Rtimi Sami, Pulgarin Cesar, Nadtochenko Victor A, Gostev Fedor E, Shelaev Ivan V, Kiwi John
Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-GPAO, Station 6, CH-1015 Lausanne, Switzerland.
N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, str. Kosygina 4, 119991 Moscow, Russia.
Sci Rep. 2016 Jul 22;6:30113. doi: 10.1038/srep30113.
This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation.
本研究首次报告了FeOx-TiO2薄膜微观结构对通过快速光谱检测到的与远程细菌灭活性能相关的瞬态现象的影响。针对每种FeOx+TiO2微观结构,报告了不同的快速动力学飞秒瞬态光谱。确定了在光照下产生的短寿命瞬态物种和氧化中间自由基的寿命。将在聚乙烯薄膜上共溅射的FeOx-TiO2(两种氧化物均呈现随机分布)与仅由最顶层的FeOx组成的顺序溅射FeOx/TiO2薄膜进行了比较。优化FeOx:TiO2的比例以实现最高的光转换。通过X射线荧光分析,发现薄膜本体中的Fe:Ti比例约为1.4,通过XPS蚀刻发现在光催化剂最顶层的比例为4:1。对于共溅射的FeOx-TiO2-PE薄膜,FeOx-TiO2异质结导致电子从FeOx注入到较低的TiO2俘获态。详细表征了薄膜的光学性质、粒径、粗糙度、疏水-亲水平移以及瞬态氧化还原状态的时间演变。具有不同微观结构的薄膜导致不同的抗菌活性。这表明控制光照射下电荷转移的是FeOx-TiO2-PE的微观结构,而不是半导体FeOx和TiO2的势能水平位置。