44601-24-3Relevant articles and documents
Fe(III)-porphyrin heterogenized on MCM-41: Matrix effects on the oxidation of 1,4-pentanediol
Molinari, Alessandra,Maldotti, Andrea,Bratovcic, Amra,Magnacca, Giuliana
experimental part, p. 64 - 69 (2011/12/21)
The metal complex iron meso-tetrakis (2,6-dichlorophenyl)porphyrin (Fe IIIP) has been covalently linked on the surface of the mesoporous material MCM-41 and of amorphous SiO2 to give the photocatalysts FeIIIP/MCM-41 and FeIIIP/SiO2 respectively. The effect of porphyrin addition on specific surface area and porosity of these materials has been evaluated by means of BET and BJH model applied to N 2 adsorption/desorption isotherms. It is seen that the MCM-41 sample presents the largest modification due to the presence of porphyrin: the pore size changes in average value and distribution, the pores formed in the presence of porphyrin being smaller and presenting a larger distribution. The photochemical characterization of FeIIIP/MCM-41 reveals that this is a robust photocatalyst able to induce the O2-assisted oxidation of 1,4-pentanediol. In particular, photoexcitation of FeIIIP/MCM-41 causes the conversion of 1,4-pentanediol to the aldehyde derivative compound with 70% regioselectivity. It is noteworthy that this product can be accumulated with no formation of further oxidized compounds. Due to its high specific surface area, which guarantees a good dispersion of the active centres, Fe IIIP/MCM-41 is about four times more efficient than Fe IIIP/SiO2. Moreover, the nature of the support controls the regioselectivity of the photocatalytic process: this is due to both uptake phenomena and steric effects, which can control the approach of the diol to the photoactive iron porphyrin.
Selective photooxidation of diols with silica bound W10 O324 -
Maldotti,Molinari,Bigi
, p. 312 - 317 (2008/09/16)
The decatungstate anion W10 O324 - has been heterogenized on silica previously functionalized with different ammonium cations covalently bound to the surface of the solid support. These materials are investigated as photocatalysts for the oxygen-assisted oxidation of 1,3-butanediol and 1,4-pentanediol. Product distribution and adsorption experiments indicate that the polarity of the environment surrounding the photoactive anion plays a crucial role in controlling the adsorption of diols on the surface and, consequently, their reaction with the photoexcited decatungstate. Proper reaction conditions are found for obtaining more than 90% of 4-hydroxy-2-butanone from 1,3-butanediol and for stopping the oxidation of 1,4-pentanediol to 4-hydroxypentanal with good yield. The employed photocatalysts present a very good stability in repeated experiments.
Regioselectivity in the Semiconductor-Mediated Photooxidation of 1,4-Pentanediol
Fox, Marye Anne,Ogawa, Haruo,Pichat, Pierre
, p. 3847 - 3852 (2007/10/02)
Optimum conditions have been established for the selective semiconductor-photocatalyzed oxidation by long-wavelength ultraviolet light of the primary alcohol functionality in 1,4-pentanediol.On platinized (2percent) TiO2 powder suspended in oxygenated aqueous (4 vol percent) acetonitrile, the initial rate ratio for oxidation of the primary/secondary alcohol site was > 7.Analysis of further oxidation products allowed for mechanistic delineation of the course of the semiconductor-mediated reaction.The selectivity is attributed to the essential role of adsorption, with the criticalphotoinduced electron transfer occurring at the surface of the irradiated particle.ZrO2 and SnO2 samples were much less active than TiO2 as photocatalysts.The effects of oxygen pressure, metal cocatalyst loading, and water content of acetonitrile are discussed.