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Surface- and Structural-Dependent Reactivity of Titanium Oxide Nanostructures with 2-Chloroethyl Ethyl Sulfide under Ambient Conditions.
Giles, Spencer L; Kastl, Anastasia M; Purdy, Andrew P; Leff, Asher C; Ratchford, Daniel C; Maza, William A; Baturina, Olga A.
Afiliação
  • Giles SL; Chemistry Division, United States Naval Research Laboratory, Washington, D.C. 20375, United States.
  • Kastl AM; NREIP Intern, Chemistry Division, United States Naval Research Laboratory, Washington, D.C. 20375, United States.
  • Purdy AP; Chemistry Division, United States Naval Research Laboratory, Washington, D.C. 20375, United States.
  • Leff AC; Sensors & Electron Devices Directorate, U.S. Army Research Laboratory, Adelphi, Maryland 20783, United States.
  • Ratchford DC; General Technical Services, Adelphi, Maryland 20783, United States.
  • Maza WA; Chemistry Division, United States Naval Research Laboratory, Washington, D.C. 20375, United States.
  • Baturina OA; Chemistry Division, United States Naval Research Laboratory, Washington, D.C. 20375, United States.
ACS Appl Mater Interfaces ; 14(7): 9655-9666, 2022 Feb 23.
Article em En | MEDLINE | ID: mdl-35134290
ABSTRACT
Robust materials capable of heterogeneous reactivity are valuable for addressing toxic chemical clean up. Synthetic manipulations for generating titanium oxide nanomaterials have been utilized to alter both photochemical (1000 nm > λ > 400 nm) and chemical heterogeneous reactivity with 2-chloroethyl ethyl sulfide (2-CEES). Synthesizing TiO2 nanomaterials in the presence of long-chain alkylphosphonic acids enhanced the visible light-driven oxidation of the thioether sulfur of 2-CEES. Photooxidation reaction rates of 99 and 168 µmol/g/h (quantum yields of 5.07 × 10-4 and 8.58 × 10-4 molecules/photon, respectively) were observed for samples made with two different alkylphosphonic acids (C14H29PO3H2 and C9H19PO3H2, respectively). These observations are correlated with (i) generation of new surface defects/states (i.e., oxygen vacancies) as a result of TiO2 grafting by alkylphosphonic acid that may serve as reaction active sites, (ii) better light absorption by assemblies of nanorods and nanowires in comparison to individual nanorods, (iii) surface area differences, and (iv) the exclusion of OH groups due to the surface functionalization with alkylphosphonic acids via Ti-O-P bonds on the TiO2. Alternatively, nanowire-form H2Ti2O5·H2O was produced and found to be capable of highly efficient hydrolysis of the carbon-chlorine (C-Cl) bond of 2-CEES in the dark with a reaction rate of 279.2 µmol/g/h due to the high surface area and chemical nature of the titanate structure.
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2022 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2022 Tipo de documento: Article