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The catalyst needs to get up to temperature before it becomes functional. That's why the car does that higher RPM "startup roar" to pre-heat it as fast as possible.
Once the catalyst gets hot, then it burns the hydrocarbons on the exhaust.
What does the exhaust smell like? Oil is really putrid, if it was a catalyst, then it would smell like unburnt fuel, coolant will have slightly sweet smell.
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