HomeKit Hub
Have more than one Apple TV. How do I specify which one Home connects to as the home hub?
Apple TV 4K, tvOS 16
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A really interesting question, which I've never considered myself.
Setting of the hub is automatic. If you have multiple HomeKit hubs they will work together in your network but only one acts as the hub, while the other devices are on 'standby'. You can see this in iOS 16 if you touch on the ... menu option at the top right of the Home app screen.
Then choose Home Settings. At the foot of the next page you will see the label Home Hubs & Bridges. Touch on that and then you will see the list of the devices in your network which are capable of being a hub. Note that only one is listed as 'Connected'. All others will be set to 'Standby'. There is no option for changing this status and there doesn't need to be. Should your 'Connected' hub device fall off the twig one of the others will be summoned into action to act as the hub.
I have two HomePods and an Apple TV; all can be a hub. The first acquired of these devices is labelled as my hub. I assume that is because it was the first one to act as the hub and when the others were activated on my network iOS told them to wait on standby - rather like a theatre understudy - because there already was a hub on the network, and that would only change if my first HomePod was removed from the Home app.
However, this might or might not change if you tried to force a change in such a way. I've never noticed an automatic change of hubs in Home, although it might happen from time to time. I'm not about to test it. Feel free to report back if you want to experiment.