While i might get “killed” here 
From a network perspective @ricardo.gomes is correct.
But from an application and firewall perspective you are opening a “HUGE Can of Worms”.
To put it simple :
You have no (easy) way of controlling what interface the “answer would come out of”.
Ie. If a device send a Pi-Hole request to IF1 , and the network stack decides to send the answer out of IF2. The device would probably reject the answer as “Bad”, and ANY firewall it would pass would REJECT the package as “Out of state” - Well it’s UDP (stateless) , but the firewall would still block the package , originating from IF2.
I order to fix (policy route) that, you would have to do some iptables tagging of the package, and policy route based on those tags.
If you have ever tried that, you would already know why an “appliance” as TrueNas would not support (allow) such a configuration.
It would to put it nicely: Be very complicated for any supporter to debug and understand.
If you want a box capable of doing such trickery, you will have to look elsewhere.
I’m not buying your “2.5Gb” IF bandwidth as a solid argument for not using aliases. You could just switch to 10Gb.
But since you have 15yr of Network experience, it strikes me as strange that you dont just create another Vlan , and put your IF2 in there. Problem solved
Hint: Don’t just put an additional def-gw on IF2 … Then you’d open up another can of worms, that quite possible would affect TN operations too.
But with your experience you should know what to do. Provided TN even allows for an advanced (tagging/policy) routing setup.
Edit1: Seems like : ip rule is present on my TN
Edit2:
IMHO - TN isn’t VMware or Proxmox, and with the current restrictions would never even aspire be. I see it as a Solid NAS system “with a bit of extras”.
And I would prob. never use it for any mission critical appliances, like DNS/DNS-Filtering or the likes.