Abstract: The photocatalytic degradation of acridine orange (AO) dye by NaBiO3 photocatalyst under visible light irradiation was investigated systematically. The NaBiO3 photocatalyst exhibited a higher photocatalytic activity compared to the P25 photocatalyst. After 160 min of photocatalytic reaction, the degradation rate of AO could reach to 99% in appropriate conditions. Factors, such as catalyst dosage, solution pH, initial AO concentration and the presence of anions, were found to influence the degradation rate. To scrutinize the mechanistic details of the dye photodegradation, the intermediates of the processes were separated, identified and characterized by the HPLC-ESI-MS technique. The analytical results indicated that the N-de-methylation degradation of AO dye took place in a stepwise manner to yield mono-, di-, tri- and tetra-N-de-methylated AO species generated during the processes. The probable photodegradation pathways were proposed and discussed.
Abstract: A method for synthesis without protecting groups of bis(indolyl)methanes by the (η3-benzyl)palladium system generated from a palladium catalyst and benzyl alcohol in water is developed. This domino protocol involves C3–H bond activation/benzylation of indole–carboxylic acids and benzylic C–H functionalization. Mechanistic studies indicate that the (η3-benzyl)palladium(II) complex, which is formed via oxidative addition of benzyl alcohol 2 to a Pd(0) species, activates the C–H bond at the C3-position of indole 1. Notably, water plays an important role in our catalytic system for sp3 C–O bond activation and stabilization of OH− by hydration for the smooth generation of the activated Pd(II) cation species, as well as for nucleophilic attack of indoles to hydrated benzyl alcohols.
Abstract: Semiconductors crystal facet engineering has become an important strategy for properly tuning and optimizing both the physicochemical properties and the reactivity of photocatalysts. In this review, a concise survey of recent results obtained in the field of specific surface-oriented anatase TiO2 crystals preparation is presented. The attention is mainly focused on the fluorine-mediated hydrothermal and/or solvothermal processes employed for the synthesis and the assembly of anatase micro/nanostructures with dominant {001} facets. Their peculiar photocatalytic properties and potential applications are also presented, with a particular focus on photocatalysis-based environmental clean up and solar energy conversion applications. Finally, the most promising results obtained in the engineering of TiO2 anatase crystal facets obtained by employing alternative, possibly more environmentally friendly methods are critically compared.
Abstract: The purpose of this study is to present an “environmental catalyst” possessing both thermocatalytic activity and visible-light activity for the decomposition of organic pollutants. Molecule-sized MnOx clusters are highly dispersed on the surface of TiO2 (anatase/rutile = 4/1 w/w, P-25, Degussa) by the chemisorption-calcination cycle technique using Mn(acac)3 complex as a precursor (MnOx/TiO2). The thermo- and photo-catalytic activities of MnOx/TiO2 were studied for the degradation of 2-naphthol used as a model water pollutant. In contrast to the FeOx/TiO2 system, MnOx/TiO2 exhibits high thermocatalytic activity exceeding those of bulk β-β-MnO2 and Mn2O3. Also, visible-light activity is induced by the surface modification of TiO2 with MnOx clusters, whereas its UV-light activity decreases.
Abstract: This work demonstrates how formation of strongly chemiluminescent 3-hydroxyphthalic hydrazide by hydroxylation of non-chemiluminescent phthalic hydrazide can be applied as a selective reaction probe to obtain information on authentic hydroxyl radical, i.e., •OHaq, formation, in black light illuminated Degussa P25 TiO2 aerated suspensions in the pH range from 3 to 11. The •OHaq formation was found to be strongly pH dependent. At alkaline pH, the apparent quantum efficiency of •OHaq formation was estimated to be at the ~10−2 level whereas at acidic pH it was near zero. Addition of phosphate and fluoride ions substantially enhanced the •OHaq production in the acidic pH range. It is suggested that •OHaq-radical formation in TiO2 photocatalysis can occur by oxidation of hydroxyl ions in the water layer adsorbed on TiO2 surfaces.
Abstract: Several important enzymatic reactions occurring in nature, such as, e.g., the digestion of fat, proceed only at the interface of two immiscible phases. Typically, these systems consist of an organic substrate, dispersed in an aqueous continuous phase, with a specialized enzyme capable of working at the interface. For adopting such a system for organic synthesis, a stable heterophase system with a large interfacial area is required. These prerequisites can be found in so-called miniemulsions. Such liquid-liquid heterophase systems feature droplets with sizes smaller than 500 nm, and more importantly, these emulsions do not suffer from Ostwald ripening, as conventional emulsions do. Consequently, the droplets show long-term stability, even throughout reactions conducted in the droplets. In this review, we will briefly discuss the physicochemical background of miniemulsions, provide a comprehensive overview of the enzymatically catalyzed reactions conducted in miniemulsions and, as data are available, to compare the most important features to conventional systems, as reverse microemulsions, (macro)emulsions and solvent-based systems.
