Preparation of environmental benign nano-structured catalysts composed of clay and metal complexes

采用简单的阳离子交换法，以联吡啶铑（I）和钴卟啉衍生物为柱撑，以粘土为原料，合成了新型纳米复合材料，并通过FT-IR、XRD、SEM、TEM和高分辨固体NMR等手段对复合材料进行了表征。通过CHN分析、UV-vis和TG-DTA检测柱络合物在LiTN中的负载量。粉末XRD测试表明，插层后纳米结构粘土的层间距扩大。具有长烷基链（n> 7）的改性带沸石显示出与原始带沸石相当的尖锐衍射峰。粘土层的高结晶度可以通过层中烷基的疏水相互作用来实现。C.由XRD计算的纳米结构粘土的间隙空间（间隙空间=基底间距（d_）-层厚度（0.96 nm））与烷基的长度成比例地增加（斜率：0.14 nm/CH_2）。<001>从纳米结构粘土的TEM图像估计的层间距与从粉末XRD测量计算的C.S.很好地一致。高分辨固体~13C NMR研究表明，纳米结构粘土中的柱撑配合物为全反式结构。合成的柱撑配合物和纳米结构粘土用于烯烃的催化加氢和环氧化反应。<13>在柱配合物中，除[Rh（COD）C23-bpy] ClO_4外，催化活性随烷基链长的增加而降低。相反，纳米结构粘土的活性随着纳米结构粘土的C. S.而增加。此外，从纳米结构的粘土中观察到的基底的形状选择性和层间距是明确的立体选择性。此外，我们发现纳米结构的粘土是可回收的催化剂在加氢。

Novel nano-structured composites were synthesized from clays and pillar complexes with long alkyl spacers by simple cation exchange methods, where pillar complexes were rhodium(I) bipyridines and cobalt porphyrins derivatives.The nano-structured clays were characterized by FT-IR,XRD,SEM,TEM and high-resolution solid state NMR. The loading amount of pillar complexes into LiTN was detected by CHN analysis, UV-vis, and TG-DTA. The powder XRD measurements revealed that the basal spacing of the nano-structured clay was expanded after the intercalation. The modified taeniolites with long alkyl chains (n>7) showed sharp diffraction peaks comparable to the original taeniolite. The high crystallinity of clay layers can be achieved by the hydrophobic interaction of alkyl groups in the layers. The C.S.(clearance space=basal spacing (d_<001>)-thickness of layer (0.96 nm)) of the nano-structured clays calculated from XRD increases in proportional to the length of alkyl groups (slope : 0.14 nm/CH_2). The interlayer space estimated from TEM image of the nano-structured clays is well consistent to the C.S.calculated from the powder XRD measurement. High-resolution solid-state ^<13>C NMR study for nano-structured clays elucidated the conformation of the pillar complexes in the clay to be all-trans.Synthesized pillar complexes and nano-structured clays were used for the catalytic hydrogenation reactions and epoxidation of olefins. In case of pillar complexes, catalytic activity was decreased with increasing the alkyl chain length except for [Rh(COD)C23-bpy]ClO_4. On the contrary, the activity of the nano-structured clays increased with C.S.of the nano-structured clays. Moreover, shape selectivity of the substrate was observed fro the nano-structured clays and the interlayer space was clearly related to the stereo selectivity. Furthermore, we found that nano-structured clays were recyclable catalysts in hydrogenation.