Dukovic Gordana, White Brian E, Zhou Zhiyong, Wang Feng, Jockusch Steffen, Steigerwald Michael L, Heinz Tony F, Friesner Richard A, Turro Nicholas J, Brus Louis E
Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, USA.
J Am Chem Soc. 2004 Nov 24;126(46):15269-76. doi: 10.1021/ja046526r.
We have investigated reversible single-wall carbon nanotube (SWNT) oxidation by quantitative analysis of the oxide-induced absorption bleaching and luminescence quenching at low pH. These data, in combination with DFT structure calculations, suggest that the nanotube oxide is a 1,4-endoperoxide. At low pH, the endoperoxide protonates to create a hydroperoxide carbocation, introducing a hole in the SWNT valence band. Nanotube luminescence is extremely sensitive to quenching by hole-doping, while the absorption is relatively robust.
我们通过在低pH值下对氧化物诱导的吸收漂白和发光猝灭进行定量分析，研究了可逆的单壁碳纳米管（SWNT）氧化。这些数据与密度泛函理论（DFT）结构计算相结合，表明纳米管氧化物是一种1,4-内过氧化物。在低pH值下，内过氧化物质子化形成氢过氧化物碳正离子，在SWNT价带中引入一个空穴。纳米管发光对空穴掺杂猝灭极为敏感，而吸收则相对稳定。
