Cu(001)-bound isocyanate species (Nco((a))) have been prepared with two distinct methods. Isocyanic acid (HNCO) exposures at room temperature resulted in adsorbed NCO(a) alone. The exposure of Cu(001) to cyanogen (C2N2) and O-2 leads to surfaces displaying co-adsorbed oxygen (O-(a)), cyanide (CN(a)), and NCO(a) species. O-2 exposure of submonolayer NCO/Cu(001), followed by brief annealing at 473 K, initiated NCO(a) oxidation, giving rise to CO2(g) desorption and a surface-bound atomic N-(a) species. CO2(g) evolution was observed over a wide range of initial O-(a) coverages. In contrast, comparable thermal treatments of CN + O + NCO/Cu(001) samples, at 473 K, yield both CO(g) and CO2(g). Both TPRD and XPS studies of pre- and post-annealed surfaces indicated the two gaseous products. The co-adsorption of CN(a) promotes the dissociation of NCO(a) into CO(g) and N-(a), and dissociation can become the dominant means for NCO(a) removal. (C) 2012 Elsevier Inc. All rights reserved.