Vagner R. de Mendonça

Nanoestruturas em fotocatálise: uma revisão sobre estratégias de síntese de fotocatalisadores em escala nanométrica

Advanced oxidative processes (AOPs) are based on chemical processes that can generate free radicals, such as hydroxyl radicals (.OH) which are strong, non-selective oxidant species that react with the vast majority of organic compounds. Nanostructured semiconductors, especially titanium dioxide (TiO2) in the anatase phase, are well-established photocatalysts for this process, which have proved to be useful in the degradation of dyes, pesticides and other contaminants. Research in different strategies for the synthesis of nanostructured semiconductors, with particular characteristic is currently a topic of interest in many studies. Thus, this paper presents a review about various synthesis strategies of nanostructured photocatalysts.

Synthesis of BiVO4via oxidant peroxo-method: insights into the photocatalytic performance and degradation mechanism of pollutants

This paper reports the synthesis of monoclinic bismuth vanadate (BiVO4) by the oxidant peroxide method with crystallization under hydrothermal conditions, and its catalytic performance on the photodegradation of pollutants under visible light. The as-synthesized BiVO4 materials were characterized by means of X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), Raman spectroscopy, Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) and scanning electron microscopy (SEM). Hydrothermal treatment above 80 °C was required to obtain pure monoclinic BiVO4 phase by releasing V5+ ions from vanadium peroxo complexes. With the increase in hydrothermal reaction temperature, the particle size decreased. All BiVO4 samples presented large size and shape distribution and band gap of approximately 2.40 eV. The as-prepared BiVO4 catalysts showed high photoactivity for decomposition of model pollutants, methylene blue (MB) and rhodamine B (RhB) dyes, under exposure to visible light. The photodegradation mechanism was evaluated by adding scavengers, DMSO and KBrO3, which were used to probe ˙OH radical and conduction band (CB) electrons, respectively. It was observed that photodegradation of MB and RhB dyes is caused by the action of ˙OH radicals, and that BiVO4 CB electrons do not have reduction potential sufficiently high to reduce dissolved oxygen to O2−˙. It was proven that the indirect mechanism, i.e. ˙OH radical formation, plays the major role on the BiVO4-assisted photodegradation process.

The Role of the Relative Dye/Photocatalyst Concentration in TiO2 Assisted Photodegradation Process.

Despite photocatalytic degradation is studied generally focusing the catalyst, its interaction with the contaminant molecule plays a fundamental role in the efficiency of that process. Then, we proposed a comparative study about the photodegradation of two well‐known dyes, with different acidity/basicity – Methylene Blue (MB) and Rhodamine B (RhB), catalyzed by TiO2 nanoparticles, varying both dye and photocatalyst concentrations. The results showed that the amphoteric character of MB molecules, even in a range of concentration of 5.0–10.0 mg L−1, did not imply in pH variation in solution. Therefore, it did not affect the colloidal behavior of TiO2 nanoparticles, independent of the relative dye/catalyst concentration. The acid–base character of RhB influenced the resultant pH of the solution, implicating in different colloidal behavior of the nanoparticles and consequently, in different degradation conditions according to dye concentration. As the isoelectric point of TiO2 is between the pH range of the RhB solutions used in this study, from 1.0 to 7.5 mg L−1, the resultant pH was the key factor for degradation conditions, from a well dispersed to an agglomerated suspension.

Heterostructure formation from hydrothermal annealing of preformed nanocrystals

One of the primary challenges in obtaining heterostructures is control of the morphology and surface features of the components that are suitable for a specific application. In this sense, the use of preformed nanoparticles as building blocks is interesting. However, to create heterojunctions between preformed nanoparticles, a further calcination step is usually needed that can result in changes in nanoparticle morphology and surface chemistry. Therefore, the main goal of this study was to explore collision-induced heteroaggregation and oriented attachment under hydrothermal conditions to obtain heterostructures from preformed nanoparticles without further thermal treatment or addition of capping agents. We use anatase TiO2 and rutile SnO2 nanoparticles as a model system. A kinetic model based on a diffusion-controlled reaction is adapted to describe the process. For tracking charge migration across the interface and, consequently, heterojunction formation, we employ an indirect method based on the detection of hydroxyl radicals formed over a semiconductor during UV radiation. The rate of hydroxyl radical formation is directly proportional to the photogenerated charge lifetime, which, in turn, depends on the number of heterojunctions formed. The insights presented here suggest the possibility of obtaining the benefits of heterostructures by using nanoparticles with controlled morphology and surface characteristics.

Vanadium pentoxide 1-D nanostructures applied to dye removal from aqueous systems by coupling adsorption and visible-light photodegradation†

This paper evaluates the photocatalytic and dye adsorption properties of highly crystalline orthorhombic vanadium pentoxide (V2O5) one-dimensional (1D) nanostructures, such as nanowires and nanorods, synthesized by a hydrothermal method. The as-synthesized samples were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), scanning and transmission electron microscopy (SEM and TEM), thermogravimetry (TGA), zeta potential, Fourier transform infrared spectrometry (FTIR), N2 adsorption isotherms and high-resolution 13C nuclear magnetic resonance (NMR). The dye adsorption capability and photocatalytic properties under visible light were mainly studied by the removal of the methylene blue dye (MB). Despite their low specific surface area (approximately 35 m2 g−1), the nanostructures showed high MB adsorption capabilities of greater than 400 mg g−1. Additionally, due to the band-gap values (approximately 2.6 eV), the nanostructures could be successfully applied to photodegradation under visible light, showing higher photoactivity than commercial V2O5. The MB adsorption mechanism onto V2O5 1D-nanostructures surface can be explained via NMe2+ interaction with the negatively charged surface of the studied samples. The observed combination of adsorbent and photocatalytic properties makes the V2O5 1D-nanostructures a promising material for organic pollutant decontamination, which appears more efficient for cationic species.

An Understanding of the Photocatalytic Properties and Pollutant Degradation Mechanism of SrTiO3 Nanoparticles

Strontium titanate nanoparticles have attracted much attention due to their physical and chemical properties, especially as photocatalysts under ultraviolet irradiation. In this paper, we analyze the effect of heating rate during the crystallization process of SrTiO3 nanoparticles in the degradation of organic pollutants. The relationship between structural, morphological and photocatalytic properties of the SrTiO3 nanoparticles was investigated using different techniques. Transmission electron microscopy and N2 adsorption results show that particle size and surface properties are tuned by the heating rate of the SrTiO3 crystallization process. The SrTiO3 nanoparticles showed good photoactivity for the degradation of methylene blue, rhodamine B and methyl orange dyes, driven by a nonselective process. The SrTiO3 sample with the largest particle size exhibited higher photoactivity per unit area, independent of the molecule to be degraded. The results pointed out that the photodegradation of methylene blue dye catalyzed by SrTiO3 is caused by the action of valence band holes (direct pathway), and the indirect mechanism has a negligible effect, i.e. degradation by O2−• and •OH radicals attack.

A building blocks strategy for preparing photocatalytically active anatase TiO2/rutile SnO2 heterostructures by hydrothermal annealing.

Effective heterostructures for photocatalysis need to present good electron-hole mobility among phases, a feature that is only attained with satisfactory interface quality. For very small sizes and with a stable colloidal state, the oriented attachment mechanism can be used to prepare suitable structures by means of a building blocks strategy, whereby preformed nanoparticles are used to control the desired amount of each phase in the heterostructure. Here, we show the success of this strategy for anatase TiO2/rutile SnO2 heterostructures, applying conventional hydrothermal annealing, where successive collisions among particles increase the probability of oriented attachment. The photodegradation of Rhodamine B in water under UV radiation was used as a probe reaction to evaluate formation of the heterostructure, as indicated by an increase in photoactivity. Increased heterostructure photoactivity was related to heterojunction formation and charge separation. The increased lifetimes of the photogenerated charges, due to heterojunction formation, enabled them to reach the oxides surface and promote photocatalytic reactions. The insights presented here may be used in a rationalized synthesis method to obtain heterostructures from preformed nanocrystals.