Thin layers of an electrostatically associated adduct RuPVP-AuNP:POM formed between the polyoxomolybdate, [S2 Mo18 O62 ]4, the polycationic metallopolymer [Ru(bpy)2(PVP)10 ](ClO4)2 and DMAP-protected gold nanoparticle...Thin layers of an electrostatically associated adduct RuPVP-AuNP:POM formed between the polyoxomolybdate, [S2 Mo18 O62 ]4, the polycationic metallopolymer [Ru(bpy)2(PVP)10 ](ClO4)2 and DMAP-protected gold nanoparticle have been deposited onto electrodes using two separate methods, alternate immersion layer-by-layer assembly and pre-assembled drop-casting; PVP is poly(4-vinylpyridine), BPY is 2,2'-bipyridyl, and DMAP is 4-dimethylaminopyridine. Significantly, the efficiency of the photocatalysis depends markedly on the structure of the [RuPVP-AuNP:POM] even when photonic properties are very similar. Strikingly, despite their similar photonic properties, an additional optical transition is observed in UV-vis and the Raman spectra of pre-assembled drop cast [RuPVP-AuNP:POM], which was not seen in dip coated [RuPVP-AuNP:POM]. Importantly, this electronic communication enhances the photocatalytic oxidation of benzaldehyde by a factor of more than four. While there is clear evidence for photosensitisation in the drop cast not present for the dip coated systems, the magnitude of the photocurrent, i.e.,(82.2 6.6) nA·cm 2for pre-assembled drop cast [RuPVP-AuNP:POM] at a ruthenium to Au nanoparticle mole ratio of 48:1, is twice as large as that those found in [Ru-PVP:POM] film.展开更多
基金Projects(07/RFP/MASF386,201109019) supported by the Science Foundation Ireland and Ministry of Environmental Protection under the Research Frontiers Program,Ireland
文摘Thin layers of an electrostatically associated adduct RuPVP-AuNP:POM formed between the polyoxomolybdate, [S2 Mo18 O62 ]4, the polycationic metallopolymer [Ru(bpy)2(PVP)10 ](ClO4)2 and DMAP-protected gold nanoparticle have been deposited onto electrodes using two separate methods, alternate immersion layer-by-layer assembly and pre-assembled drop-casting; PVP is poly(4-vinylpyridine), BPY is 2,2'-bipyridyl, and DMAP is 4-dimethylaminopyridine. Significantly, the efficiency of the photocatalysis depends markedly on the structure of the [RuPVP-AuNP:POM] even when photonic properties are very similar. Strikingly, despite their similar photonic properties, an additional optical transition is observed in UV-vis and the Raman spectra of pre-assembled drop cast [RuPVP-AuNP:POM], which was not seen in dip coated [RuPVP-AuNP:POM]. Importantly, this electronic communication enhances the photocatalytic oxidation of benzaldehyde by a factor of more than four. While there is clear evidence for photosensitisation in the drop cast not present for the dip coated systems, the magnitude of the photocurrent, i.e.,(82.2 6.6) nA·cm 2for pre-assembled drop cast [RuPVP-AuNP:POM] at a ruthenium to Au nanoparticle mole ratio of 48:1, is twice as large as that those found in [Ru-PVP:POM] film.
