The effect of the solvent on the electronic properties of the triarylmethane dye rosolic acid (RA) is investigated by means of UV-VIS and resonance Raman (RR) spectroscopies. The comparison of the solvatochromic behavior of both neutral and dianionic species of RA in acetonitrile, dimethylsulfoxide, and methanol illustrates the effect of polarity and hydrogen bonding on their electronic transitions. The resonance Raman analysis revealed two distinct chromophores in both neutral and dianionic species: i) one located at the central carbon atom, acting as an electron acceptor, and ii) the other involving the π-system of the donor groups. The observed resonance Raman excitation profiles are solvent dependent and could be interpreted as the effect of the solvent on the planarity of the aromatic rings in relation to the central carbon atom. In the case of neutral RA species, having C2 symmetry, specific hydrogen bonding interactions are responsible for inducing a symmetry increase. The opposite effect was observed for the dianionic species [RA]2-, having D3 propeller symmetry, where the interactions with the solvent induces a lowering of the symmetry.

The first step of electrophilic aromatic substitution reactions generally involves the formation of charge transfer complexes. Tetracyanoethylene (TCNE) in the presence of aromatic amines forms π-type complexes that subsequently lead to tricyanovinylation reaction. Although this kind of reaction was investigated in the past, the spectroscopic characterization of the charge transfer complexes is still lacking, since in many cases the first step of the reaction is too fast to allow their characterization by conventional techniques. In this paper, it is shown the UV-Vis and resonance Raman characterization of the charge transfer complexes formed between TCNE and substituted anilines. The magnitude of the charge transfer could be linearly correlated with the electronic absorpion energies, as well as to the Raman shifts observed for the characteristic ν(C≡N) mode of TCNE. In addition, the results were correlated to ionization potentials of amines, and theoretical calculations by density functional theory/time-dependent density functional theory (DFT/TDDFT) methods were performed to support the experimental data.

No presente trabalho foram confeccionados de maneira simples e eficiente fotoeletrodos baseados em ZnO produzidos a partir de síntese de combustão, diretamente na superfície de óxido de índio dopado com estanho (ITO), na presença de diferentes combustíveis: ácido cítrico, glicina e ureia, submetidos a tratamento térmico em 500 e 600 ºC. Os filmes foram caracterizados por análise termogravimétrica, difratometria de raios X, Raman, refletância difusa, microscopia eletrônica de varredura e medidas eletroquímicas, na presença e ausência de luz. O poder redutor de cada combustível investigado, bem como baixas temperaturas de tratamento térmico foram determinantes para a área superficial disponível dos materiais de ZnO formados. A completa conversão a óxido de zinco a baixas temperaturas de calcinação, bem como o tamanho das partículas foram determinantes para a eficiência fotoeletrocatalítica. O fotoeletrodo obtido ao utilizar a glicina como combustível da síntese e tratado a 500 ºC, por 2 h, apresentou melhor resposta em relação a fotocorrente (103 µA cm-2 mg-1) e aos parâmetros cinéticos (22,9 × 10-3 min-1 cm-2 mg-1) para a fotoeletrocatálise do corante azul de metileno, sob irradiação UV.

In this work photoelectrodes based on ZnO produced from combustion synthesis were prepared in a simple and efficient way, directly on the surface of indium tin oxide (ITO), in the presence of different fuels: citric acid, glycine and urea, and undergoing heat treatment at 500 and 600 ºC. The films were characterized by thermogravimetric analysis, X-ray diffraction, Raman, diffuse reflectance spectroscopy, scanning electron microscopy and electrochemical measurements in the presence and absence of light. The reducing power of each fuel was investigated, as well as low temperature heat treatment was crucial to the available surface area of the formed ZnO materials. The complete conversion to zinc oxide at low calcination temperatures, as well as the particle size were crucial for the photoeletrocatalytic efficiency, since the photoelectrode fuel obtained with glycine and treated at 500 ºC showed better response of the photocurrent (103 µA cm-2 mg-1) and the kinetic parameters (22.9 × 10-3 min-1 cm-2 mg-1) for the photoelectrocatalysis of methylene blue dye under UV irradiation.

O vanadato de bismuto (BiVO4) é um semicondutor que tem atraído muita atenção devido à eficiência fotocatalítica na região da luz visível. O objetivo deste trabalho foi sintetizar o BiVO4 monoclínico por síntese de combustão em solução, com diferentes combustíveis e surfatantes e aplicá-los como fotoeletrodos. A caracterização por espectroscopia de infravermelho e Raman mostrou que todas as amostras apresentaram bandas características da estrutura monoclínica do BiVO4. As amostras sintetizadas com glicina e glicina/Tween® 80 apresentaram V2O5. O filme obtido a partir da alanina/Tween® 80 apresentou maior fotocorrente, o que pode ser relacionado ao menor tamanho das partículas (200 a 300 nm) verificado pelas imagens de microscopia eletrônica de varredura. Os filmes obtidos usando alanina apresentaram maiores valores de constante de velocidade observada e percentagem de descoloração do azul de metileno.

The bismuth vanadate (BiVO4) is a semiconductor that has attracted much attention due to the photocatalytic efficiency in the visible light region. The objective of this work was to synthesize monoclinic BiVO4 by solution combustion synthesis, with different surfactants and fuels and apply it as photoelectrodes. The characterization by infrared spectroscopy and Raman spectroscopy showed that all samples showed characteristic bands of the monoclinic structure BiVO4. The samples synthesized with glycine and glycine/Tween® 80 had V2O5. The film obtained from the alanine/Tween® 80 showed highest photocurrent values, which may be related to smaller size particles (200 to 300 nm) observed by scanning electron microscopy images. The films obtained using alanine showed highest values of rate constant reaction and percentage discoloration of methylene blue.