Journal
JOURNAL OF MATERIALS CHEMISTRY
Volume 20, Issue 39, Pages 8639-8645Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0jm02192j
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Funding
- US Department of Energy [DE-FG02-05ER15667, DE-AC02-98CH10886]
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We report the direct determination of surface enthalpies for nanophase TiO2 anatase with different morphologies derived from drop solution calorimetry in a molten sodium molybdate (3Na(2)O center dot 4MoO(3)) solvent at 702 degrees C. The energetics of surface hydration has been measured using a Calvet microcalorimeter coupled with a gas dosing system. The surface enthalpies of hydrated surfaces for anatase TiO2 nanoparticles, nanowires and sea-urchin-like assemblies are 0.51 +/- 0.05, 1.07 +/- 0.28, and 1.29 +/- 0.16 J m(-2), respectively, whereas those of anhydrous surfaces are 0.74 +/- 0.04, 1.24 +/- 0.28, and 1.41 +/- 0.16 J m(-2), respectively. The trend in TiO2, which shows higher surface enthalpies for more complex nanostructures, is consistent with that reported in ZnO. The shape-dependent surface enthalpy at the nanoscale level is discussed in terms of exposed surface structures. The enthalpies of hydration appear to be similar for all morphologies.
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