"Do they buy rice at the supermarket?"
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There are two ways to express right now: 现在 and 正在. The difference between the two is somewhat nuanced, and some people use them interchangeably, but 现在 generally means "now" and 正在 emphasizes at the very moment.
Your sentence is almost correct, but you'll need to add a second 在 because both characters in 正在 belong together to express time (right now), and the second 在 expresses the location (at the supermarket): 他们正在在超市买大米吗？
Technically you could, but it really isn't done that way. Think of the structure X 不 X sort of like "do or do not" in English: "Do they, or do they not, buy rice in the supermarket?" In certain conditions you would ask the question that way (say, trying to establish the facts), but the question as stated is more like, "So, do they buy the rice at the supermarket?" (as opposed to somewhere else).
....or do they buy it somewhere else? I can't help but think that, translating from the Mandarin to English, it would make more sense to say "Are they buying rice at the supermarket" or "Are they at the supermarket to buy rice?" rather than "Do they buy rice at the supermarket?" (There is quite a difference in meaning.) Maybe a native Mandarin speaker could comment.....