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TWC exposure to extreme temperature could result in irreversible damage or thermal failure. Thus, a strategy embedded in the engine control unit (ECU) called catalyst overheating protection (COP) will be activated to prevent TWC overheating. When COP is activated, the command air-fuel ratio will be enriched to cool the catalyst monolith down. Fuel enrichment has been proven a main prerequisite for ammonia formation in hot TWCs as a by-product of NOx reduction. Hence, COP events could theoretically be a source of post-catalyst ammonia from petrol vehicles, but this theory is yet to be confirmed in published literature. This paper validated this hypothesis using a self-programmed chassis-level test. The speed of the test vehicle was set to constant while the TWC temperature was raised stepwise until a COP event was activated.