Please upload a debug log and post just the token URL that is generated after the log is uploaded by running the following command from the Pi-hole host terminal:
Why do you have two IP's assigned to the eth0 interface on the Pi?
*** [ DIAGNOSING ]: Setup variables
PIHOLE_INTERFACE=eth0
*** [ DIAGNOSING ]: Network interfaces and addresses
2: eth0@if274: <BROADCAST,MULTICAST,UP,LOWER_UP> mtu 1500 qdisc noqueue state UP group default qlen 1000
inet 10.0.100.21/27 metric 1024 brd 10.0.100.31 scope global dynamic eth0
valid_lft 74145sec preferred_lft 74145sec
inet 10.0.100.20/27 scope global secondary eth0
valid_lft forever preferred_lft forever
Open a terminal window to the Pi and start tailing the Pi-hole log with the command pihole -t.
The, while still tailing, run the nslookup command from the client again. Do you see a burst of activity in the log, including the nslookup command from the client?
Both of your Pi-hole's have an entry to block discord.com:
((\.|^)discord\.com$
And your nslookup results demonstrates that each of them correctly blocks discord.com, as would be expected.
You haven't disclosed what the Query Logs look like, but the replies would imply that both nslookups registered with the respective Pi-hole.
Please run that nslookup against your .20 virtual keepalived IP and share the results, also watching your Pi-holes' Query Log for the respective DNS requests.
You haven't disclosed that yet for the nslookups above, but assuming that they did not register with Pi-hole, that would be a strong indication that your router may forcefully redirect DNS requests from one of your subnets to a DNS resolver of its own choice.
You should check your router's firewall configuration in that regard.
I resolved it by disabling Content Filtering on UniFi network:
piadmin@pihole01:~$ sudo grep discord.com /var/log/pihole/pihole.log
Aug 10 08:19:46 dnsmasq[325]: query[A] discord.com from 10.0.100.6
Aug 10 08:19:46 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:19:46 dnsmasq[325]: query[AAAA] discord.com from 10.0.100.6
Aug 10 08:19:46 dnsmasq[325]: regex blacklisted discord.com is ::
Aug 10 08:24:34 dnsmasq[325]: query[A] discord.com from 10.0.100.13
Aug 10 08:24:34 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:25:53 dnsmasq[325]: query[A] discord.com from 10.0.107.17
Aug 10 08:25:53 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:27:44 dnsmasq[325]: query[A] discord.com from 10.0.1.13
Aug 10 08:27:44 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:30:18 dnsmasq[325]: query[A] discord.com from 10.0.1.13
Aug 10 08:30:18 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:47:48 dnsmasq[325]: query[A] discord.com from 10.0.1.13
Aug 10 08:47:48 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:48:53 dnsmasq[325]: query[A] discord.com from 10.0.1.13
Aug 10 08:48:53 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:50:02 dnsmasq[325]: query[A] discord.com from 10.0.100.13
Aug 10 08:50:02 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 08:50:49 dnsmasq[325]: query[A] discord.com from 10.0.107.17
Aug 10 08:50:49 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 09:26:33 dnsmasq[325]: query[A] discord.com from 10.0.105.7
Aug 10 09:26:33 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 09:27:07 dnsmasq[325]: query[A] discord.com from 10.0.105.7
Aug 10 09:27:07 dnsmasq[325]: regex blacklisted discord.com is 0.0.0.0
Aug 10 09:27:07 dnsmasq[325]: query[HTTPS] discord.com from 10.0.105.7
Aug 10 09:27:07 dnsmasq[325]: regex blacklisted discord.com is NODATA
piadmin@pihole01:~$