Immobilization of gold on short -channel mesoporous SBA-15 functionalized with thiol and hydrophobic groups for oxidation reactions

Nanosized gold entities immobilized on short -channel SBA -15 mesoporous materials functionalized solely with mercaptopropyl groups and together with propyl and octyl moieties have been prepared following a two-steps procedure. These materials have been used as catalysts for the oxidation of cyclohexene with molecular oxygen in liquid phase at atmospheric pressure. First, SBA -15 materials functionalized only with mercaptopropyl groups and with a combination of these groups with two hydrophobic moieties, namely propyl and octyl, have been synthesized in the presence of the non-ionic surfactant P104. Small particles having short channel length have been identified by TEM and SEM. In order to study the influence of the nature of the sulphur functional group, these S -bearing materials were also oxidized with hydrogen peroxide or dimethyldioxirane (DMD) to sulfonic groups prior to gold immobilization. The effectiveness of these oxidation methods was assessed by 29 Si MAS NMR, 13 C CP MAS NMR, XPS, chemical and thermal analysis, and it has been found that DMD oxidized effi- ciently thiol groups to sulfonic groups, but H 2 O 2 leaves a fraction of unreacted thiol. In a second step, nanosized gold entities have been prepared by a two -liquid phases route involving rosemary oil as organic phase and an aqueous phase formed by dissolving gold in a solution of ammonium chloride in concentrated nitric acid ( aqua regia ). Following this method, a fraction of the Au dissolved in the aqua regia solution is spontaneously reduced and transferred to the essential oil phase. Upon contacting the gold -bearing organic layer with the mesoporous materials, gold is actually immobilized on them, rendering metal contents in the range 1.1-0.2 wt.%, being those functionalized with alkyl chains the least efficient in capturing gold from the organic phase. No surface plasmon resonance band at 520 nm characteristic of gold nanoparticles has been detected by UV-vis spectroscopy in these Au -containing materials. All of them are active and selective for the allylic oxidation of cyclohexene, but their specific activity varies as a function of the nature of the functional groups. It has been found that the most active catalysts are those pre -oxidized with DMD. The presence of hydrophobic octyl groups increases substantially the turnover number of the reaction (TON), while the short -chain propyl moieties hardly affect the activity. It has been found that the nanosized gold entities initially present in the catalysts evolve in the reaction medium towards the formation of nanoparticles.