Chen Jennifer I L, Freymann Georg von, Kitaev Vladimir, Ozin Geoffrey A
Materials Chemistry Research Group, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.
J Am Chem Soc. 2007 Feb 7;129(5):1196-202. doi: 10.1021/ja066102s.
Optically amplified photochemistry with slow photons has been realized in our previous work when a photoactive material such as TiO(2) was molded into a photonic crystal and the corresponding energy of photonic bands overlapped with the electronic excitation. While numerous applications of photonic crystals have been proposed, the real practicality depends on the extent of structural imperfection that can be tolerated before significant deterioration in the optical response deems it unrealistic to use. As a result, it is important to evaluate the amount of structural disorder that can be tolerated in inverse TiO(2) opals if they are to be used as amplified photocatalysts for photolytic degradation of organics in environmental remediation and water purification. We present a systematic study on the effect of disorder with relation to the photocatalytic efficiency of oxidizing methylene blue dye adsorbed on inverse TiO(2) opals by introducing different fractions and sizes of guest spheres into the opal template. Our results show that half of the enhancement originally achieved by the inverse opal made from monodispersed 150-nm spheres is conserved when the domain size of the host spheres remains above a critical threshold. The substitution fraction can be as high as 0.4 when the guest spheres are 1.2 times larger than the host spheres. Such a high tolerance to structural disorder provides strong support for the potential use of inverse TiO(2) opals in environmental cleanup and water treatment applications.
在我们之前的工作中,当将诸如TiO₂之类的光活性材料制成光子晶体且光子带的相应能量与电子激发重叠时,已实现了利用慢光子进行光放大光化学。虽然已经提出了光子晶体的众多应用,但实际实用性取决于在光学响应显著恶化到认为使用不切实际之前能够容忍的结构缺陷程度。因此,如果要将反相TiO₂蛋白石用作环境修复和水净化中光催化降解有机物的放大光催化剂,评估其能够容忍的结构无序量就很重要。我们通过向蛋白石模板中引入不同比例和尺寸的客体球体,对无序与吸附在反相TiO₂蛋白石上的氧化亚甲基蓝染料的光催化效率之间的关系进行了系统研究。我们的结果表明,当主体球体的畴尺寸保持在临界阈值以上时,由单分散的150纳米球体制成的反相蛋白石最初实现的增强效果的一半得以保留。当客体球体比主体球体大1.2倍时,取代比例可高达0.4。这种对结构无序的高耐受性为反相TiO₂蛋白石在环境清理和水处理应用中的潜在用途提供了有力支持。