I don't know how to make it 'blackhole' as you say, but I think what you are looking for is for postfix to REJECT (550 - unknown user). If you are in a shared environment, co-lo, etc, the default postfix in Zimbra will accept emails from any IP in your subnet and then bounce for unknown users rather than reject. Bouncing is bad for a number of reasons: see this thread for discussion:
Postfix - how to make zimbra respond 550 unknown user rather than bounce?
To fix this, you need to change the default postfix mynetworks_style from subnet to host.
See bug here for fix:
http://bugzilla.zimbra.com/show_bug.cgi?id=12724
Please consider voting for the bug also if it makes sense to you.