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affected indicating that luminol degradation is primarily initiated
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•−
by O2•− species. In addition, it was observed that generation of O2
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is significantly lower with TcPPM than with TcPPM/TiO2. Photocat-
possibly due to enhanced radiationless excited state dissipation,
therefore quantum yields of oxygen active species generation is
affected [81,82]. When the sensitizer is supported and well dis-
persed onto the TiO2 surface it is likely that the above phenomena
do not play a significant role due to site isolation [79].
4. Conclusion
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The EPR results suggest that bond formation between the por-
phyrin carboxyl group and TiO2 did not influence the signals of the
porphyrin ring of TcPPM and TcPPM/TiO2 (M = H, Fe, Co, Ni, Cu and
Zn). The EPR signals are produce by both unpaired electrons on the
-system of the porphyrin and oxygen radicals. The paramagnetic
centers are protected by both a resonant effect and by the functional
groups. Therefore, the free radicals produced on the porphyrin are
stable and even could be measured by EPR directly at room tem-
perature. In addition, the nature of the central metal atom affected
also the EPR signals.
DFT study of the hyperfine coupling constants of Cu in TcPPM
showed that it can accurately reproduce isotropic experimental
hfcc’s data, and in particular the UB3LYP functionals in combination
with specialized basis sets such as the 6–31G(df) perform well. The
calculated isotropic constants are in good agreement with experi-
mental data from EPR measurements, showing that DFT is a useful
tool for the calculation of hfccs in close or open-shell species.
Degradation of luminol indicated the presence of the super-
oxide anion (O2•−) produced by the interaction of O2 and the
conduction band electrons (e−CB), generated by photosensitization
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(ꢀ > 420 nm) of TiO2 with the porphyrin dye. The anchored metallo-
•−
porphyrins were much more efficient catalysts (generation of O2
)
than the porphyrins in solution. The effect is attributed to site isola-
tion preventing the formation of photo-inactive dimers. The central
metal ion has a visible effect on the photocatalytic performance
of unsupported and supported porphyrins. In homogeneous sys-
tem, photoactivity was higher for TcPPZn and TcPPH, which exhibit
long-lived singlet excited states. By contrast, in heterogeneous sys-
tem, TcPPCu/TiO2 showed the higher photoactivity. The tendencies
•−
suggest that the way of formation of O2 by TcPPM in solution is
different to that in TcPPM/TiO2.
Acknowledgments
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This work was supported by COLCIENCIAS (project no. 1102-
05-13560). We thank to COLCIENCIAS for the financial support of
grants: Programa de Apoyo a Doctorados Nacionales (GGO) and
movilidad 2005 (FMO); the Coordenac¸ ão de Aperfeic¸ oamento de
Pessoal de Nível Superior (CAPES-Brazil) for the financial support
through fellowship grants; and the EPR Division of Bruker-BioSpin
GmbH (Germany) for recording the spectra in Q-band.
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