Keyboard Maestro is the only app I know of that can do this, but it’s not the way I’d do it.
If you launch the app and the drive isn’t mounted, Photos won’t see the drive immediately and will probably complain or create a new photoslibrary on your internal drive.
Instead I’d do it the other way: have mounting the drive trigger the Photos.app to launch.
You could do that with launchd or keyboard Maestro.
Keyboard Maestro is a worthy investment for any Mac power user. There are dozens of things you can find to do with it once you have.
You could also use it to unmount the drive when Photos quits.
Using Mountain is a 2-second step of clicking on the menubar and selecting an unmounted volume. I’d just continue to do it manually.
And no, there’s no reason not to always have it connected to a desktop machine.
(For backup drives it’s a different story for me; I prefer to disconnect at least one set of backup drives to prevent electrical spikes - something that happened once and destroyed my connected drives during a blackout.)
I have been using Keyboard Maestro to automatically mount my Synology volumes when my Macbook Pro is connected to my wireless LAN (= when I am at home). It works like a charme.
Gabe Weatherhead published an awesome blog post back in 2012. It still works to this day: