Dave M, Streb C
Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany.
Dalton Trans. 2015 Nov 21;44(43):18919-22. doi: 10.1039/c5dt03134f.
A comparative study investigating the effects of metal substitution on the photocatalytic activity of metal oxide cluster anions is presented. The study shows that metal functionalization can be used to alter the photochemical properties of monolacunary tungstate - based Keggin clusters (α-TM(H2O)SiW11O39 (M = Co(2+), Cu(2+), Ni(2+), Mn(2+))). It is demonstrated that the photoactivity for the photooxidation of the model pollutant basic blue 41 is dependent of the type of metal employed and increases in the order Co < Cu < Ni < Mn under aerobic conditions and 390 nm monochromatic irradiation. A significant increase of the reaction rate is observed under aerated conditions compared with de-aerated conditions, suggesting that oxygen serves as a re-oxidant for the reduced clusters. Radical scavenging experiments suggest that the photocatalysis proceeds via formation of hydroxyl radicals.
本文呈现了一项关于金属取代对金属氧化物簇阴离子光催化活性影响的对比研究。该研究表明，金属功能化可用于改变基于单缺位钨酸盐的Keggin簇（α-TM(H₂O)SiW₁₁O₃₉ （M = Co²⁺、Cu²⁺、Ni²⁺、Mn²⁺））的光化学性质。结果表明，在有氧条件和390 nm单色照射下，模型污染物碱性蓝41的光氧化光活性取决于所用金属的类型，且活性按Co < Cu < Ni < Mn的顺序增加。与脱气条件相比，在曝气条件下观察到反应速率显著增加，这表明氧气作为还原簇的再氧化剂。自由基清除实验表明，光催化通过羟基自由基的形成进行。
