Photosensitization Behavior of Oligomeric Porphyrin Derivatives in Photocatalytic CO<SUB>2</SUB> Reduction by Re(I)-Complex-Anchored TiO<SUB>2</SUB> Catalytic Particle.
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Herein we report that porphyrin oligomers (D-ZnP and T-ZnP) derived from M-ZnP can be applied as photosensitizers in photocatalytic systems. Butadiyne-linked porphyrin oligomer has light-harvesting ability even from low-energy light source due to their extended conjugation length. These results support the significant improvement of the CO2 conversion efficiency in the photocatalytic system using the porphyrin oligomer as a photosensitizer. Indeed, the photocatalytic CO2 conversion efficiency in binary hybrid system using Re(I) doped TiO2 is improved when using porphyrin oligomer instead of M-ZnP. Although the CO2 conversion efficiency of porphyrin oligomer is relatively lowered than M-ZnP in the homogeneous system due to the lowered electron reduction power and the weaker driving force of ED, the radical anion of the porphyrin oligomer, which is generated by receiving electrons from the ED, has much higher intensity and longer lifetime than that of M-ZnP.