Converting water to steam takes ~5-6 times as much energy as heating it from cold water or room temperature to the boiling point. The boiling water can absorb a bit less energy before it’s gone, but the difference isn’t that big. If you have enough water then you still have the other effect – removing the oxygen supply.
Pure steam can put our a fire, too, by displacing the oxygen (and potentially cooling the fire a bit, depending on its temperature – but not as efficient as water). But you’ll need a lot of steam to do so, and probably some closed room. Which is dangerous on its own.
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