Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan.
Dalton Trans. 2014 Jan 21;43(3):1132-8. doi: 10.1039/c3dt52408f. Epub 2013 Oct 29.
A series of materials containing the tris(2,2'-bipyridine)iron(ii) (Fe(bpy)3(2+)) complex inside zeolite Y cavities with alkaline earth metals (Mg(2+), Ca(2+), Sr(2+), Ba(2+)) as charge compensating cations have been synthesized via a "ship in the bottle" method. The influence of the alkaline earth metal cations on the physicochemical properties and catalytic activity was investigated. The successful formation of the Fe(bpy)3(2+) complex was verified by XRD, diffuse-reflectance UV-vis spectroscopy, and Fe K-edge XAFS measurements. The BET surface area and the Fe content decreased in the presence of the larger alkaline earth metal, but the intensity of the MLCT adsorption band of Fe(bpy)3(2+) increased with the heavier cation. The electron density of the Fe atoms decreased, and the average interatomic bond distance Fe-N/O and the coordination number increased with the heavier alkaline earth metal cation. The encapsulation of Fe(bpy)3(2+) resulted in the creation of a photocatalytic system able to oxidize styrene to benzaldehyde and styrene oxide under visible light irradiation (λ > 430 nm) in the presence of molecular oxygen.
一系列含有三（2,2'-联吡啶）铁（II）（Fe(bpy)3(2+)）配合物的沸石 Y 笼内的材料，其中碱性土金属（Mg(2+)、Ca(2+)、Sr(2+)、Ba(2+)）作为电荷补偿阳离子，通过“瓶中船”方法合成。研究了碱性土金属阳离子对其物理化学性质和催化活性的影响。通过 XRD、漫反射紫外可见光谱和 Fe K 边 XAFS 测量验证了 Fe(bpy)3(2+)配合物的成功形成。BET 表面积和 Fe 含量随着较大碱性土金属的存在而降低，但 Fe(bpy)3(2+)的 MLCT 吸附带强度随着阳离子的增加而增加。Fe 原子的电子密度降低，平均原子间键距 Fe-N/O 和配位数随着较重的碱性土金属阳离子增加。Fe(bpy)3(2+)的包封导致在可见光照射下（λ>430nm），在分子氧存在下，形成能够将苯乙烯氧化为苯甲醛和苯乙烯氧化物的光催化体系。
