Mechanothermal Approach for N-, S-, P-, and B-Doping of Carbon Nanotubes: Methodology and Catalytic Performance in Wet Air Oxidation

The texture and the surface chemistry of carbon nanotubes (CNTs) were modified using a solvent-free methodology involving a ball-milling mechanical treatment and thermal treatment under nitrogen in the presence of adequate precursors (melamine, sodium thiosulfate, sodium dihydrogen phosphate, and boric acid) of different heteroatoms (N, S, P, and B, respectively). The incorporation of these heteroatoms promotes significant changes in the pristine textural and chemical properties. This easy post-doping method allows the introduction of large concentrations of heteroatoms. Their effect on the catalytic activity of the materials was evaluated in the oxidation of oxalic acid by catalytic wet air oxidation (CWAO), as an alternative to the noble metal and rare earth oxide catalysts traditionally used in this process. Improved catalytic activities were obtained using the N-, P-, and B-doped CNTs in oxalic acid oxidation, while the S-doped CNT sample underperformed in comparison to the pristine material.