Methods of oxidizing multiwalled carbon nanotubes are provided. The multiwalled carbon nanotubes are oxidized by contacting the carbon nanotubes with gas-phase oxidizing agents such as CO2, O2, steam, N2O, NO, NO2, O3, and ClO2. Near critical and supercritical water can also be used as oxidizing agents. The multiwalled carbon nanotubes oxidized according to methods of the invention can be used to prepare rigid porous structures which can be utilized to form electrodes for fabrication of improved electrochemical capacitors.