This looks like the same thing @acebmxer ran into in July (https://xcp-ng.org/forum/topic/12339), and your libuv reading matches what the XO devs wrote in https://github.com/vatesfr/xen-orchestra/pull/10587.
As I read their write-up, with a hard mount every background operation on the dead remote (listing backups, retries) holds one of xo-server's file-access threads until the NAS comes back, and once they're all taken the web UI can't be served either.
Olivier's advice back then (https://xcp-ng.org/forum/post/106632) was to disable the remote while the NAS is still up and only then power it off, and acebmxer scripted that on the Synology so the remote gets disabled at shutdown and enabled again at startup through the XO API.
If XO is already stuck, XO 6.10.0 added xo-server-db disable-remote <id>, which you run while xo-server is stopped so the remote isn't mounted again on the next start; your November 1 build should have it if I read the dates right, but I haven't tried it myself.
About UV_THREADPOOL_SIZE I'm only guessing, but since a hung NFS call never gives its thread back I'd expect a bigger pool to just take longer to fill, and the PR says they tried capping the threads one remote can use and dropped the idea for now. @Team-XO-Backend will know better than me whether more is planned.