Progress in the Raman spectra analysis of covalently functionalized multiwalled carbon nanotubes: unraveling disorder in graphitic materials

Raman spectroscopy is highly sensitive to the morphology and electronic structures of graphitic materials, but a convenient interpretation model has been lacking for multiwalled carbon nanotubes (MWCNTs), in particular for the discrimination of spectral changes induced by covalent functionalization. The present work describes a systematic investigation of the Raman analysis of covalently functionalized MWCNTs by diazonium chemistry and oxidation methodologies, with typically different mechanisms and reaction sites. A multi-peak deconvolution system and spectral band assignment were proposed based on the chemical and structural modifications identified by X-ray photoelectron spectroscopy, thermogravimetry, X-ray diffraction, specific surface areas and the comparative analysis of the first and second order regions of the Raman spectra. Diazonium functionalization takes place mainly in the π-system of the external sidewall, while oxidation occurs on defects and leads to structure burning. This allowed us to distinguish between spectral features related to aromaticity disruptions within the sidewalls and spectral features related to changes within the inner tubes. The model was validated extending the studies to the functionalization of MWCNTs by the Bingel reaction. Improved Raman interpretation of covalently functionalized MWCNTs arises from the distinction between spectral features related to aromaticity disruptions within the sidewalls and within the inner tubes.