This article highlights the potential use of multi‐walled carbon‐nanotube modified screen‐printed electrodes (SPEs) for the amperometric sensing of ciprofloxacin and compares the association of batch‐injection analysis (BIA) and flow‐injection analysis (FIA) with amperometric detection. Both analytical systems provided precise (RSD<5 %) and sensitive determination of ciprofloxacin (LOD<0.1 μmol L−1) within wide linear range (up to 200 μmol L−1). Accuracy of both methods was attested by recovery values (93–107 %) and comparison with capillary electrophoresis. The BIA system is completely portable (especially due to association with SPEs) and provided faster analyses (130 h−1) and more sensitive detection than the FIA system due to the higher flow rates of injection.
Este trabalho apresenta o estudo do comportamento fotoquímico de hidrocarbonetos policíclicos aromáticos (HPAs), potenciais poluentes secundários em reações em aerossóis, através de espectroscopia Raman em comparação com seu comportamento eletroquímico. Os HPAs estudados incluem pireno, antraceno, fenantreno e fluoreno. Esses foram adsorvidos sobre o catalisador TiO 2 e irradiados com radiação ultravioleta (254 nm). A oxidação eletroquímica foi estudada via espectroscopia Raman intensificada pela superfície (SERS) in situ e levou à formação de produtos carbonilados. Intermediários oxidados contendo o grupo C=O foram também observados nos processos de fotodegradação. A comparação entre os intermediários formados nos processos fotoquímicos e eletroquímicos revela produtos idênticos para o antraceno, mas não para o pireno. Esse resultado advém da diferença de mecanismo para esses dois processos. A degradação fotocatalítica sobre TiO 2 é iniciada por radicais hidroxila, enquanto a oxidação eletroquímica é iniciada por transferência eletrônica direta com o HPA adsorvido no eletrodo, gerando cátions radicais do HPA que desencadeiam as reações subseqüentes. This paper presents the study of photochemical behavior of polycyclic aromatic hydrocarbons (PAHs), potential pollutants in secondary reactions in aerosols, through Raman spectroscopy compared with its electrochemical behavior. The PAHs studied include pyrene, anthracene, phenanthrene and fluorene. These were adsorbed onto TiO 2 and irradiated with ultraviolet light (254 nm). Their electrochemical oxidation was studied by in situ Surface-enhanced Raman Scattering (SERS) and led to the formation of carbonyl-containing products. Oxidized intermediates bearing the C=O group were also formed during photodegradation. The joint analysis of the photodegradation data with those produced by electrochemical means -using spectroscopic techniques for the identification and characterization of the products -revealed the formation of identical products for anthracene, but not for pyrene. A reasonable explanation for this difference in results is that photochemical and electrochemical oxidation reactions proceed via different mechanisms. While photocatalytic degradation over TiO 2 is initiated by hydroxyl radicals, electrochemical oxidation is initiated by the direct electron transfer from adsorbed PAH to the electrode, generating PAH cation radicals that undergo subsequent reactions.Keywords: advanced oxidative processes, photocatalysis, TiO 2 , spectroelectrochemistry, SERS IntroductionExcessive concentrations of particulate matter in the atmosphere are cause for significant concern in many metropolitan areas around the world. This particulate matter exhibits dynamic behavior owing to potential chemical and photochemical reactions, changing its composition according to time and environment. Polycyclic aromatic hydrocarbons (PAHs), a class of chemicals present in particulate matter, are of special interest due to their mutagenic and carcinogenic properties. 1,2 PAHs are character...
Praseodymium doped TiO2 nanoparticles were successfully prepared by the sol–gel method and characterized by X-ray powder diffraction, N2 adsorption–desorption isotherm, and UV–vis spectroscopy. The effects of the dopant on the crystallite size, specific surface area, average pore diameter, pore volume, and bandgap energy were investigated. The photocatalytic activity of the catalysts was evaluated by bisphenol A degradation and mineralization, which is a representative endocrine disruptor. Furthermore, under visible light irradiation the Pr-modified TiO2 photocatalysts exhibited higher photocatalytic efficiency than unmodified TiO2. When praseodymium was loaded (1.0–5.0%) onto the surface of TiO2, the rates of degradation and mineralization were increased 3–5 times.
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