ABSTRACT
IR laser-induced gas-phase photolysis of Fe(CO)(5)-SiH(4) mixtures occurs as SiH(4)-photosensitized decomposition of Fe(CO)(5) is accelerated by products of this decomposition and it results in deposition of amorphous Si/Fe nanocomposite films. Analyses of the deposited and subsequently annealed solid films were made by FTIR, Raman and X-ray photoelectron spectroscopy, X-ray diffraction and electron microscopy. The deposited films are amorphous, contain crystalline nanostructures of iron silicide FeSi(2) and undergo atmospheric oxidation in topmost layers to iron oxide and hydrogenated silicon oxide. Upon annealing they develop nanocrystalline structures of ferrisilicate, Fe(1.6)SiO(4), carbon-encaged iron disilicide, FeSi(2), and very rare hexagonal (high-pressure) Fe surviving at ambient conditions. The mechanism of formation of these nanostructures is discussed in terms of gas-phase and solid-phase reactions.
Subject(s)
Iron Compounds/chemistry , Iron/chemistry , Nanostructures/chemistry , Nanotechnology , Silicates/chemistry , Silicon/chemistry , Crystallization , Lasers , Nanostructures/ultrastructure , Nanotechnology/methods , Photolysis , Spectroscopy, Fourier Transform Infrared , Spectrum Analysis, RamanABSTRACT
Degradation of 4,6-dimethyldibenzothiophene (DMDBT), persistent sulfur contaminant in fuel oils has been achieved in non-polar phase by laser-irradiating DMDBT alone and in the presence of hydrogen peroxide and molecular oxygen. The most efficient degradation in the presence of molecular oxygen is judged to be the first example of self-sensitized photo-oxygenation of thiophenes, in which DMDBT sequentially acts as 1O2 sensitizer and reactant.
