To simulate the active site cavity structure function and axial coordination of cytochrome P-450 enzymes, mesoporous chitosan(mesp-CTS) was used as a scaffold for a meso-sized cavity to immobilize cobalt tetrakis(p-sulphophenyl)porphyrin chloride(Co TPPS). Immobilization was achieved via an acid-base reaction and axial coordination of the H 2 N-C group to the Co ion in Co TPPS, thus forming the biomimetic catalyst Co TPPS/mesp-CTS. Several approaches, including scanning electron microscopy (SEM), the Brunauer-Emmett-Teller (BET)technique, Fourier transform infrared (FT-IR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, thermogravimetric and differential scanning calorimetry (TG-DSC), and X-ray photoelectron spectroscopy (XPS), were used to characterize the grafted catalyst. The catalytic performance of Co TPPS/mesp-CTS in ethylbenzene oxidation without any solvents and additives was investigated. The results showed that only 0.96 × 10 mol of Co TPPS grafted onto mesp-CTS could be recycled three times for 200 mL of ethylbenzene oxidation, with an average yield of 44.6% and selectivity of 68.8%. The highly efficient catalysis can be attributed to promotion by mesp-CTS, including the effect of the mesoporous structure and the axial coordination to the Co ion in Co TPPS. This biomimetic methodology provides a method for clean production of acetophenone via ethylbenzene oxidation.
Manganese tetrakis(4-sulfonatophenyl)porphyrin chloride was grafted onto powdered chitosan via an acid–base reaction and ligation. The grafted catalyst was characterized by transmission electron microscopy, ultraviolet and visible spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectrometry and thermogravimetry. Ethylbenzene oxidation with O[Formula: see text] by the catalyst in the absence of additives and solvents can achieve moderate yields (approximately 30%) of acetophenone and phenethyl alcohol. The grafted catalyst can be reused four times for oxidation reactions. The results indicate that the catalytic activity of manganese tetrakis(4-sulfonatophenyl)porphyrin chloride is promoted by the ligation and grafting function of the amino groups in the powdered chitosan.
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