Influence of TiO2 electronic structure and strong metal-support interaction on plasmonic Au photocatalytic oxidations

Aiming at understanding how plasmonic reactions depend on important parameters such as metal loading and strong metal-support interaction (SMSI), we report the plasmonic photodegradation of formic acid (FA) under green LED irradiation employing three TiO2 supports (stoichiometric TiO2, N-doped TiO2, black TiO2) modified with Au nanoparticles (NPs) 3-6 nm in size. The rate of FA photo-oxidation follows different trends depending on Au loading for stoichiometric and doped Au/TiO2 materials. In the first case, the only contribution of hot electron transfer produces a volcano-shaped curve of photoreaction rates with increasing the Au loading. When TiO2 contains intra-bandgap states the photoactivity increases linearly with the Au NPs amount, thanks to the concomitant enhancement produced by hot electron transfer and plasmonic resonant energy transfer (PRET). The role of PRET is supported by Finite-Difference Time-Domain simulations, which show that the increase of both Au NPs inter-distance and of SMSI enhances the probability of charge carrier generation at the Au/TiO2 interface

New Insights into the Mechanism of Visible Light Photocatalysis

ABSTRACT: In recent years, the area of developing visible-lightactive photocatalysts based on titanium dioxide has been enormously investigated due to its wide range of applications in energy and environment related fields. Various strategies have been designed to efficiently utilize the solar radiation and to enhance the efficiency of photocatalytic processes. Building on the fundamental strategies to improve the visible light activity of TiO2-based photocatalysts, this Perspective aims to give an insight into many contemporary developments in the field of visible-light-active photocatalysis. Various examples of advanced TiO2 composites have been discussed in relation to their visible light induced photoconversion efficiency, dynamics of electron− hole separation, and decomposition of organic and inorganic pollutants, which suggest the critical need for further development of these types of materials for energy conversion and environmental remediation purposes

Caracterização do gene vip3A e toxicidade da proteína Vip3Aa50 à lagarta-do-cartucho e à lagarta-da-soja

O objetivo deste trabalho foi caracterizar o gene vip3A de Bacillus thuringiensis e verificar a toxicidade da proteína Vip3Aa50 a larvas da lagarta-do-cartucho (Spodoptera frugiperda) e da lagarta-da-soja (Anticarsia gemmatalis). O gene vip3A foi amplificado por PCR, com iniciadores específicos, e gerou um fragmento de 2.370 pb. Esse fragmento foi clonado em vetor pGEM-T Easy e, em seguida, sequenciado, subclonado em vetor de expressão pET-28a (+) e inserido em células de Escherichia coli BL21 (DE3). A expressão da proteína Vip3Aa50 foi induzida por isopropil-β-D-1-tiogalactopiranosídeo (IPTG), visualizada em SDS-PAGE e detectada por "Western blot". Os ensaios de toxicidade revelaram alta atividade da proteína Vip3Aa50 contra as larvas neonatas da lagarta-da-soja e da lagarta-do-cartucho, com CL50 de 20,3 e 79,6 ng cm-2, respectivamente. O gene vip3Aa50 é um novo gene da classe vip3A

Experimental study on the link between optical emission, crystal defects and photocatalytic activity of artist pigments based on zinc oxide

The historical knowledge inherited from house paint documents and the experimental research on synthetic pigments show that production methods have an important role in the performance of paint. In this regard, this work investigates the links existing between the optical emission, crystal defects and photocatalytic activity of zinc white pigment from different contemporary factories, with the aim of elucidating the effects of these characteristics onto the tendency of the pigment to induce paint failures. The analysed samples display highly similar crystallite structure, domain size, and specific surface area, whilst white pigments differ from pure ZnO in regards to the presence of zinc carbonate hydrate that is found as a foreign compound. In contrast, the photoluminescence measurements categorize the analysed samples into two groups, which display different trap-assisted emissions ascribed to point crystal defects introduced during the synthesis process, and associated to Zn or O displacement. The photocatalytic degradation tests infer that the emerged defective structure and specific surface area of ZnO-based samples influence their tendency to oxidize organic molecules under light irradiation. In particular, the results indicate that the zinc interstitial defects may be able to promote the photogenerated electron-hole couples separation with a consequent increase of the overall ZnO photocatalytic activity, negatively affecting the binding medium stability. This groundwork paves the way for further studies on the link between the photoluminescence emission of the zinc white pigment and its tendency to decompose organic components contained in the binding medium