If you follow your suggested procedure, the new 3TB drive you insert will format to 2TB to mirror the size of your existing drive (and I'm not sure if your data will be lost).
Here is the safest procedure:
(1a) If you have a Linux PC, then simply install the 2TB drive on your PC and you should be able to directly see your data
(1b) If you have a Windows PC, there is a freeware application called EXT2Explorer that will allow your Windows PC to mount and see the data on the Linux formatted (EXT) drive (DNS-325 formats drives using the Linux filesystem). You can place the 2TB drive in your PC or use an external USB drive enclosure.
(1c) If you have the capacity on your PC, you can copy all of your files over to your PC and copy them back again, although this will consume extra time.
(2) Place two 3TB drives in your DNS-325 and create a RAID 1 array
(3) Copy the data from your 2TB in your Windows PC / Linux PC to the DNS-325