All DNS traffic will be sent to the main node. The satellite node also sends DNS to the main node.
To use your pi-hole, you need to change the DNS on the main node. If you enabled Access Control, then the DNS settings specified in the profiles is used. Unless DNS is set to “System Default”, then system level DNS is used (i.e., DNS under the Internet Settings page).
If Access Control is not enabled, the DNS defined in the Internet Settings page is used. By default, it’s your ISP DNS servers. You can override that by checking the “Use custom DNS servers” box and entering your own IP addresses.