In a way we already do! It is possible to use the heat trapped in the earth to generate electricity by heating water to steam. This is called geothermal energy and is already used widely in lots of places, especially with active volcanoes like in Iceland. To harness the power during an actual eruption would be very difficult though. The more explosive eruptions can destroy the volcano itself, so an buildings there would also probably be demolished, and volcanic eruptions like this are usually single events, so any power you would get would be available only for a short time. But it would be amazing if we could!
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