The influence of Zn and K promoters on N2O decomposition over Co3O4 was investigated by work function measurement and temperature-programmed surface reaction. The beneficial effect of the promoters resulting in spectacular decrease in the temperature of 50% conversion by 200 degrees C was found to be essentially of electronic origin. The strong correlation between the catalyst work function and deN(2)O activity allowed for the optimization of the doping level of both additives. The pilot plant tests in real nitric acid tail gases revealed that the optimized double promoted (Zn, K) cobalt spinel catalyst maintained its remarkable activity in N2O decomposition (conversion > 95% at the target temperature of 350 degrees C) for more than 60 h.