AbstractThe interaction of nitrogen monoxide (nitric oxide, NO) with pyrolysed polyacrylonitrile (PANP) has been examined together with the feasibility of the use of PANP based catalysts for the removal of small quantities of NO from the exhaust systems of internal combustion engines. Kinetic studies indicated that PANP was capable of interacting with and removing NO from an inert carrier gas and that the initial specificity of this interaction was little affected by hydrogen, hydrocarbons, carbon monixide or oxygen, the initial rates of removal being appreciably higher than those obtainable with conventional inorganic catalysts or graphitised carbon. The activation energy and kinetic features of the reaction suggested that the interaction involved the odd electron nature of NO and the free spin generated at the polymer surface. Once adsorbed the nitric oxide decomposes to form dinitrogen oxide (N2O) which is further reduced to nitrogen with concurrent assimilation and rearrangement of oxygen within the polymer structure. As a result the PANP gradually loses its capacity to adsorb and decompose NO. In addition, it appears that the structural features which promote the oxidative instability of PANP also govern its NO removal ability. Consequently, the lifetime and therefore practical utility of these systems is governed by the limits of oxidative stability and catalytic capacity.