Electroless ultrasonic functionalization of diamond nanoparticles using aryl diazonium salts

We report a novel and very handful strategy for the functionalization of diamond nanoparticles (NDs), based on the ultrasound-assisted grafting of aryl groups from the electroless reduction of diazonium salts. For this study, 4-nitrobenzenediazonium salt was used as a model molecule and the reaction was investigated in neutral and acidic aqueous media. Spectroscopic evidence for the successful attachment of aryl groups to nanodiamonds (NDs) was given by IR and XPS which clearly detect characteristic NO₂ peaks. Moreover, the absence of any peaks from the ⁺N≡N group in the IR spectra is a clear indication of the chemical reduction of the parent diazonium salt at the surface of NDs. This spontaneous chemical modification of NDs by aryl diazonium salts was confined to the surface of the ND particles; indeed, XRD measurements have shown that the crystalline structure of the bulk of the particles was unaffected. It opens up new possibilities towards the control of the surface chemical composition of NDs using simple protocols operated in very soft conditions, i.e. in water at room temperature. It shows conclusively that the chemistry toolbox of experts interested in nanodiamonds should contain aryl diazonium salts, given their versatility in forming active platforms.