Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Highly Active Catalysis of Cobalt Tetrakis(pentafluorophenyl)porphyrin Promoted by Chitosan for Cyclohexane Oxidation in Response‐Surface‐Methodology‐Optimized Reaction Conditions

“…Sixth, under the~60 ppm of cobalt loading amount, Co TPFPP/np-CTS could be reused 4 times for the cyclohexane oxidation ( Table 3 and Figure 8), which was twice as muchas the recycling ability of the previous catalysts: Co TCPP/ZnS, [17] and Fe(III) TPPS/pd-CTS. [18] For each reuse, it showed the highest catalytic activity (TOF) relative to the two others just mentioned. It is more important that, the total TOFs (TON) of the cyclohexane oxidation catalyzed by Co TPFPP/np-CTS high reached 3.25 × 10 6 h À 1 (1.14 × 10 7 ).…”

“…These changes can be seen and assigned in Table 2 and Figure 6. [17,18] The nucleophilic substitution of the 4-F atom on the benzene ring of Co TPFPP by the NH 2 À C unit in np-CTS and nonp-CTS took place. That is, the covalently grafting of the nitrogen atom of the amino group (À NH 2 ) in np-CTS and nonp-CTS to the 4-C atom on the benzene ring of Co TPFPP; the 4-C atoms of the C=CÀ F unit in Co TPFPP were changed to the 4-C atoms of the C=CÀ NH unit in Co TPFPP/np-CTS and Co TPFPP/nonp-CTS.…”

“…The successful researches and the challenge above inspired us to use the various metalloporphyrins immobilized on the different carries as catalysts for investigating how the axial coordination enhanced their catalytic activities. [17,18] We have not only found that, a sulfur-or nitrogen-containing ligand in the corresponding support could affect the binding energy of the metal center in metalloporphyrins and then promote the catalytic activity of the immobilized metalloporphyrin, but also found that, each of the catalysts (Co TCPP/ZnS, or Fe TPPS/pd-CTS) could be only reused 2 times respectively for the oxidation of cyclohexane. [17,18] The experiences above [8,14,17,18] encouraged us to consider the stability issue of immobilized metalloporphyrin catalyst: the hexane diacid produced in the cyclohexane oxidation system, will affect the activity and reusability of the immobilized metalloporphyrin catalysts.…”

“…[20,27,28] Based on the consideration of practical application in green chemical industry, the improved Lyon system was preferred for us. [10,17,18] We aimed at elevating catalytic performances (activity and reusability) of cobalt tetrakis(pentafluorophenyl)porphyrin (Co TPFPP), and report in here that, cobalt tetrakis(pentafluorophenyl)porphyrin was covalently and coordinately bound to np-and nonp-CTS, forming new catalysts, Co TPFPP/np-or nonp-CTS. Both catalysts were used for cyclohexane oxidation under optimized reaction conditions via a response surface methodology (RSM).…”

Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox‐Active Fe(II/III) Sites in a Metal−Organic Framework

“…Over recent decades, all manner of catalysts have been reported for cyclohexane oxidation; carbon materials, [5] polymers, [6] silica, [7] MetalÀ organic frameworks, [8] organometallic complex [9] and zeolites. [10] Metal-incorporated zeolites [1b] and silica [2b,11] are some of the most promising catalysts.…”