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Controlled Electropolymerization of Ruthenium(II) Vinylbipyridyl Complexes in Mesoporous Nanoparticle Films of TiO2

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  • This research was supported primarily by the UNC EFRC: Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0001011; supporting Z.F., S.K., and L.A.). H.L. is supported by a Royster Society Fellowship at UNC. Support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-FG02-06ER15788) to A.I. is acknowledged. We thank the Chapel Hill Analytical and Nanofabrication Laboratory for XPS measurements. We also thank Prof. Wenbin Lin for support with the BET measurements.

Abstract

Surface-initiated, oligomeric assemblies of ruthenium(II) vinylpolypyridyl complexes have been grown within the cavities of mesoporous nanoparticle films of TiO2 by electrochemically controlled radical polymerization. Surface growth was monitored by cyclic voltammetry as well as UV/Vis and X-ray photoelectron spectroscopy. Polymerization occurs by a radical chain mechanism following cyclic voltammetry scans to negative potentials where reduction occurs at the π* levels of the polypyridyl ligands. Oligomeric growth within the cavities of the TiO2 films occurs until an average of six repeat units are added to the surface-bound initiator site, which is in agreement with estimates of the internal volumes of the pores in the nanoparticle films.

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