The Nitric Oxide Dimer Reaction in Carbon Nanopores

When confined within nanoporous carbons (activated carbon fibers or carbon nanotubes) having pore widths of about 1 nm, nitric oxide is found to react completely to form the dimer, (NO)2, even though almost no dimers are present in the bulk gas phase in equilibrium with the pore phase. Moreover, the yield of dimer is unchanged upon varying the temperature over the range studied in the experiments. Earlier molecular simulation studies showed a significant increase in dimer formation in carbon nanopores, but the dimer yield was considerably less than that found in the experiments, and decreased rapidly as the temperature was raised. Here, we report an ab initio and molecular simulation study of this reaction in both slit-shaped pores and single-walled carbon nanotubes. The ab initio calculations show that the nitric oxide dimer forms a weak chemical bond with the carbon, and the bonding energy is more than 20 times stronger than the van der Waals energy assumed in the previous studies. When this is accounte...