Fung Annie K M, Chiu Brenda K W, Lam Michael H W
Department of Biology & Chemistry, Centre for Coastal Pollution and Conservation, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong.
Water Res. 2003 Apr;37(8):1939-47. doi: 10.1016/S0043-1354(02)00567-5.
A new ruthenium(II) photosensitizer, Ru(II)(py-pzH)(3) (where py-pzH=3-(2'-pyridyl)pyrazole), has been synthesized. The complex displayed outstanding excited state redox properties (estimated Ru(III)/Ru(II)* approximately -1.24 V vs. NHE) and was expected to sensitize the injection of electrons into the conduction band of anatase TiO(2) upon visible irradiation. The photosensitizer was anchored onto the surface of anatase TiO(2) particles via in situ silylation. The silyl-linkage displayed excellent stability in both aqueous media, over a wide pH range, and in common organic solvents. The resultant material, TiO(2)-[Ru(II)(py-pz-Si identical with )(3)], was found to be able to mediate degradation of CCl(4) in neutral aqueous medium under broad band visible irradiation (lambda>450 nm). The relation between the rate of degradation and concentration of substrate was explored and the mechanism of the photodegradation of the perhalogenated organic was discussed.
一种新型钌（II）光敏剂[Ru（II）（py - pzH）₃]²⁺（其中py - pzH = 3 - （2'-吡啶基）吡唑）已被合成。该配合物表现出出色的激发态氧化还原性质（相对于标准氢电极，估计Ru（III）/Ru（II）*约为 -1.24 V），并且预计在可见光照射下能敏化电子注入锐钛矿型TiO₂的导带。通过原位硅烷化将光敏剂锚定在锐钛矿型TiO₂颗粒表面。硅烷基键在宽pH范围的水性介质和常见有机溶剂中均表现出优异的稳定性。发现所得材料TiO₂ - [Ru（II）（py - pz - Si≡）₃]能够在宽带可见光照射（λ>450 nm）下介导中性水性介质中CCl₄的降解。探索了降解速率与底物浓度之间的关系，并讨论了全卤代有机物的光降解机理。
