Local Environment of Superoxide Radical Formed on the TiO2 Surface Produced From Ti(OiPr)4 Exposed to H2O2.

Autor: Samoilova, Rimma I., Dikanov, Sergei A.
Zdroj: Applied Magnetic Resonance; Sep2022, Vol. 53 Issue 7-9, p1089-1104, 16p
Abstrakt: A selective heterogeneous catalyst with the superoxide anion O2•− stable at room temperature, generated by treating Ti(OR)4 (R = iPr, nBu) with H2O2, was previously reported and used for the oxidation of organic compounds. It was proposed that exceptional stability of the O2•− is resulted from its stabilization near Ti+4 cation on the TiO2 surface with the participation of water molecules and/or OH groups. In this article, we performed high-resolution pulsed EPR study on the O2•− in this catalyst with the aim to obtain quantitative information about its interactions with the surrounding molecules. Our data has shown that the O2•− is involved in weak hyperfine interactions with protons in the nearest environment, which do not exceed a value of 2 MHz. It corresponds to an Os...H distance of ≥ 3 Å that excludes the formation of hydrogen bonds. The analysis of possible structures of O2•− adsorption on TiO2 surface taking into account our results and lack of radical mobility at room temperature previously observed in EPR spectra led us to suggest that the O2•− is stabilized in the form of superoxo bridge coordinated with two titanium atoms. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index