I tried to root pepper cuttings once, in a glass of water - got nothing for my efforts. May have been the wrong time of year though.
From what I have read, peppers will only make adventitious roots at a (former) leaf node, ie if you remove cotyledons and plant them deep enough they may root from there. I can say from experience I've not seen any roots from the stem below that level - I never seem to pot them quite deep enough to cover the leaf node, but when you tip them to repot, the upper soil is root free and just tumbles off.
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