ct6b00519_si_001.pdf (6.14 MB)
Effect of Size and Structure on the Ground-State and Excited-State Electronic Structure of TiO2 Nanoparticles
journal contribution
posted on 2016-07-05, 00:00 authored by Daeheum Cho, Kyoung
Chul Ko, Oriol Lamiel-García, Stefan T. Bromley, Jin Yong Lee, Francesc IllasWe investigated the
influence of size and structure on the electronic
structure of TiO2 nanoparticles 0.5–3.2 nm in diameter,
in both vacuum and water, using density functional theory (DFT) calculations.
Specifically, we tracked the optical and electronic energy gap of
a set of (TiO2)n nanoparticles ranging from
small non-bulklike clusters with n = 4, 8, and 16,
to larger nanoparticles derived from the anatase bulk crystal with n = 35 and 84. As the difference between these two energy
gaps (the exciton binding energy) becomes negligible in the bulk,
this magnitude provides an indicator of the bulklike character of
the electronic structure of the nanoparticles under study. Extrapolating
our results to larger sizes, we obtain a rough estimate of the nanoparticle
size at which the electronic structure will begin to be effectively
bulklike. Our results generally confirmed that the electronic structure
of the nanoparticle ground state and excited state has a more pronounced
structure dependency than size dependency within a size range of 0.5–1.5
nm. We also showed that the thermodynamic preference for the photocatalytic
species is the first S1 exciton. This S1 exciton
is stable under vacuum but may evolve to free charge carriers upon
structural relaxation in an aqueous environment for particles 0.5–1.5
nm in size studied in the present article. An analysis of ionization
potentials and electron affinities, relative to the standard reduction
potential for the water splitting half-reactions, revealed the importance
of considering the structural relaxation in the excited states and
the presence of water for assessing the thermodynamic conditions for
photocatalytic water splitting.
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Keywords
electron affinitiesbulklike charactercharge carriersexciton binding energynanoparticle sizephotocatalytic speciesanatase bulk crystalenergy gapsstructure dependencyS 1 excitonphotocatalytic water splittingsize rangeTiO 2 Nanoparticlesnanoparticle ground statenmTiO 2DFTionization potentialssize dependencyn nanoparticlesenergy gap
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