Surface modification of TiO2 nanocrystals by WOx coating or wrapping: Solvothermal synthesis and enhanced surface chemistry

TiO2 anatase nanocrystals were prepared by solvothermal processing of Ti chloroalkoxide in oleic acid, in the presence of W chloroalkoxide, with W/Ti nominal atomic concentration (Rw) ranging from 0.16 to 0.64. The as-prepared materials were heat-treated up to 500 °C for thermal stabilization and sensing device processing. For R0.16, the as-prepared materials were constituted by an anatase core surface-modified by WOx monolayers. This structure persisted up to 500 °C, without any WO3 phase segregation. For Rw up to R0.64, the anatase core was initially wrapped by an amorphous WOx gel. Upon heat treatment, the WOx phase underwent structural reorganization, remaining amorphous up to 400 °C and forming tiny WO3 nanocrystals dispersed into the TiO2 host after heating at 500 °C, when part of tungsten also migrated into the TiO2 structure, resulting in structural and electrical modification of the anatase host. The ethanol sensing properties of the various materials were tested and compared with pure TiO2 and WO3 analogously prepared. They showed that even the simple surface modification of the TiO2 host resulted in a 3 orders of magnitude response improvement with respect to pure TiO2.Authors acknowledge CSIC/CNR Project No. 2010IT0001 (SYNCAMON) and the SOLAR Project No. DM19447. J.A. and A.Z. acknowledge ICN2 Severo Ochoa Excellence Grant.Peer Reviewe