Matrix isolation combined with EPR and FT-IR technique at low temperature has been used to study the gas phase species involved in HC-SCR over a highly active Ag/alumina catalyst. A combination of heterogeneous and homogeneous (radical) reactions is proposed to take place over a Ag/alumina catalyst during HC-SCR. Radicals of low molecular weight were trapped in a growing argon matrix behind the Ag/alumina catalyst. In the same matrix, cyanogen isocyanate was detected and is suggested to be a key intermediate for the formation of amines and ammonia via the hydrolysis of isocyanate species. (c) 2004 Elsevier B.V. All rights reserved.