Mapping surface-modified titania nanoparticles with implications for activity and facet control

The use of surface-directing species and surface additives to alter nanoparticle morphology and physicochemical properties of particular exposed facets has recently been attracting significant attention. However, challenges in their chemical analysis, sometimes at trace levels, and understanding their roles to elucidate surface structure-activity relationships in optical (solar cells) or (photo) catalytic performance and their removal are significant issues that remain to be solved. Here, we show a detailed analysis of TiO2 facets promoted with surface species (OH, O, SO4, F) with and without post-treatments by 31P adsorbate nuclear magnetic resonance, supported by a range of other characterization tools. We demonstrate that quantitative evaluations of the electronic and structural effects imposed by these surface additives and their removal mechanisms can be obtained, which may lead to the rational control of active TiO2 (001) and (101) facets for a range of applications.