Functionalizing Fullerene Soot Nanoparticles with Energetic Groups Using Copper-Catalyzed Oxidative Deboration of Nitrophenylboronic Acid

In this study, 4-nitrophenylboronic acid is used as a radical precursor for functionalizing fullerene soot nanoparticles with 4-nitrophenyl and 4-nitrophenoxy groups. The oxidative deboration of 4-nitrophenylboronic acid for the formation of 4-nitrophenyl radical is carried out by employing potassium persulfate as oxidant and copper (II) sulfate as catalyst dissolved in water/dichloromethane under autoclave, oil-bath, or microwave heating conditions. The 4-nitrophenoxy radical is formed from the corresponding phenolic byproduct in the presence of persulfate/copper (II). The potentially energetic solid containing 4-nitrophenoxy groups involved in ether linkages is produced in the absence of fullerene soot. The 4-nitrophenyl and 4-nitrophenoxy radicals are efficiently trapped in the presence of fullerene soot to eventually afford samples with high nitrogen contents. The reaction conditions are optimized against temperature, time, and the amounts of starting materials. The characterization of products is performed by EDX and elemental maps, FT-IR, XRD, FESEM, and TGA-DSC. Results show that the oxidative deboration reaction can occur even in the absence of a catalyst. However, copper (II) catalyst can be used to obtain samples with more nitrogen content (up to 19.60 wt.% by EDX line scan) and better energetic performance. DSC thermograms of these samples exhibit a significant exothermic peak assigned to the decomposition of energetic groups. Highlights · 4-Nitrophenylboronic acid is used as radical precursor for functionalizing fullerene soot. · The oxidative deboration of 4-nitrophenylboronic acid is carried out by employing potassium persulfate as oxidant and copper(II) sulfate as catalyst. · Cupper(II) catalyst can be used to obtain samples with more nitrogen content (up to 19.60 wt.%) and better energetic performance. · The samples prepared in the longer reaction times and the higher temperatures have more energetic properties. · The sample prepared in the presence of catalyst in oil-bath has higher nitrogen content and better energetic performance among others. · The equiv. ratio of 1:3:0.2 for reactant, oxidant and catalyst is preferred. · These findings may be helpful for the development of novel energetic compositions from carbon nanomaterials.