Role of Black Carbon Electrical Conductivity in Mediating Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) Transformation on Carbon Surfaces by Sulfides

Recent research has demonstrated that black carbons catalyze the transformation of a range of nitrated explosives sorbed to the carbon surfaces in the presence of sulfides. Although surface oxygenated functional groups, particularly quinones, and electrical conductivity have both been hypothesized to promote these reactions, the importance of these properties has not been tested. In this work, the importance of electrical conductivity was addressed by producing chars of increasing electrical conductivity via pyrolysis of wood shavings at increasing temperature. The reactivity of chars with respect to transformation of the explosive RDX in the presence of sulfides correlated with electrical conductivity. Oxygenated functional groups were apparently not involved, as demonstrated by the elimination of reactivity of an activated carbon after ozone treatment or sorption of model quinones to the activated carbon surface. Although RDX transformation correlated with char electrical conductivity, no RDX transformation was observed when RDX was physically separated from sulfides but electrically connected through an electrochemical cell. RDX transformation occurred in the presence of a surface-associated sulfur species. The correlation with char electrical conductivity suggests that sulfides are oxidized on carbon surfaces to products that serve as potent nucleophiles promoting RDX transformation.