Reactive Porphyrin Adsorption on TiO2 Anatase Particles: Solvent Assistance and the Effect of Water Addition.

The surface functionalization of metal oxide nanoparticles with complex organic molecules can lead to optoelectronically very different material properties, depending on whether adsorption occurs at the solid-gas or solid-liquid interface. Here, we report on two different approaches to decorate anatase TiO2 nanoparticle powders with 2 H-tetraphenylporphyrin (2HTPP) molecules: (i) porphyrin adsorption in dispersions of organic liquids and (ii) gas-phase functionalization where evaporated porphyrin molecules attach to dehydrated particle surfaces in the absence of solvent molecules. In the latter case, a bottom-up approach is pursued to explore both the impact of organic solvent molecules and the impact of spurious water on the surface chemistry of porphyrin-sensitized TiO2 nanoparticles. Vis diffuse reflectance and photoluminescence emission spectroscopy provide clear evidence for the promotion of interfacial reorganization processes of the adsorbate species by coadsorbed solvent molecules in liquids. Moreover, traces of spurious water were found to induce protonation-deprotonation reactions on the adsorbed porphyrins with a strong impact on the optical properties of the resulting hybrid materials.