Trap States in Reduced Colloidal Titanium Dioxide Nanoparticles Have Different Proton Stoichiometries

Gentry, Noreen E.; Gibson, Noah J.; Lee, Justin L.; Peper, Jennifer L.; Mayer, James M.

doi:10.1021/acscentsci.4c01074

Title: Trap States in Reduced Colloidal Titanium Dioxide Nanoparticles Have Different Proton Stoichiometries

Journal Article · 22 November 2024 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.4c01074 · OSTI ID:2483777

Gentry, Noreen E. ^[1];

^[1];

^[1]

Yale University, New Haven, CT (United States)

Added electrons and holes in semiconducting (nano)materials typically occupy “trap states,” which often determine their photophysical properties and chemical reactivity. However, trap states are usually ill-defined, with few insights into their stoichiometry or structure. Our laboratory previously reported that aqueous colloidal TiO₂ nanoparticles prepared from TiCl₄ + H₂O have two classes of electron trap states, termed Blue and Red. Herein, we show that the formation of Red from oxidized TiO₂ requires 1e^– + 1H⁺, while Blue requires 1e^– + 2H⁺. The two states are in a protic equilibrium, Blue ⇌ Red + H⁺, with K_eq = 2.65 mM. The Blue states in the TiO₂ NPs behave just like a soluble molecular acid with this K_eq as their K_a, as supported by solvent isotope studies. Because the trap states have different compositions, their population and depopulation occur with the making and breaking of chemical bonds and not (as commonly assumed) just by the movement of electrons. In addition, the direct observation of a 2H⁺/1e^– trap state contradicts the emerging H atom transfer (1H⁺/1e^–) paradigm for oxide/solution interfaces. Finally, this work emphasizes the importance of chemical stoichiometries, not just electronic energies, in understanding and directing the reactivity at solid/solution interfaces.

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Research Organization:: Yale University, New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021298

OSTI ID:: 2483777

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Journal Issue: 12 Vol. 10; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Trap States in Reduced Colloidal Titanium Dioxide Nanoparticles Have Different Proton Stoichiometries

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