Porphyrin dyes on TiO2 surfaces with different orientations: a photophysical, photovoltaic, and theoretical investigation.
Porphyrin dyes with a triphenylamino group as an electron donor, para- or meta-benzoic acids as electron acceptors, and hydrogen (H) or mesityl (M) substituents on the meso position as auxiliary groups were synthesized. Their photophysical properties and photovoltaic performance in dye-sensitized solar cells were investigated. All four porphyrins exhibited similar photophysical properties in the solution and dye-loading densities on the surface of TiO2 nanoparticles; however, the p-benzoic acid functionalized porphyrins, p-H(M)PZn, gave better photovoltaic performance than m-benzoic acid functionalized porphyrins, m-H(M)PZn. Theoretical calculations indicated that the electron density on the frontier molecular orbital was more delocalized to p-benzoic acid than to m-benzoic acid. Absorption spectra indicated the stronger H-aggregation in m-H(M)PZn than that in p-H(M)PZn on the surface of TiO2 nanoparticles. The mesityl groups in the meso positions reduced the dye-loading density due to steric hindrance between dyes. As a result, the p-MPZn exhibited the best energy conversion efficiency among the four porphyrins studied. This efficiency was further enhanced when a complementary dye BET was used.
Department of Chemistry, Eastern Illinois University , Charleston, Illinois 61920, United States.
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