In femtosecond-laser processing of titania in water, light can induce reduction and oxidation simultaneously. We follow this redox energy partitioning, in this perspective, from colloidal titania synthesis to hot-electron devices. Femtosecond ablation/fragmentation of an aqueous anatase suspension (515 nm, 230 fs,
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In femtosecond-laser processing of titania in water, light can induce reduction and oxidation simultaneously. We follow this redox energy partitioning, in this perspective, from colloidal titania synthesis to hot-electron devices. Femtosecond ablation/fragmentation of an aqueous anatase suspension (515 nm, 230 fs,
J, fluence
J cm
−2/pulse at clamped intensity ∼
W cm
−2) yields surface-reduced, Ti
3+-rich bluish TiO
2−x, while the same optical breakdown generates reactive oxygen species (ROS), among them H
2O
2 and HO
• radicals, which compete by re-oxidising Ti
3+. When the reduced titania is decorated with plasmonic nanoparticles (e.g., Au), an n-type plasmonic photo-electrode is realised:
hot electrons are injected over the Schottky barrier, while the deep
d-band supplies oxidising holes. The oxygen evolution reaction (OER) proceeds in stages at potentials well above the formal
V via the two-electron peroxide route (∼
V) or, for sufficiently energetic holes, via the one-electron HO
• route (∼
V). In a biased cell, H
2 evolves on Pt through the adsorbed (H
2+)
ad intermediate. The same Au/semiconductor physics on silicon enables sub-band-gap hot-electron photo-detection. Energy-level diagrams (flat-band and in-contact) and the
- vs.
d-band origin of the injected carriers are discussed.
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