Synthesis and characterization of mesoporous silica supported metallosalphen-azobenzene complexes: efficient photochromic heterogeneous catalysts for the oxidation of cyclohexane to produce KA oil.

The oxidation of cyclohexane to produce KA oil (cyclohexanone and cyclohexanol) is important industrially but faces challenges such as low cyclohexane conversion at high KA oil selectivity, and difficult catalyst recyclability. This work reports the synthesis and evaluation of new heterogeneous catalysts consisting of Co(ii), Mn(ii), Ni(ii) and Cu(ii) salphen-azobenzene complexes [ML] immobilized on amino-functionalized mesoporous silica (SBA-15, MCM-41, MCM-48) through coordination bonding. In the first step, the salphen-azobenzene ligand was synthesized and complexed with Co, Mn, Ni and Cu metal ions. In the second step, aminopropyltriethoxysilane (APTES) was grafted onto the surface of different types of commercial mesoporous silica. The immobilization of [ML] onto the mesoporous silica surface and the thermal stability of the obtained materials were confirmed using different characterization techniques such as FT-IR, powder XRD, SEM, TEM, BET, and TGA. The obtained results revealed high dispersion of [ML] through the silica surface. The catalytic activity of the prepared materials Silica-N-ML was evaluated on the cyclohexane oxidation to produce KA oil using various oxidants. The - isomerization of the azobenzene upon UV irradiation was found to affect the catalytic performance of Silica-N-ML. The isomer of SBA-15-N-CoL exhibited the highest cyclohexane conversion (93%) and KA selectivity (92%) under mild conditions (60 °C, 6 h) using -CPBA as oxidant. Moreover, The SBA-15-N-CoL showed high stability during four successive cycles.