As Matti said, ExFAT has never been supported for Photos Libraries. Through a number of older OSs lots of folks complained about corruption of their Photos Libraries, so Photos now just refuses to open Libraries on corrupting formats. Photos Library an external drive must be formatted in either APFS format or Mac OS Extended (Journaled) format. The drive must be connected directly to the Mac by cable, not networked, clouded, NASed, etc. Additionally, the drive can not have had Time Machine on it since it was formatted. See this:
Move your Photos library to save space on your Mac - Apple Support
You should stop accessing Photos with on an ExFAT drive immediately! A Photos Library can sit on an incompatible drive, but running it may corrupt the database.
Just drag the Library to a properly formatted volume. You may need to repair the Library --close Photos and re-launch by option-command-clicking the app icon. If you use iCloud Photos, it’s possible that this will cause a re-sync that lasts long enough to make you nervous.