosts. One of the main conclusions was that the solid support can deeply affect or even control the photochemistry of an adsorbed probe. A simple new methodology for lifetime distribution analysis of the decay of the probes included into calixarenes and other nanocavities was applied with success for decay data obtained with the use of intensified charge couple devices, i.e. intensified charge couple devices, ICCDs. Diffuse reflectance laser flash photolysis and gas chromatography - mass spectrometry techniques also provided complementary information, the former about transient species and the latter regarding the final products formed after light absorption.

Surface photochemistry: Diffuse reflectance studies of thioketones included into p-tert-butylcalix[6 and 8]arenes

This paper presents time resolved laser induced luminescence (LIL) and diffuse reflectance laser flash-photolysis (DRLFP) studies of solid powdered samples of xanthione (XT) and 4H-1-benzopyran-4-thione (BPT). These thioketones form inclusion complexes with p-tert-butylcalix[6]arene (CLX[6]) and p-tert-butylcalix[8]arene (CLX[8]). Room temperature air equilibrated LIL studies for XT/CLX[8] inclusion complex have shown the existence of both fluorescence and delayed fluorescence emission (S 2 → S 0 emissions in the nanosecond and microsecond time ranges, respectively) peaking at ca. 460 nm while phosphorescence peaks at about 670 nm with a half life of about 4 μs. For the BPT/CLX[8] inclusion complex, the emissions now peak at ca. 450 and 630 nm, respectively. When these two thioketones are included into the CLX[6] nanocavities similar luminescence spectra were detected. The phosphorescence spectra in all cases present a clear vibrational structure characteristic of non-polar environments, in accordance with the non-polar character of the calixarene‘s cavities. Diffuse reflectance transient absorption spectra revealed in all cases the presence of the triplet state of the thioketones and also of longer lived species. The use of chromatographic methods (GC-MS) allowed us to identify the formation of xanthone, chromone and hydroxy-thioketones following laser irradiation at 355 or 337 nm.

Environmental Photochemistry on Semiconductor Surfaces. Visible Light Induced Degradation of a Textile Diazo Dye, Naphthol Blue Black, on TiO2 Nanoparticles

Visible light induced degradation of the textile diazo dye Naphthol Blue Black (NBB) has been carried out on TiO2 semiconductor nanoparticles. Diffuse reflectance transient absorption and FTIR techniques have been used to elucidate the mechanistic details of the dye degradation. The failure of the dye to degrade on insulator surfaces such as Al2O3 or in the absence of oxygen further highlights the importance of semiconducting properties of support material in controlling the surface photochemical processes. The primary event following visible light excitation is the charge injection from the excited dye molecule into the conduction band of the semiconductor TiO2, producing the dye cation radical. This was confirmed by diffuse reflectance laser flash photolysis. The surface-adsorbed oxygen plays an important role in scavenging photogenerated electrons, thus preventing the recombination between the dye cation radical and photoinjected electrons. Diffuse reflectance FTIR study facilitated identification of r...

Observation and characterization of excimer emission from anthracene included in NaX zeolite

We observed for the first time an excimer emission of anthracene included in the supercages of zeolite X at high ratios of anthracene to supercage. The mechanism giving rise to the excimer emission was ascribed to charge recombination of anthracene cation—anion radical pair on the basis of picosecond time-resolved diffuse reflectance transient absorption studies as well as picosecond fluorescence measurements.

Photochemistry on surfaces: Fluorescence emission of monomers and dimers and triplet state absorption of acridine orange adsorbed on microcrystalline cellulose

Prompt fluorescence as well as delayed fluorescence emission of acridine orange was detected at room temperature from samples where this dye is adsorbed on microcrystalline cellulose. Ground state absorption studies provided evidence for dimer formation of the dye when adsorbed on cellulose, and the equilibrium constant for dimerisation was determined as 1.6±0.1 × 10 6mol −1g. At low loadings of acridine orange on cellulose (<1 μmol g −1) the fluorescence emission is mainly due to the monomer and is similar to that observed in ethanolic solutions where little aggregation occurs, and peaks at 530 nm. A linear dependence of the fluorescence intensity on the amount of light absorbed by the dye was established for these “diluted” samples. However, at higher loadings (>20 μmol g −1), the fluorescence intensity decreases, and the emission is broad with its maximum at 620 nm, and is mainly due to the dimer. By assuming that the excited monomer and dimer of acridine orange are the only emitting species, it was possible to determine the fluorescence quantum yields for these two species when adsorbed on microcrystalline cellulose as 0.95±0.05 and 0.40±0.10, respectively. Pulsed emission studies at room temperature in the millisecond time-range also revealed monomer and dimer emissions on this longer time-scale. These are shown to be due to thermally activated delayed fluorescence arising from the triplet states of monomer and dimer acridine orange as confirmed by diffuse reflectance transient absorption studies.

ChemInform Abstract: Triplet Energy Transfer as a Probe of Surface Diffusion Rates: A Time‐Resolved Diffuse Reflectance Transient Absorption Spectroscopy Study

Chemischer InformationsdienstVolume 17, Issue 3 Article ChemInform Abstract: Triplet Energy Transfer as a Probe of Surface Diffusion Rates: A Time-Resolved Diffuse Reflectance Transient Absorption Spectroscopy Study N. J. TURRO, N. J. TURROSearch for more papers by this authorM. B. ZIMMT, M. B. ZIMMTSearch for more papers by this authorI. R. GOULD, I. R. GOULDSearch for more papers by this authorW. MAHLER, W. MAHLERSearch for more papers by this author N. J. TURRO, N. J. TURROSearch for more papers by this authorM. B. ZIMMT, M. B. ZIMMTSearch for more papers by this authorI. R. GOULD, I. R. GOULDSearch for more papers by this authorW. MAHLER, W. MAHLERSearch for more papers by this author First published: January 21, 1986 https://doi.org/10.1002/chin.198603066Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume17, Issue3January 21, 1986 RelatedInformation

Triplet energy transfer as a probe of surface diffusion rates: time-resolved diffuse reflectance transient absorption spectroscopy study

Triplet energy transfer as a probe of surface diffusion rates: time-resolved diffuse reflectance transient absorption spectroscopy study