Howdy, @Nighthawk , and welcome to PhotoStructure! Apologies that PhotoStructure is misbehaving for you.
There are a couple things going on (and possibly more): your library like like it’s on a remote filesystem, so PhotoStructure should detect that automatically and switch to “replica” mode. Read more here: What's PS_FORCE_LOCAL_DB_REPLICA?
It looks like PhotoStructure couldn’t write to the root directory of that share, so there’s no volume UUID for that mountpoint. It should defer to storing references with psnet URIs, but those can be problematic. Read more about this here: PhotoStructure | What's a “drive,” or “volume?”
If you can set PS_LOG_LEVEL=info and restart PhotoStructure, wait a bit, and then send me logs, that might shed more light on the situation as well. Detailed instructions are here: PhotoStructure | What are in my logs and error reports?