Surface Molecularly Imprinted TiO2 Nanoparticle for Photoreduction of Viologen

Abstract

ABSTRACTWhen small organic molecules (e.g. amino acids, nucleotides, and so on) are incorporated in metal oxide particles formed from metal alkoxide in the sol-gel process, the organic moieties can be removed readily by solvent washing or by degradative oxidation. Under proper conditions, nano-sized cavities corresponding to the shape of the individual organic moiety are produced within the metal oxide network as molecularly imprinted material such as surface molecularly imprinted TiO2. We tried to fabricate nano-sized particle of TiO2 to increase the effective contact area for the reactants, and further additional function for molecular recognition was intended to introduce through the surface modification of the molecular imprinting method in order to enhance the photoreduction of viologen. In this context, we prepared viologen imprinted TiO2 as an active and stable photocatalyst for photoreduction of viologen as a well-defined and readily identifiable and reversible electron carrier with appropriate redox potential for photoactivated TiO2. The basic concept of molecularly imprinting in this system is as follows. Oxidized viologen is generally twisted and dication molecule. While, reduced viologen is planar and monocation radical. Once TiO2 has such recognition site on its surface, it would be distinguishable through shape or charge recognition or both factors and facilitate the inclusion or exclusion of the target molecule result the enhancement of the reduction. After the preparation of the template, sol-gel imprinting was performed. Measuring its dynamic light scattering monitored changes of the particle sizes and the diameter was stabilized ca 120 nm after 1 week stirring. X-ray diffraction pattern of the TiO2 powder after the dryness without calcination indicates the dominant peak for anatase. Removal of the template was almost 36% after the alkaline rinsing by measuring its UV vis spectra of the washings. A buffered solution of Tris including viologen was irradiated through a xenon lamp under stirring in a quartz cuvett in Ar with or without the TiO2 with cut-off filter at room temperature. The formation of viologen monocation radical whose color is blue was easily recognized only in the reaction with TiO2. The formation of viologen monocation radicals from three types of (methyl, hexyl, and pentacarboxyl) viologens with time in the presence of the imprinted TiO2 and blank one was monitored spectrophotometrically. Blank means that it was fabricated similar way to the imprinted one without the template. Among these results, aliphatic C6 side chains of bipyridinium and terminal carboxyl groups were not effective to enhance. On the other hand, the less bulkiness methyl viologen resulted the highest yield. The most important result is that higher conversion was observed in every case of imprinted TiO2 compared with blank one. Therefore, the key point for recognition is not peripheral part, but bipyridinium part of the viologen.