I have pi-hole installed on Ubuntu 22.04, which has a static IP address as 192.168.1.9. Setting DNS to only 192.168.1.9 in my DHCP options works great, but when I set it to 192.168.1.9, 1.1.1.1, and 8.8.8.8, pi-hole does not block any ads. DHCP is setup on my Ubuiquiti UDM Pro.
Actual Behavior
No ads are blocked, able to re-produce on iOS 16.5.1, Firefox Desktop (Secure DNS off) on macOS 13.4.1, and others.
This is the expected behavior. Pi-hole should be your only DNS server.
If you provide alternate DNS servers to clients, they are free to use any of them at any time, with the result that some of your DNS traffic will bypass Pi-hole.