Can I use Empoleon's "Diving Draw" Ability if I have no cards left in my deck, and just discard a card from my hand?
Yes, you can. The first sentence of Diving Draw says to discard a card from your hand. Then if you can do that, you do as much of the rest of the Ability as you can, which in this case is draw no cards.
Source: TPCi Rules Team (2012-10-04)