We aimed at elevating catalytic performances of cobalt tetrakis(pentafluorophenyl)porphyrin (Co TPFPP) through axial coordination, nanocavities, and covalently grafting action. The Co TPFPP was immobilized onto nanoporous and nonporous chitosan, forming Co TPFPP/np‐ and nonp‐CTS catalysts, respectively. The catalysts were characterized by various spectroscopic techniques. The catalytic performances of these catalysts for cyclohexane oxidation under response‐surface‐methodology‐optimized oxidation reaction conditions were estimated and compared. Co TPFPP/np‐CTS was an excellent catalyst at aspect of catalytic activity, exhibiting the considerable potential reusability, 24.2 mol % yields (KA oil : cyclohexanone and cyclohexanol) in average, and total turnover frequencies (TOFs) of 3.25×106 h−1. This is attributed to the structural characteristics of the Co TPFPP/np‐CTS catalyst: the cobalt porphyrin molecules could be highly scattered on CTS, forming the independent active sites, and were not leached. The axial coordination exerted the most important effect on the catalytic activity, and the covalent grafting action had a decisive effect on the increase of the total TOFs and on the reusability of the catalyst.

How was the catalytic performance of the title catalyst influenced and enhanced by the Response Surface Methodology optimized-reaction conditions? Based on our experimental data, the effects of the Response Surface Methodology optimized reaction conditions on the catalytic performance were investigated in this paper. The experimental results show that, the micro alterations of various reaction parameter values resulted in the micro changes of cyclohexane conversion, further causing the positive and negative effects, and resulting in the synergy or the antagonism to cyclohexane conversion. The statistic study via Response Surface Methodology showed that, (1) the size order of the effects of the parameters on cyclohexane conversion was that, the quadratic terms > the mutual interaction terms ≈ the single variable terms; (2) compared to Traditional Optimization Method, Response Surface Methodology could more quickly offer the precise optimum values of reaction conditions. In the five recycle applications of the title catalyst, on average, the catalytic activity and the catalytic efficiency were respectively increased 50% and 25% than those obtained from the Traditional Optimization Method-optimized reaction conditions; (3) compared to the other similar catalysts reported in literatures, the present catalyst was a biomimetic catalyst with the highest Turnover Frequency value (6.5 × 10 5 h −1).

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