Search results for "PHOTOCHEMISTRY"
showing 10 items of 2034 documents
Effect of titanium dioxide crystalline structure on the photocatalytic production of hydrogen
2011
The effect of the crystalline phase of TiO 2 (anatase, rutile and brookite) on its photocatalytic activity in hydrogen production from methanol-water vapours has been investigated by testing a series of both home-made and commercial TiO 2 photocatalysts, either bare or surface-modified by deposition of a fixed amount, i.e. 1 wt%, of platinum as co-catalyst. For all of the TiO 2 samples the rate of hydrogen production increased by one order of magnitude upon Pt deposition, because of the ability of Pt to enhance the separation of photoproduced electron-hole pairs. Under irradiation in the 350-450 nm wavelength range, brookite and anatase showed similar photoactivities, both superior to that …
Preparation and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin films
2006
Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions
Highly stable defective TiO2-x with tuned exposed facets induced by fluorine: Impact of surface and bulk properties on selective UV/visible alcohol p…
2020
Abstract Titanium dioxide samples were prepared in the presence of different amounts of fluorine via hydrothermal method. It has been found that the presence of fluoride influenced the physico-chemical properties of TiO2 in various ways as polymorphic form stability, surface hydroxylation, generation of hydroxyl radicals under irradiation and formation of Ti3+ centers and oxygen vacancies. The generation rate of OH radicals was investigated by the photoluminescence technique in the presence of terephthalic acid. X-ray diffractometry indicated that fluorine stabilized the anatase TiO2. X-Ray photoelectron spectroscopy (XPS) revealed the presence of fluorine on the surface and the shift of th…
Photocatalytic oxidation of gaseous toluene on anatase TiO2 catalyst: Mechanistic aspects and FT-IR investigation
1999
Abstract Photo-oxidation of toluene has been carried out in gas–solid regime by using polycrystalline anatase TiO2 as the catalyst. The reacting gaseous mixture was toluene, air and water in various molar ratios. A pyrex fixed-bed continuous photoreactor irradiated by a medium pressure Hg lamp was used for performing the photoreactivity experiments. The main oxidation product was benzaldehyde but benzene, benzyl alcohol and traces of benzoic acid, phenol and unidentified compounds were also detected. The molar conversion to benzaldehyde with respect to the initial amount of toluene was ca. 20% in the best experimental conditions. Benzene was produced only as a transient product during the f…
Polymerization with heterogeneous metalorganic catalysts. VI. Differences in polymerization activity of α-olefins and some kinetic results on butene-…
1967
Relative changes in polymerization activity of ethylene, propylene, and butene-1 in Ziegler-Natta polymerization were compared by use of TiCl3 samples contaminated with O2 and H2O to various extents. Catalyst depletion varied for the three monomers which supported the existence of different active centers. In butene-1 polymerizations with the system Al(C2H5)2Cl–TiCl3, the formation of active centers involves an irreversible and a reversible (adsorption) reaction, the former pertaining to the formation of Al(C2H5)Cl2 and dependent upon the purity of the TiCl3. The kinetic treatment of the rate curves suggests a mixed order of catalyst deactivation and again points to the importance of Al(C2H…
Ring splitting of azetidin-2-ones via radical anions
2012
The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by alpha-cleavage. The preference for beta-cleavage is supported by DFT theoretical calculations on the energy barriers associated with the involved transition states. Thus, injection of one electron into the azetidin-2-one moiety constitutes a complementary activation strategy which may be exploited to produce new chemistry.
Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair
2021
Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocyc…
The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX3(PMe3)3 Catalysts
2005
The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order ClBrI) for the one-electron oxidation wave. Addition of X(-) changes the voltammogram, indicating the formation of MoX(4)(PMe(3))(3) f…
Recent advances in electrochemical meso- and β-functionalization of porphyrins and electrografting of diazonium porphyrins
2020
Abstract Recent studies on electrochemical meso- and β-functionalization of porphyrins and electrografting of diazonium porphyrin are presented. First, the electrochemical oxidative C–C coupling between porphyrins will be presented, followed by the intermolecular and intramolecular meso- and β-substitutions of porphyrins. Then, the latest results on diazonium porphyrin electrografting will be reviewed.
Highly selective fluorescence detection of hydrogen sulfide by using an anthracene-functionalized cyclam-CuII complex
2013
An anthracene-functionalised cyclam-copper(II) complex for the detection of HS- in aqueous environments has been prepared. This probe displays poor fluorescence but can selectively and sensitively detect HS- anions in water over other anions, biothiols and common oxidants such as H2O2 through remarkably enhanced emission. This turn-on response in the presence of the HS- anion is ascribed to a demetallation reaction that inhibits emission quenching observed in the initial complex as a result of the presence of the paramagnetic Cu2+ centre. Moreover, real-time fluorescence imaging measurements confirm that probe [Cu(1)](2+) can be easily used to detect intracellular HS- at micromolar concentr…