Water-Assisted
Hole Trapping at the Highly Curved
Surface of Nano-TiO2 Photocatalyst
Version 2 2018-04-20, 23:49
Version 1 2018-01-22, 05:35
Posted on 2018-04-20 - 23:49
Heterogeneous
photocatalysis is vital in solving energy and environmental
issues that this society is confronted with. Although photocatalysts
are often operated in the presence of water, it has not been yet clarified
how the interaction with water itself affects charge dynamics in photocatalysts.
Using water-coverage-controlled steady and transient infrared absorption
spectroscopy and large-model (∼800 atoms) ab initio calculations,
we clarify that water enhances hole trapping at the surface of TiO2 nanospheres but not of well-faceted nanoparticles. This water-assisted
effect unique to the nanospheres originates from water adsorption
as a ligand at a low-coordinated Ti–OH site or through robust
hydrogen bonding directly to the terminal OH at the highly curved
nanosphere surface. Thus, the interaction with water at the surface
of nanospheres can promote photocatalytic reactions of both oxidation
and reduction by elongating photogenerated carrier lifetimes. This
morphology-dependent water-assisted effect provides a novel and rational
basis for designing and engineering nanophotocatalyst morphology to
improve photocatalytic performances.
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Shirai, Kenji; Fazio, Gianluca; Sugimoto, Toshiki; Selli, Daniele; Ferraro, Lorenzo; Watanabe, Kazuya; et al. (2018). Water-Assisted
Hole Trapping at the Highly Curved
Surface of Nano-TiO2 Photocatalyst. ACS Publications. Collection. https://doi.org/10.1021/jacs.7b11061
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AUTHORS (11)
KS
Kenji Shirai
GF
Gianluca Fazio
TS
Toshiki Sugimoto
DS
Daniele Selli
LF
Lorenzo Ferraro
KW
Kazuya Watanabe
MH
Mitsutaka Haruta
BO
Bunsho Ohtani
HK
Hiroki Kurata
CV
Cristiana Di Valentin
YM
Yoshiyasu Matsumoto
KEYWORDS
terminal OHWater-Assisted Hole Trappingabsorption spectroscopycharge dynamicsTiO 2 nanosphereswater-assisted effectwell-faceted nanoparticlesphotocatalytic reactionsmorphology-dependent water-assisted effectnanosphere surfaceinteractionphotocatalytic performancesCurved Surfaceab initio calculationswater adsorptionNano-TiO 2 Photocatalyst Heterogeneous photocatalysiselongating photogenerated carrier lifetimesengineering nanophotocatalyst morphology