Abstract DFT calculations were employed in order to gain insight about the mechanism of the oxidation reaction catalyzed by anionic iron(III) porphyrin ([Fe(TSPP)Cl]4−) with different counter ions (H+ and Na+) immobilized onto Zn4Al2(OH)12(CO3).4H2O layered double hydroxide. The immobilization of these porphyrinates was modelled by the construction of a LDH slab and the CI-NEB method was used to obtain the reaction path of the H2O2 cleavage and the subsequent formation of the oxoiron species. The computational simulations predicted that the counter ion affects the energy barriers of the oxoiron species formation. On the experimental side, the solid catalysts were synthesized and their catalytic performances were tested for the oxidation reaction of cyclohexane. The experiments showed that the immobilization process of the catalysts led to a selectivity of alcohol formation compared to the catalysis in homogeneous media. Furthermore, the reaction yield of the iron(III) porphyrin with H+ was higher, confirming that the consideration of the counter ion for the catalyst is important for oxidation reactions.

中文翻译：

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铁（III）卟啉在 2:1 Zn/Al-CO3 层状双氢氧化物上的吸附及其作为具有不同反离子的氧化催化剂的用途：实验和 DFT 研究

摘要 采用 DFT 计算以深入了解阴离子铁 (III) 卟啉 ([Fe(TSPP)Cl]4−) 与固定在 Zn4Al2(OH) 上的不同抗衡离子（H+ 和 Na+）催化氧化反应的机理。 )12(CO3).4H2O 层状双氢氧化物。这些卟啉酸盐的固定化通过构建 LDH 板进行建模，并使用 CI-NEB 方法获得 H2O2 裂解的反应路径和随后的氧铁物种形成。计算模拟预测反离子会影响氧化铁物质形成的能垒。在实验方面，合成了固体催化剂并测试了它们对环己烷氧化反应的催化性能。实验表明，与均相介质中的催化相比，催化剂的固定化过程导致了醇形成的选择性。此外，铁 (III) 卟啉与 H+ 的反应产率更高，这证实了考虑催化剂的抗衡离子对于氧化反应很重要。