XJIPC OpenIR  > 资源化学研究室
Thesis Advisor高林 ; 赵文军
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline有机化学
KeywordNhpi 环己烷 高价铁 配合物 负载

饱和烃C-H键的活化选择性氧化是全世界学者研究的焦点,由于饱和C-H键键能大,极性小,导致反应活性小,容易深度氧化。寻找一种在温和条件下有效活化 饱和C-H键,并具有高选择性的催化剂体系,是一个极具挑战性的工作。本文利用铁化合物协助N-羟基邻苯二甲酰亚胺催化活化饱和C-H键。以环己烷为氧化 底物,氧气作为氧化剂。 首先,利用负载型铁氧化物与N-羟基邻苯二甲酰亚胺(NHPI)相组合,研究了催化氧化环己烷的效果以及可能存在的机理。用浸渍法制备了多种负载型铁氧化 物催化剂,研究了用不同载体、不同铁来源制备的催化剂与NHPI共同催化氧化环己烷,其结果要比非负载型铁盐与NHPI相组合催化氧化环己烷好得多。利用 NHPI与Fe/ZrO2在 100℃下,氧压0.6MPa下反应6小时,环己烷转化率可达到53%,负载型铁氧化物晶体缺陷产生的Fe4+是激发NHPI为PINO自由基的来源。 之后,为了增强铁化合物协助N-羟基邻苯二甲酰亚胺(NHPI)催化氧化环己烷的效果,合成了各种类型配体包括N、N,N、O和O、O配位式的有机铁配合 物,铁与不同有机配体配位后增强了助催化能力,其中0.5g四对氯苯基卟啉铁协助10%molNHPI在100℃下,氧压0.6Mpa,反应6小时后环己 烷转化率为46%。有机铁配合物在氧化过程中形成了活性高价态铁中间体,把NHPI氧化为PINO自由基,提高了氧化性能,不同配体的助催化能力为N、N 配位>N、O配位>O、O配位,这与高价铁活性中间体形成难易程度有关。

Other Abstract

Selective activation and oxidation of C-H bond of saturated hydrocarbons are the fo-cus of scholars around the world. As a result of high strength and weak polarity of C-H bond, the activation of the C-H bond is small and the deeper oxidation of C-H bond occurs easily. To find a high selective catalytic system which can effectively activate saturated C-H bond in the mild conditions is a very challenging work. In this article, iron compounds were used assisting N-hydroxyphthalimide (NHPI) activing and oxidizing saturated C-H bond, cyclohexane as the oxidation substrate and oxygen as the oxidant. First, N-hydroxyphthalimide (NHPI) and supported iron oxides were used as catalysts for catalytic oxidation of cyclohexane and the catalytic effects and possible mechanisms were investigated. Different kinds of supported iron oxides containing different supports and iron precursors were prepared, which, when combined with N-hydroxyphthalimide, had catalytic properties superior to those of Fe (Ⅲ) salts /N-hydroxyphthalimide. Cyclo-hexane conversion of 53% was obtained over N-hydroxyphthalimide/Fe/ZrO2 under 100℃, O2 pressure of 0.6 MPa and reaction time of 6 h. Mössbauer spectrum showed that Fe4+ generated from the crystal defects was the PINO radical initiator. Then, to enhance the effect of Co-catalytic effect of iron compounds for catalytic oxidation of cyclohexane over NHPI, different organic iron complexes involving N/N,N/O and O/O coordination were synthesized. Co-catalytic capability of iron compounds were greatly improved after the coordination by different organic ligands. Cyclohexane conver-sion of 46% was obtained under the following condition: 100℃, O2 pressure 0.6MPa, reac-tion for 6h over 10%(mol) NHPI and 0.5 g tetra-(p-chlor)phenylporphyrin iron(Ⅲ). During the oxidative process, the complex formed active high valence iron intermediate, which oxidized NHPI into PINO radicals and enhanced the oxidation capability. The co-catalytic ability of different ligands declined in the following order: N/N>N/O>O/O coordination, which might be related with the likelihood for formation of active high active valence iron intermediates.

Document Type学位论文
Recommended Citation
GB/T 7714
张延路. 铁化合物与N-羟基邻苯二甲酰亚胺催化氧化环己烷研究[D]. 北京. 中国科学院研究生院,2009.
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