Selective hydroxylation of benzene to phenol via C[sbnd]H activation over mesoporous Fe2O3-TiO2 using H2O2

Abstract

The omnipresence of CH bonds in organic molecules enamors chemists for the functionalization of CH bonds towards value-added molecular scaffolds. Mesoporous Fe2O3-TiO2 mix-oxide catalyst has been successfully synthesized via a triblock-copolymer (P123) mediated sol-gel method and catalytically tested in selective hydroxylation of benzene. The as-synthesized catalysts were comprehensively characterized by powder XRD, Raman spectroscopy, FT-IR, N2-physisorption, FESEM, HRTEM, XPS, and NH3-TPD techniques. The physicochemical characterizations evidence that Fe(III) ions incorporate into the pure anatase TiO2 lattice framework and the crystallite size decreases as iron concentration increases. The XPS analyses confirm the Fe3+ state (BE 710.3 eV) in Fe-O-Ti with a peak at 712.1 eV for Fe3+ of Fe2O3. The NH3-TPD results show that the 5 wt% Fe-TiO2 has a higher total acidity of 105 µmol/g. Interestingly, a further increase in iron amount decreases the total acidity. Herein, we observe that the surface acidity directs the selectivity towards phenol. The effect of different reaction parameters was carefully investigated. Under the optimized conditions, 5% Fe-TiO2 with notified strong acid sites gives a higher phenol yield of 31.2% with > 99% selectivity; moreover, the catalyst is reusable at least four times.