The reaction of mixtures of NO, CO, and H 2 over Pt/SiO 2 in combination with Al 2 O 3 has been investigated with on-line Fourier transform infrared spectroscopy as the principal analytical method. With Pt/SiO 2 alone isocyanic acid (HNCO) can be observed directly as a substantial product. It comprises up to 45% of the CO converted in the temperature range from 200 to 300°C. The yield is maximized when the amounts of H 2 and CO in the input stream are equal. No HNCO can be observed in experiments in which Al 2 O 3 is placed downstream of the Pt/SiO 2 or with a Pt/Al 2 O 3 catalyst. Hydrolysis to NH 3 and CO 2 is then complete. For this reason it is unlikely that HNCO will escape a catalytic converter in vehicle use but it may be a significant intermediate during the warm-up phase. The formation of HNCO can be rationalized as resulting from the hydrogenation of NCO groups present in small concentrations on the Pt surface under conditions of high CO coverage. The yield of HNCO falls steeply above 300°C when the CO coverage is falling. It is unclear if hydrolysis of HNCO occurs by direct reaction of molecular HNCO on the Al 2 O 3 surface or proceeds via the ubiquitious support-bound isocyanate species which have been observed in many previous studies. Previous observations of isocyanate formation in hydrogen-free systems can be rationalized as arising from HNCO formation by reverse spillover of hydrogen from OH groups on the support to generate HNCO on the platinum metal. This is then transported back to the support through the gas phase to form NCO groups.