I see a few difficulties.
Configuring an icon for the button would be very difficult.
It's impossible to attach a recast timer to the button unless the spell already exists in another real hotbar. Not unless you want to pre-program the key with a recast value manually and deal with it being inaccurate due to varing ability speed, ability reuse and the random inability to cast at all.
The most straight-forward option would be to edit the spell list outside the game. Otherwise it's hard to impossible to save changes. (I've never messed with POI data saving)
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