Oxidation of pinane over phthalocyanine complexes supported on activated carbon: Effect of the support surface treatment

The oxidation of cis-pinane with tert-butyl hydroperoxide, at room temperature and atmospheric pressure, was carried out in the presence of iron-phthalocyanines supported on activated carbons. The carbon supports were prepared from a NORIT activated carbon, which was modified by different chemical and thermal treatments (including oxidation in the gas and liquid phases). The carbon samples were characterized by nitrogen adsorption, mass titration and temperature programmed desorption (TPD). The TPD profiles were analysed by a simple deconvolution method, allowing for the determination of the amount of oxygen containing functional groups on the carbon surface. The main reaction product is 2-pinane hydroperoxide (77% selectivity at 91% conversion). Formation of 2-pinanol, pinocampheol and verbanol and the respective ketones was also observed. The influence of the surface chemistry of the carbon supports on catalytic activity and product selectivity is studied. The catalysts prepared from supports with very high or very low oxygen content exhibit low activity, whereas for supports with intermediate oxygen contents a good correlation between the amount of phenols and lactones and catalytic activity is obtained. (C) 2003 Elsevier Ltd. All rights reserved.