Factors affecting the selectivity of the photocatalytic conversion of nitroaromatic compounds over TiO2 to valuable nitrogen-containing organic compounds

The photocatalytic conversion of various nitroaromatic compounds in alcohols employing four different types of TiO2 (Sachtleben Hombikat UV100 as anatase, Crystal Global R34 as rutile, Evonik-Degussa Aeroxide P25 as an anatase-rutile mixture, and home-made mesoporous anatase) has been studied. The effect of platinization of these different types of TiO2 on the reaction sequence has also been investigated. Upon irradiation of an ethanolic solution of m-nitrotoluene, as a model reaction, in the presence of the bare photocatalyst, different products were obtained according to the applied photocatalyst. It was found that the surface properties of the photocatalyst play an important role in the reaction pathway and thus in the selectivity of the products. In all cases, a simultaneous reduction of the nitro compound and an oxidation of the alcohol are induced by the photogenerated electrons and holes, respectively. An imine is then produced upon condensation of the generated aldehyde and amino compounds. Rutile was found to be more selective towards the primary amino compound (m-toluedine) while anatase catalysts gave a mixture of m-toluidine and its imine (N-ethylidene-3-methylaniline). A cyclization reaction of the produced imine to generate methyl quinoline was observed when Aeroxide P25 was used as a photocatalyst. Employing platinized TiO2, the hydrogenation of the produced imine yielding N-alkylated products was found to occur in all cases. However, the selectivity towards the mono N-alkylated product was the best using platinized Hombikat UV100. This selectivity was found to be also influenced by the loaded amount of Pt, the platinization method, and the illumination time but not by the light intensity.© 2013 the Owner Societies

Reaction rate study of the photocatalytic degradation of dichloroacetic acid in a black body reactor

The light-induced degradation of dichloroacetic acid in aqueous suspensions containing the TiO2 photocatalyst Hombikat UV 100 was investigated. The reactions were performed in a black body reactor in which the rate of conversion, defined as the time derivative of the extent of conversion, is not affected by the light scattering properties of the photocatalysts. At sufficiently high concentrations of both the probe compound and the photocatalyst the rate of conversion was found to be unswayed by the initial concentration of the probe compound, the mass concentration of the photocatalyst, and the suspension volume. Thus, the chosen experimental conditions enable the determination of the rate of conversion and the quantum yield of the light induced degradation of dichloroacetic acid in aqueous photocatalyst suspension with sufficiently good reproducibility. The experimental procedure employed here seems to be generally applicable to determine rates of conversion and quantum yields that possibly allow a comparison of the activities of photocatalysts in aqueous suspensions

Ruthenium-modified zinc oxide, a highly active vis-photocatalyst: the nature and reactivity of photoactive centres

We recently reported a highly active photocatalyst, ruthenium-modified zinc oxide, which was found to be able to utilise the red part of the visible light spectrum for photocatalytic reactions [Bloh et al., Environ. Sci. Pollut. Res., 2012, 19, 3688-3695]. However, the origin and mechanism of the observed activity as well as the nature of the photoactive centres are still unknown. Herein, we expand on that by reporting a series of experiments specifically designed to unravel the mechanism of the visible light induced photocatalytic reactions. The absolute potentials of the valence and the conduction band edge are identified by the combined use of electrochemical impedance and UV-vis diffuse reflectance spectroscopy. The conduction band electron and the valence band hole activity are assessed through a novel approach tracing their signature oxidative species, i.e., hydrogen peroxide and hydroxyl radicals, respectively. Oxygen reduction currents are measured at different potentials to investigate the role of molecular oxygen as an electron scavenger as well as the underlying reduction pathways. Additionally, the photocatalytic activity of the samples is verified using another (ISO standard) degradation test, the gas-phase oxidation of nitric oxide. The experimental results reveal that the employed synthetic route yields a unique mixture of ruthenium(VI)-doped zinc oxide and ruthenium(VI) oxide particles with both forms of the ruthenium playing their own independent role in the enhancement of the photocatalytic activity. The ruthenium ions acting as dopants enable a better charge separation as well as the absorption of red light resulting in the direct promotion of electrons from the Ru(VI)-species to the conduction band. Both, the conduction band electrons and the thus formed Ru(VII) subsequently participate in the degradation of the pollutant molecules. The ruthenium dioxide particles, on the other hand, act as catalysts increasing the efficiency of the reaction by improving the oxygen reduction properties of the material.BMBF/HelioClean/03X0069

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

Light-Induced Reactions of Chlorpromazine in the Presence of a Heterogeneous Photocatalyst

A commercial carbon-modified titanium dioxide, KRONOClean 7000, was applied as a UV(A) and visible-light active photocatalyst to investigate the conversion of the antipsychotic pharmaceutical chlorpromazine in aqueous phase employing two monochromatic light sources emitting at wavelengths of 365 and 455 nm. Photocatalytic and photolytic conversion of chlorpromazine under both anaerobic and aerobic conditions was analyzed using a HPLC-MS technique. Depending on the irradiation wavelength and presence of oxygen, varying conversion rates and intermediates revealing different reaction pathways were observed. Upon visible light irradiation under aerobic conditions, chlorpromazine was only converted in the presence of the photocatalyst. No photocatalytic conversion of this compound under anaerobic conditions upon visible light irradiation was observed. Upon UV(A) irradiation, chlorpromazine was successfully converted into its metabolites in both presence and absence of the photocatalyst. Most importantly, chlorpromazine sulfoxide, a very persistent metabolite of chlorpromazine, was produced throughout the photolytic and photocatalytic conversions of chlorpromazine under aerobic conditions. Chlorpromazine sulfoxide was found to be highly stable under visible light irradiation even in the presence of the photocatalyst. Heterogeneous photocatalysis under UV(A) irradiation resulted in a slow decrease of the sulfoxide concentration, however, the required irradiation time for its complete removal was found to be much longer compared to the removal of chlorpromazine at the same initial concentration

Evaluating carbon dots as electron mediators in photochemical and photocatalytic processes of NiFe2O4

Spinel ferrites such as nickel ferrite are promising energy conversion photocatalysts as they are visible-light absorbers, chemically stable, earth abundant, and inexpensive. Nickel ferrite shows poor photocatalytic activity due to fast electron-hole recombination upon illumination. This study evaluates the capability of carbon dots (CDs) to improve charge-carrier separation in NiFe2O4. We report a facile solvothermal approach for synthesizing NiFe2O4 and CDs/NiFe2O4 nanoparticles at 200-215 °C. The photocatalysts were characterized using transmission and scanning electron microscopy, x-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, UV-VIS-NIR spectroscopy, photoelectrochemical analysis, and laser flash photolysis. Photocatalytic oxidation of methanol to formaldehyde under visible light was employed to test the effect of CDs on the photocatalytic efficacy of NiFe2O4. UV-VIS-NIR spectroscopy depicted a total quenching of NIR absorption and a diminished absorption of a peak at ∼745 nm in CDs/NiFe2O4 compared with NiFe2O4, indicating a transfer of electrons from NiFe2O4 to CDs. A 12-fold increment in the incident-photon-to-charge-efficiency was achievable with CDs/NiFe2O4 (0.36%) compared with NiFe2O4 (0.03%). Impedance spectroscopy exhibited a more efficient charge separation and faster interfacial charge transfer in CDs/NiFe2O4 compared with pure NiFe2O4. This was accounted for by the lower initial quantity of charge carrier upon irradiation in CDs/NiFe2O4 compared with NiFe2O4 as detected from laser flash photolysis, indicating that CDs acted as electron acceptors and reservoirs in CDs/NiFe2O4. Compared with NiFe2O4, CDs/NiFe2O4 showed an enhanced photocatalytic activity toward formaldehyde formation. Consequently, CDs are good electron mediators for NiFe2O4, capable of improving charge-carrier separation and the photocatalytic activity of NiFe2O4

The Relevance of ATR-FTIR Spectroscopy in Semiconductor Photocatalysis

Attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy has a high potential for investigating a wide range of samples and systems. In photocatalysis, various interfacial phenomena can be studied using this technique, including pH-dependent adsorption and photodegradation of probe molecules. The analysis of the processes occurring at the interface of thin particle films deposited on the surface of an ATR crystal, either in the liquid or the gas phase, is perhaps the best way to elucidate the mechanism of adsorption and heterogeneous photocatalytic reactions. This chapter summarizes the recent advances and applications of ATR-FTIR techniques in semiconductor photocatalysis. A brief outlook at some of the possible investigations in this area is provided and the different proposed adsorption and photocatalytic degradation mechanisms are discussed

Photodegradation of herbicide imazapyr and phenol over mesoporous bicrystalline phases TiO2: A kinetic study

Mesoporous TiO2 nanoparticles were synthesized at different temperatures (400–800 °C). The resulting mesoporous anatase–rutile TiO2 mixtures between 27 and 82% were found to have different structural properties (morphology, mesoporosity, crystallite phases, and sizes) affected through the calcination process. They were tested for the photocatalytic degradation of the herbicides imazapyr and phenol, compared with the nonporous TiO2 P-25. The present work is an extension of a previously published study discussing the influence of the rutile content on the photocatalytic performance of the nanocrystals, based on the modified first order kinetic model, where the degradation rate is a function of the specific surface area of the material. The apparent degradation rate using T-800 is 10-fold higher than in the case using TiO2 P-25. The material with the lowest anatase content (T-800) exhibits the highest photocatalytic activity in terms of initial reaction rate per unit surface area. It is considered that mixed-phase photocatalysts with rutile–anatase exhibit enhanced photoactivity with the increase of the rutile proportion

Light intensity dependence of the kinetics of the photocatalytic oxidation of nitrogen(ii) oxide at the surface of TiO2

Air pollution by nitrogen oxides represents a serious environmental problem in urban areas where numerous sources of these pollutants are concentrated. One approach to reduce the concentration of these air pollutants is their light-induced oxidation in the presence of molecular oxygen and a photocatalytically active building material which uses titanium dioxide as the photocatalyst. Herein, results of an investigation concerning the influence of the photon flux and the pollutant concentration on the rate of the photocatalytic oxidation of nitrogen(ii) oxide in the presence of molecular oxygen and UV(A) irradiated titanium dioxide powder are presented. A Langmuir-Hinshelwood-type rate law for the photocatalytic NO oxidation inside the photoreactor comprising four kinetic parameters is derived being suitable to describe the influence of the pollutant concentration and the photon flux on the rate of the photocatalytic oxidation of nitrogen(ii) oxide. © 2013 the Owner Societies

In-Situ Synthesis of Nb2O5/g-C3N4 Heterostructures as Highly Efficient Photocatalysts for Molecular H2 Evolution under Solar Illumination

This work focuses on the synthesis of heterostructures with compatible band positions and a favourable surface area for the efficient photocatalytic production of molecular hydrogen (H2). In particular, 3-dimensional Nb2O5/g-C3N4 heterostructures with suitable band positions and high surface area have been synthesized employing a hydrothermal method. The combination of a Nb2O5 with a low charge carrier recombination rate and a g-C3N4 exhibiting high visible light absorption resulted in remarkable photocatalytic activity under simulated solar irradiation in the presence of various hole scavengers (triethanolamine (TEOA) and methanol). The following aspects of the novel material have been studied systematically: the influence of different molar ratios of Nb2O5 to g-C3N4 on the heterostructure properties, the role of the employed hole scavengers, and the impact of the co-catalyst and the charge carrier densities affecting the band alignment. The separation/transfer efficiency of the photogenerated electron-hole pairs is found to increase significantly as compared to that of pure Nb2O5 and g-C3N4, respectively, with the highest molecular H2 production of 110 mmol/g·h being obtained for 10 wt % of g-C3N4 over Nb2O5 as compared with that of g-C3N4 (33.46 mmol/g·h) and Nb2O5 (41.20 mmol/g·h). This enhanced photocatalytic activity is attributed to a sufficient interfacial interaction thus favouring the fast photogeneration of electron-hole pairs at the Nb2O5/g-C3N4 interface through a direct Z-scheme