RESUMEN
TiO2/WO3 heterojunctions are one of the most investigated systems for photocatalytic applications. However, distinct behavior can be found in the literature depending on the pollutant to be degraded and the photocatalyst preparation conditions. Some authors reported improved photocatalytic activities in relation to TiO2, while others a deleterious effect. Different factors have been identified to influence the activity of such systems. In this work, a systematic investigation of TiO2/WO3 samples with different W/Ti ratios (0-100%) was carried out using different pollutants as targets (gaseous NO, acetaldehyde and aqueous methylene blue solutions). A detailed structural investigation along with transient absorption studies and photoelectrochemical measurements allowed the rationalization of some of the previously reported factors that control the TiO2/WO3 photoactivity, i.e. the inability to reduce molecular oxygen, the stabilization of the anatase phase and the adsorption surface properties. The investigations also identified a factor not previously reported: in TiO2/WO3 systems, a fraction of long-lived holes do not take part in the interfacial charge transfer to efficient hole quenchers, such as methanol. This behavior seems to be related to the doping of the TiO2 matrix with W(vi) and plays a key role in the photocatalytic activity.
RESUMEN
The preparation of lamellar nanostructures through exfoliation of stacked niobates is an interesting approach to the development of photocatalysts for energy conversion and environmental remediation. These materials exhibit a rich surface chemistry and several nanocomposites can be produced through intercalation or impregnation of suitable precursors. In this work, the influence of the physico-chemical preparation conditions on the photocatalytic activity of Pt-hexaniobate nanocomposites was investigated aiming at the establishment of the main factors that control their photoreactivities. Modification of hexaniobate layers were carried out by adsorption and impregnation methods, using [Pt(NH3)4]Cl2 (Pt1) and H2PtCl6 (Pt2), respectively. The addition of platinum precursors (1% wt.) were performed in the presence of the exfoliating agent tert-butylammonium hydroxide, sNb, or after acidic precipitation followed by resuspension in plain water, eNb. All samples were submitted to photoirradiation to reduce the platinum precursors and the effect of a previous thermal treatment was also evaluated. It was observed that H2 evolution from aqueous methanol solutions is more favored on hexaniobate nanosheets (eNb-Pt1 and eNb-Pt2) instead of scrolled layers (sNb-Pt1 and sNb-Pt2), independent on the platinum precursor. Moreover, residual tert-butylammonium can act as hole scavenger and decrease the degradation rates for methanol oxidation in sNb samples. The curled layers observed for sNb samples seem to favor the photodegradation of cationic species, such as methylene blue. Thermal treatment at 500 °C leads to morphological changes with a decrease of the specific surface area due to restacking of the individual layers along with some curling. As a result, the H2 evolution rates strongly decreases in relation to the non-sintered samples, suggesting that the 'soft' photoreduction of platinum precursors is the best method for preparation of these photocatalysts. The correlations between the preparation conditions and the photocatalytic activity for different photoreactions can allow the development of optimized materials for specific applications.
RESUMEN
The photophysical behavior and reactive oxygen species (ROS) generation by chloroaluminum phthalocyanine (AlClPc) are evaluated by steady state absorption/emission, transient emission, and electron paramagnetic resonance spectroscopies in the presence of graphene oxide (GO), reduced graphene oxide (RGO), and carboxylated nanographene oxide (NGO). AlClPc and graphene oxides form a supramolecular structure stabilized by π-π interactions, which quantitatively quenches fluorescence emission and suppresses ROS generation. These effects occur even when graphenes are previously functionalized with Pluronic F-127. A small part of quenching is due to an inner filter effect, in which graphene oxides compete with AlClPc for light absorption. Nonetheless, most of the (static) quenching arises on the formation of a nonemissive ground state complex between AlClPc and graphene oxides. The efficiency of graphene oxides on the fluorescence quenching and ROS generation suppression follows the order: GO < NGO < RGO.
RESUMEN
The dynamics of the transfer of electrons stored in TiO2 nanoparticles to As(III) , As(V) , and uranyl nitrate in water was investigated by using the stopped-flow technique. Suspensions of TiO2 nanoparticles with stored trapped electrons (etrap (-) ) were mixed with solutions of acceptor species to evaluate the reactivity by following the temporal evolution of etrap (-) by the decrease in the absorbance at λ=600â nm. The results indicate that As(V) and As(III) cannot be reduced by etrap (-) under the reaction conditions. In addition, it was observed that the presence of As(V) and As(III) strongly modified the reaction rate between O2 and etrap (-) : an increase in the rate was observed if As(V) was present and a decrease in the rate was observed in the presence of As(III) . In contrast with the As system, U(VI) was observed to react easily with etrap (-) and U(IV) formation was observed spectroscopically at λ=650â nm. The possible competence of U(VI) and NO3 (-) for their reduction by etrap (-) was analyzed. The inhibition of the U(VI) photocatalytic reduction by O2 could be attributed to the fast oxidation of U(V) and/or U(IV) .
RESUMEN
The dynamics of the transfer of electrons stored in TiO2 nanoparticles to Cr(VI) in aqueous solution have been investigated using the stopped flow technique. TiO2 nanoparticles were previously irradiated under UV light in the presence of formic acid, and trapped electrons (e(trap)(-)) were made to react with Cr(VI) as acceptor species; other common acceptor species such as O2 and H2O2 were also tested. The temporal evolution of the number of trapped electrons was followed by the decrease in the absorbance at 600 nm, and the kinetics of the electron-transfer reaction was modeled. Additionally, the rate of formation of the surface complex between Cr(VI) and TiO2 was determined with the stopped flow technique by following the evolution of the absorbance at 400 nm of suspensions of nonirradiated TiO2 nanoparticles and Cr(VI) at different concentrations. An approximately quadratic relationship was observed between the maximum absorbance of the surface complex and the concentration of Cr(VI), suggesting that Cr(VI) adsorbs onto the TiO2 surface as dichromate. The kinetic analyses indicate that the electron transfer from TiO2 to Cr(VI) does not require the previous formation of the Cr(VI)-TiO2 surface complex, at least the complex detected here through the stopped flow experiments. When previously irradiated TiO2 was used to follow the evolution of the Cr(VI)-TiO2 complex, an inhibition of the formation of the complex was observed, which can be related to the TiO2 deactivation caused by Cr(III) deposition.
RESUMEN
The structuring of materials in the form of photonic crystals for photocatalytic applications is a quite new strategy aiming to enhance the performance of the photocatalysts at wavelength ranges where their absorption is poor. It is of particular interest to successfully manufacture an efficient photocatalytic system that could make use of solar light. Thus, the key of the strategy is the "slow photon effect", occurring at the edges of a forbidden band for photons. In this Perspective we have chosen some questions that we consider of relevance and that are well worth being addressed both theoretically and experimentally. It is the aim of this discussion to eventually lead to a more productive use of inverse opals as photonic photocatalytic materials.