You are right - Pihole is running in a Docker container and attached to the host network. The host is a LXC container which is hosted by PVE. This LXC container has a vlan interface for each subnet. Meaning Pihole is connected to each vlan interface (see the ss -tulpn below). The device with the mac is in vlan 220 (i.e. 192.168.220.0/24).
Anything specific I need to (double)check here?
ss -tulpn | grep 53
udp UNCONN 0 0 127.0.0.1:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=42))
udp UNCONN 0 0 192.168.10.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=40))
udp UNCONN 0 0 192.168.240.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=38))
udp UNCONN 0 0 192.168.210.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=36))
udp UNCONN 0 0 192.168.110.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=34))
udp UNCONN 0 0 192.168.100.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=32))
udp UNCONN 0 0 192.168.120.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=30))
udp UNCONN 0 0 192.168.220.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=28))
udp UNCONN 0 0 192.168.200.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=26))
udp UNCONN 0 0 192.168.230.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=24))
udp UNCONN 0 0 172.20.235.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=22))
tcp LISTEN 0 32 192.168.100.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=33))
tcp LISTEN 0 32 192.168.110.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=35))
tcp LISTEN 0 32 192.168.200.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=27))
tcp LISTEN 0 32 192.168.210.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=37))
tcp LISTEN 0 32 192.168.240.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=39))
tcp LISTEN 0 200 192.168.10.235:88 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=53))
tcp LISTEN 0 32 192.168.10.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=41))
tcp LISTEN 0 32 127.0.0.1:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=43))
tcp LISTEN 0 32 192.168.220.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=29))
tcp LISTEN 0 32 172.20.235.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=23))
tcp LISTEN 0 32 192.168.230.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=25))
tcp LISTEN 0 32 192.168.120.235:53 0.0.0.0:* users:(("pihole-FTL",pid=291070,fd=31))