Synthesis and Characterization of Tungstophosphoric Acid/Pentaethylenehexamine/ZrSBA-15 and Its Use in the Selective Oxidation of Benzyl Alcohol under Solvent-Free Conditions

Graphical A layer-by-layer deposition strategy was used for the preparation of a tungstophosphoric acid/pentaethylenehexamine/ZrSBA-15 composite. This recyclable material was stable at high temperatures and in polar solvents, and it exhibited excellent catalytic properties (84.7 % conversion, >99 % selectivity) in the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (BzH). A layer-by-layer deposition strategy was employed for the immobilization of tungstophosphoric acid (HPW) onto a pentaethylenehexamine (PEHA)-grafted ZrSBA-15 framework to a give HPW/PEHA/ZrSBA-15 composite. The resulting composite was characterized by XRD, SEM, TEM, FTIR, thermogravimetric analysis, N 2 sorption, and X-ray photoelectron spectroscopy, and these methods showed that the composite was stable in polar environments. These properties were attributed to the method of preparation, which ensured that a dense and stable array of HPW was encapsulated within the pores of PEHA-modified ZrSBA-15. In the H 2 O 2 -mediated oxidation of benzyl alcohol, the 25 % HPW/PEHA/ZrSBA-15 catalyst exhibited high selectivity (>99 %) for benzaldehyde. Moreover, the oxidation reaction was performed under solvent-free conditions, and the catalyst was recycled several times with negligible loss in selectivity and conversion. This HPW-based catalyst was also efficient at selectively oxidizing other benzylic and alkyl alcohols to the corresponding aldehydes.