Role of Synthetic Parameters on the Structural and Optical Properties of N,Sn-Copromoted Nanostructured TiO: A Combined Ti K-Edge and Sn L-Edges X-ray Absorption Investigation.

Sn-modification of TiO photocatalysts has been recently proposed as a suitable strategy to improve pollutant degradation as well as hydrogen production. In particular, visible light activity could be promoted by doping with Sn species, which are, however, thermally unstable. Co-promotion with N and Sn has been shown to lead to synergistic effects in terms of visible light activity, but the underlying mechanism has, so far, been poorly understood due to the system complexity. Here, the structural, optical, and electronic properties of N,Sn-copromoted, nanostructured TiO from sol-gel synthesis were investigated: the Sn/Ti molar content was varied in the 0-20% range and different post-treatments (calcination and low temperature hydrothermal treatment) were adopted in order to promote the sample crystallinity. Depending on the adopted post-treatment, the optical properties present notable differences, which supports a combined role of Sn dopants and N-induced defects in visible light absorption. X-ray absorption spectroscopy at the Ti K-edge and Sn L-edges shed light onto the electronic properties and structure of both Ti and Sn species, evidencing a marked difference at the Sn L-edges between the samples with 20% and 5% Sn/Ti ratio, showing, in the latter case, the presence of tin in a partially reduced state.