Yes, you can use ScreenTime rules to block a device from your network by making that rule 24/7. To do so, just choose each day of the week and set the time of the rule from 12:00 AM to 12:00 AM. The device must have been connected to the Starry Station network previously in order to add it from your device list.
Starry Station: Can I Permanently Block a Device From My Network?
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