Functionalization of Multiwall Carbon Nanotubes by Ozone at Basic pH. Comparison with Oxygen Plasma and Ozone in Gas Phase

Abstract

The selective functionalization of carbon nanotube surfaces is crucial for many potential applications of these materials. For this purpose several oxidants, among other substances, are used. The aim is to reach a large degree of functionalization which depends on the oxidant character of the reagent. For this reason the functionalization of multiwall carbon nanotubes (MWCNTs) by treatment with ozone in basic solution is studied. At basic pHs, ozone results into hydroxyl radicals whose reduction potential is very high (E° = 3.06 V). The results have been compared to those obtained by ozone in gas phase and with cold oxygen plasma. The oxidation with ozone in basic solution seems to be kinetically restricted. As a consequence, the degree of oxidation in this medium is smaller than this of ozone gas, in spite of the larger oxidation capacity of the former. The oxygen-containing groups fixed by these two treatments are mainly attached to defects of the nanotubes. Moreover, no modification of the graphene layers and no porosity result from these treatments. The oxygen plasma treatment stands out in the content of oxygen groups fixed to the MWCNTs, as it is by far more effective, although some of these groups have relatively low thermal stability. Nevertheless, this treatment mainly fixes the oxygen groups on the walls of the nanotubes.