Hello, thats my second day with ipfire. I never have used a firewall or anything like it. I have somehow managed to install ipfire and blocked tor. I have set up DNS (cleanbrowsing). But somehow I dont know what rules I have to put in to block Psiphone. I can connect without any trouble.
first, make sure the default policy of your firewall is to drop anything that was not explicitly allowed before. This is more secure and easier to maintain than blocking everything unwanted one by one.
Second, blocking Tor is impossible. You are able to block known Tor relays (some IPS rulesets come with corresponding categories), but users might just use Tor bridges instead, which are designed for circumventing censorship.
Since I have no experience on Psiphone, I am unable to help you with this.