Selective Organic Synthesis using Montmorillonite Clay supported Metalloporphyrin Catalysts

1.粘土纳米空间中卟啉的合成：在回流条件下，用1.0M硝酸水溶液处理蒙脱石粘土。经硝酸处理后的粘土对合成卟啉表现出较高的催化活性。其活性明显高于市售的蒙脱石K-10催化剂。经硝酸处理的粘土中存在平均孔径接近3.0 nm的介孔结构，从而大大提高了卟啉的产率。2.在蒙脱石中嵌入钴卟啉配合物催化环己烯分子氧氧化反应：发现粘土负载的钴卟啉配合物是一种在实验条件下稳定的高效催化剂。这可能是由于负载催化剂的择优取向，使环己烯接近假定的活性钴中心。3.钴卟啉配合物插层到烷基铵交换的膨胀层硅酸盐中：通过固-固反应将四-(N-乙基-3-吡啶)卟啉钴(CoTEPyP)插层到十六烷基三甲基季铵蒙脱土(CTA-MT)中。插层化合物(CoTEPyP/CTA-MT)的层间距(CoTEPyP/CTA-MT)从钠蒙脱土的1.26 nm增加到2.82 nm。减去硅酸盐厚度(0.96 nm)，CoTEPyP/CTA-MT的廊道高度为1.86 nm。这种通道高度的增加表明，插层的卟啉阳离子可能是以垂直于蒙脱石片层的分子平面排列的。

1.Porphyrin Synthesis in Clay Nanospaces : Montmorillonaite clays were treated with 1.0M nitric acid aqueous solution under reflux conditions. The resulting nitric acid-treated clays exhibited considerable catalytic activity for porphyrin synthesis. Its activity was significantly higher than that of a commercial available montmorillonite K-10 catalyst.It was considered that a great increase in the porphyrin yield is due to the presence of mesopores with the average pore diameter of nearly 3.0nm in nitric acid-treated clays.2.Oxidation of Cyclohexene with Molecular Oxygen catalyzed by Cobalt Porphyrin Complexes intercalated into montmorillonaite : It was found that clay supported cobalt porphyrin complexes are highly active catalysts which are stable under the experimental conditions. This is probably due to a prefered orientation of the supported catalyst for an approach of the cyclohexene to the presumed active cobalt site.3.Intercalation of Cobalt Porphyrin Complexes into Alkylammonium-Exchanged Swelling Layred Silicates : Intercalation of cobalt tetra- (N-ethyl-3-pyridyl) porphyrin (CoTEPyP) into cetyltrimethy lammonium-montmorillonaite (CTA-MT) was carried out by solid-solid reactions. The basal spacing of the intercalation compound (CoTEPyP/CTA-MT) increased to 2.82nm from 1.26nm of Na-mont. The gallery height of CoTEPyP/CTA-MT was 1.86nm when the thickness of silicate layrs (0.96nm) was subtracted. This increase in the gallery hight was suggested that the intercalated porphyrin cations were possibly arranged with the molecular plane perpendicular to the interlamellar layrs of monmorillonite.