Wei Tong, Niu Baoling, Zhao Guohua
Institute of Translational Research, Tongji Hospital, Tongji University School of Medicine, Shanghai 200065, P.R. China.
School of Chemical Science and Engineering, Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, 1239 Siping Road, Shanghai 200092, China.
ACS Appl Mater Interfaces. 2020 Sep 2;12(35):39273-39281. doi: 10.1021/acsami.0c11101. Epub 2020 Aug 25.
Exploring the adsorption and selective removal mechanism of target pollutants on the catalytic interface is an important research topic in the field of environmental sewage treatment. However, the molecular recognition based on the surface of single crystals is still unclear. Single crystal molecularly imprinted TiO (001-MI-TiO) with a highly exposed {001} plane was prepared by a hydrothermal method to characteristically adsorb and degrade phenol. The kinetics of phenol oxidation on 001-MI-TiO was 12.93 times that of polycrystal nonimprinted TiO. The phenol adsorption quantity of 001-MI-TiO was 1.68 times that of the polycrystal molecularly imprinted TiO (MI-TiO). Compared with MI-TiO, the significantly increased removal of phenol on 001-MI-TiO mainly attributed to the enhanced adsorption quantity and better photocatalytic performance. The recognition mechanism of phenol on the 001-MI-TiO during the adsorption process was studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), which indicated enhanced adsorption of phenol when compared with MI-TiO. The recognition between the phenol molecule and the imprinted sites mainly relied on the hydrogen bond between the π bond of the benzene ring and the hydroxyl group on the surface of TiO. Besides, the interferent ATR-FTIR results showed that the single crystal surface can significantly reduce noncharacteristic adsorption, indicating good selectivity for the targets. In addition, the degradation intermediates during the photocatalytic process were further analyzed by in situ infrared technology.
探索目标污染物在催化界面上的吸附和选择性去除机制是环境污水处理领域的一个重要研究课题。然而，基于单晶表面的分子识别仍不清楚。通过水热法制备了具有高度暴露{001}面的单晶分子印迹TiO₂（001-MI-TiO₂），用于特异性吸附和降解苯酚。001-MI-TiO₂上苯酚氧化的动力学是多晶非印迹TiO₂的12.93倍。001-MI-TiO₂的苯酚吸附量是多晶分子印迹TiO₂（MI-TiO₂）的1.68倍。与MI-TiO₂相比，001-MI-TiO₂上苯酚去除率的显著提高主要归因于吸附量的增加和更好的光催化性能。利用衰减全反射傅里叶变换红外光谱（ATR-FTIR）研究了吸附过程中苯酚在001-MI-TiO₂上的识别机制，结果表明与MI-TiO₂相比，苯酚的吸附增强。苯酚分子与印迹位点之间的识别主要依赖于苯环的π键与TiO₂表面羟基之间的氢键。此外，ATR-FTIR干扰结果表明单晶表面可显著降低非特性吸附，表明对目标物具有良好的选择性。此外，利用原位红外技术进一步分析了光催化过程中的降解中间体。
