The earliest shotgun that I have seen with steel barrels was a Thomas Horsley hammer gun #1968, circa 1872. This gun was unusual because the barrels were engraved," steel"! I have seen one other early gun by this maker that also had steel barrels.
I was browsing older threads and came across the above. In case anyone is interested I thought I'd add a note.
I have the remains of Horsley gun #1890 which, other than the barrels, is in horrible condition having been re-actioned in an extremely crude manner. In its heyday it was a classic Horsley bar in wood hammer gun with side cam mechanical extractors. Despite its demise, the barrels are in good condition and are similarly engraved "Steel" on the under side of the rib. I believe this is an 1871 gun based on David Baker's list of SNs.
Just some more data for those interested.
Perhaps one day I'll bring it back from the dead but it would definitely not be an economically viable proposition.
Jeremy