Comparative study of two mesoporous magnetic and MCM-41 supported Cu complex: High-performance heterogeneous catalysts for aqueous synthesis of tetrazole

The effects of the carrier were studied in the synthesis of tetrazole. Copper catalysts supported on CoFe2O4 and MCM-41 with serine ligands were prepared. Two mesoporous catalysts, CoFe2O4/Ser/Cu and MCM-41/Ser/Cu, (denote Serine with (Ser)) were synthesized and compared the activity of these catalysts in converting nitrile to tetrazole. The prepared material was characterized using powder X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), energy-dispersive X-ray spectrometer (EDS), elemental mapping, vibrating-sample magnetometer (VSM), and nitrogen adsorption-desorption isotherm. The relation between the textural properties of the catalysts and the catalytic performance was investigated. The X-ray diffraction patterns showed the spinel ferrite type for CoFe2O4/Ser/Cu and amorphous SiO2 for MCM-41/Ser/Cu. The distinctive diffraction peaks in the diffraction curves of CoFe2O4/Ser/Cu, and MCM-41/Ser/Cu were identical to those of CoFe2O4, and MCM-41, confirming the preservation of these phases of supports throughout the functionalization processes and formation of -Ser/Cu moiety on the crystalline CoFe2O4 structure and non-crystalline silica structure. FE-SEM images showed the particles in CoFe2O4/Ser/Cu had an average diameter of 20-50 nm and in MCM-41/Ser/Cu had an average diameter of 50-250 nm. The images showed the uniformity and well-ordering of the particles. The slight aggregation in CoFe2O4/Ser/Cu particles implied that their clustering may be the result of modest attraction forces between them. MCM-41/Ser/Cu sample exhibited a type IV isotherm with an H1-type hysteresis loop and diagrams of the CoFe2O4/Ser/Cu showed a type IV isotherm (type H2 hysteresis loop). The MCM-41/Ser/Cu and CoFe2O4/Ser/Cu showed a mesoporous structure and capillary condensation occurred in the nearly cylindrical and ink bottle channels with non-uniform size or shape. The CoFe2O4/Ser/Cu showed surface area by BET and t-plot of 71.17 m(2)/g and 64.92 m(2)/g respectively, mean pore size of 14.06 nm, and pore volume of 0.250 cm(3)/g. The MCM-41/Ser/Cu showed surface area by BET and t-plot of 639.2 m(2)/g and 484.6 m(2)/g respectively, with a mean pore size of 5.44 nm, and pore volume of 0.869 cm(3)/g. The BJH pore size distribution was between 1 and 10 nm for the MCM-41/Ser/Cu and 1-20 nm for the CoFe2O4/Ser/Cu. Two catalysts were used for the synthesis of tetrazole. The CoFe2O4/Ser/Cu shows better activity in the synthesis of 5-substituted 1H-tetrazoles than the MCM-41/Ser/Cu sample despite its lowest surface area (71.17 m(2)/g). There is no reduction in the conversion of nitrile to tetrazole after the 6 cycles for CoFe2O4/Ser/Cu and after the 4 cycles for MCM-41/Ser/Cu.