Hi Sky,
I'm not a postgres expert, but the driver source code suggests that
that the problem may be with the tempfile table not having exactly one
sequence associated with it.
https://metacpan.org/source/TURNSTEP/DBD-Pg-3.9.1/Pg.pm#L401
The error seems to come either from line 401 or 408, where it seems to
be looking at the catalog to find an appropriate sequence. Perhaps
check that the table is set up with a SERIAL as expected? I don't
remember how tempfile is used, but you may be able to delete and
recreate it if there are no writes happening.
Hope that helps,
Dave