Abstract

Layered titanate nanostructures offer promising photoelectronic properties that are subject to surface chemistry-induced morphology changes. For a systematic evaluation of the bulk and surface contributions to the photoactivity of these structures, we investigated their photoelectronic properties and in particular their dependence on the condition of the gas-solid interface. We comprehensively explored the stability of Na(2)Ti(3)O(7) nanowires and scrolled up H(2)Ti(3)O(7) nanotubes by means of transmission electron microscopy, Raman, and FT-IR spectroscopy and subjected both titanate sheet-based structures to controlled thermal activation treatment under high vacuum conditions. We found that throughout thermal annealing up to T = 870 K the structure and morphology of Na(2)Ti(3)O(7) nanowires are retained. Consistent with the significant photoluminescence emission that is attributed to radiative exciton annihilation in the bulk, UV-induced charge separation is strongly suppressed in these structures. H(2)Ti(3)O(7) nanotubes, however, undergo transformation into elongated anatase nanocrystals during annealing at temperatures T >OR= 670 K. Photoexcitation experiments in O(2) atmosphere reveal that these structures efficiently sustain the separation of photogenerated charges. Trends in the abundance of trapped holes and scavenged electrons were characterized quantitatively by tracking the concentration of paramagnetic O(-) and O(2)(-) species with electron paramagnetic resonance spectroscopy EPR, respectively. An incisive analysis of these results in comparison to those obtained on airborne anatase nanocrystals underlines the critical role of surface composition and structure on charge separation and, in consequence, on the chemical utilization of photogenerated charge carriers.