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Boiling/freezing depends on pressure as well as temperature, I think water would actually turn into steam if sprayed into space. There's a story of a spacesuit technician being accidentally exposed to a vacuum and he says his last memory is feeling the saliva bubble on his tongue.
https://www.spacesafetymagazine.com/aerospace-engineering/space-suit-design/early-spacesuit-vacuum-test-wrong/
It will do both. The initial boiling will draw heat away from the other molecules, eventually freezing them. So I suppose it wold depend on how fine the spray pattern is as well as the beginning temperature as to how much goes to gas vs. solid.