I have pi hole configured to using unbound as the recursive DNS server. I'm a newbie to using Unbound and Pi Hole recursive so I may very well have missed some configuration setup.
I have Quad 9 setup as my WAN on my router instead of my ISP.
Unbound uses DNSSEC to validate DNS replies, and that may fail if the time wouldn't be correct on your Pi-hole machine.
As a result, DNS lookups would also fail, including the lookup of any NTP server domain.
Please verify whether your Pi-hole machine's time and time zone information is correct.
Resolution would also fail if Pi-hole (or one of its upstreams) would block your configured NTP server domain, or if the upstream would time-out.
Please verify that you don't block your NTP server domain accidentally, e.g. via Tools | Search Lists.