Is there any difference between playing 3.g3 and 3.Nf3 in the Catalan system (after 1.d4, Nf6 2.c4, e6), if so, which one is generally preferred?
You can play Nf3/c4/g3/d4 in any order.
There are thousands of subtleties. It depends what you are going to reach and what you are going to prevent.
Early g3 prevents b6 setups I suppose.
3.Nf3 allows black the option of avoiding the Catalan by playing 3...b6, entering the Queen's Indian Defense.