Generation of singlet molecular oxygen from H2O2 with molybdate-exchanged layered double hydroxides:: Effects of catalyst composition and reaction conditions

(Mg, All-layered double hydroxides (LDHs) with different Mg/Al ratios in the octahedral layer were prepared via the coprecipitation method and were exchanged with varying amounts of molybdate, The composition of the LDH supports and the state of the molybdate in these materials were studied with X-ray diffractometry, X-ray photoelectron spectroscopy and Raman, As was proven by NIR luminescence, aqueous H2O2 is converted at the surface of these catalysts into excited, singlet molecular dioxygen (O-1(2)). The singlet dioxygen diffuses away from the O-1(2) generating centers and can perform selective oxygenations, such as endoperoxidations of dienes, or hydroperoxidations of olefins, Catalyst composition and reaction conditions (temperature, solvent) have major effects on the catalyzed O-1(2) generation and the subsequent substrate oxygenation. In order to maximize the efficiency of the H2O2 use and to limit the epoxidation side reaction, it is advisable to limit the amount of exchanged molybdate to similar to0.2 mmol per g and to use an LDH with Mg0.9Al0.1 composition in the octahedral layer. The latter material provides the optimum basicity for the catalytic activity of the exchanged molybdate, (C) 2001 Academic Press.