Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 10, Issue 19, Pages 16836-16842Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.8b00894
Keywords
hybrid materials; porphyrin adsorption; optical properties; solvent-assisted adsorption; nanoparticle functionalization
Funding
- Deutsche Forschungsgemeinschaft (DFG) within the Research Unit FOR 1878 funCOS, Functional Molecular Structures on Complex Oxide Surfaces
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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 2H-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.
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