In Situ Electrochemical Raman Spectroscopy of Air-Oxidized Semiconducting Single-Walled Carbon Nanotube Bundles in Aqueous Sulfuric Acid Solution

In this study, we oxidized approximately 90% semiconducting, highly crystalline single-walled carbon nanotube (hc-SWCNT) bundles in the atmosphere at 450 degrees C for 30 min to obtain SWCNTs modified with oxygen-containing functional groups and investigated not only the influence of air oxidation on the electrochemical doping of the air-oxidized SWCNT (AO-SWCNT) bundles in aqueous sulfuric acid solution using in situ Raman spectroscopy, but also the relationship between the in situ electrochemical Raman data and the properties of electric double-layered supercapacitors (EDLSCs). By oxidizing the hc-SWCNTs in air, AO-SWCNTs with a small diameter distribution could be prepared. When a negative charge was applied to the AO-SWCNTs used as a working electrode in a three-electrode electrochemical cell for in situ Raman spectroscopy, a large downshift of the G(+) line of the AO-SWCNTs was observed compared to that before air oxidation. On increasing the ratio of small-diameter nanotubes/total nanotubes, the Raman data obtained in situ revealed that the effect of the weakening of the C-C bond was stronger than that of the renormalization of the phonon energy. In contrast, in the case of applying a positive charge to the AO-SWCNTs, the magnitude of the upshift of the G(+) line for the AO-SWCNTs was slightly larger than that for the hc-SWCNTs. The influent electric charges per unit mass and the specific capacitances of the AO-SWCNT electrodes for the maximum magnitude of the shift of the G(+) line (10.7 cm(-1)) were 60.1 C/g and 50.1 F/g, respectively, which are larger than those of hc-SWCNT electrodes. In situ Raman spectroscopy is a useful method to simultaneously assess the increase or decrease in the diameter distribution of small nanotubes and the specific capacitances of electric double-layered supercapacitors of chemically functionalized SWCNTs by the magnitude of the shift of the G(+) line compared to unfunctionalized SWCNTs.