Broken crystal symmetry of MWCNTs as the key factor in improvement of carboxyl functionalization

Carbon nanotubes functionalized with carboxyl groups (COOH-CNTs) find their application in energy storage, sensing, improving mechanical stability and biomedicine. So a facilitation of COOH-groups bonding to CNTs is one the modern scientific challenges. In this study untreated multi-walled CNT (MWCNTs), nitrogen-doped MWCNT (N-MWCNTs) and ion-beam irradiated N-MWCNTs (irr-N-MWCNTs) were synthesized using the CVD method. Characterizations were performed via HRTEM, Raman, XPS, and NEXAFS spectroscopy. Irr-N-MWCNTs demonstrated the largest amount of carbon crystallites, the presence of Stone-Welles defects as well as the regions of tensile-compressive, shear and torsional deformation. All these factors contributed to increase of carboxyl functionalization at the tube's surface. On the base of experimental data, the atomic supercells of N-MWCNTs and irr-N-MWCNTs were built by the self-consistent-charge density-functional tight-binding method (SCC DFTB). Through SCC DFTB, we quantified atomic rearrangements, electronic structures, charge transfers, total energies, and the forces and energy barriers relevant to COOH bonding. The twisting of irr-N-MWCNTs supercells by 45 degrees decreased the barrier to the carboxyl formation in 2.5 times in comparison to undeformed nanotubes. Our findings reveal that nitrogen addition, ion-beam irradiation, and induced deformations create the necessary conditions for COOH functionalization by altering the physicochemical surface properties of MWCNTs.