Metalloporphyrin Assemblies on Pyridine-Functionalized Titanium Dioxide

Porphyrin adsorption on TiO2 nanoparticles has been achieved for multiple porphyrins, and in mixed porphyrin assemblies, via axial ligation to surface-bound pyridine anchored by either para carboxylic or phosphonic functionalizations. Homogenous assemblies were prepared and characterized, while mixed metalloporphyrin assemblies were demonstrated by controlling the concentration ratios of respective porphyrins in the modifying solution. Evaluation of the assemblies using spectroscopic techniques and electrochemistry confirms high porphyrin retention, while exhibiting their surface bound optical and electrochemical properties. A thorough study is discussed where several metalloporphyrins have been evaluated (Ru(CO)OEP, Ru(CO)TPP, and ZnTPP) for relative comparisons and relationships to pyridyl axial binding strengths. The systematic study evaluates multiple background cases using either H2TPP, TiO2 modification with benzoic acid, or unmodified TiO2 to confirm the high affinity of Ru and Zn porphyrins for surface-anchored pyridyl sites. The simple method of step-by-step coordinative anchoring of porphyrins to TiO2 using small, commercially available molecules is highly adaptable for use in dye-sensitized solar cells (DSSC) where intimate contact between the absorbing dye and the semiconductor is required. DSSC devices with novel mixed porphyrin assemblies were shown to give higher power performance than DSSCs utilizing sensitization with only one type of porphyrin.