Você precisa ajustar o parâmetro notify_classes para ser notificado sobre os e-mails rejeitados. Você pode adicionar o policy
para ser notificado sobre emails rejeitados por políticas. As opções são explicadas aqui:
notify_classes (default: resource, software)
The list of error classes that are reported to the postmaster. The default is to report only the most serious problems. The paranoid may wish to turn on the policy (UCE and mail relaying) and protocol error (broken mail software) reports.
NOTE: postmaster notifications may contain confidential information such as SASL passwords or message content. It is the system administrator's responsibility to treat such information with care.
The error classes are:
bounce (also implies 2bounce)
Send the postmaster copies of the headers of bounced mail, and send transcripts of SMTP sessions when Postfix rejects mail. The notification is sent to the address specified with the bounce_notice_recipient configuration parameter (default: postmaster).
2bounce
Send undeliverable bounced mail to the postmaster. The notification is sent to the address specified with the 2bounce_notice_recipient configuration parameter (default: postmaster).
data
Send the postmaster a transcript of the SMTP session with an error because a critical data file was unavailable. The notification is sent to the address specified with the error_notice_recipient configuration parameter (default: postmaster). This feature is available in Postfix 2.9 and later.
delay
Send the postmaster copies of the headers of delayed mail (see delay_warning_time). The notification is sent to the address specified with the delay_notice_recipient configuration parameter (default: postmaster).
policy
Send the postmaster a transcript of the SMTP session when a client request was rejected because of (UCE) policy. The notification is sent to the address specified with the error_notice_recipient configuration parameter (default: postmaster).
protocol
Send the postmaster a transcript of the SMTP session in case of client or > server protocol errors. The notification is sent to the address specified with the error_notice_recipient configuration parameter (default: postmaster).
resource
Inform the postmaster of mail not delivered due to resource problems. The > notification is sent to the address specified with the error_notice_recipient configuration parameter (default: postmaster).
software
Inform the postmaster of mail not delivered due to software problems. The > notification is sent to the address specified with the error_notice_recipient configuration parameter (default: postmaster).
Examples: notify_classes = bounce, delay, policy, protocol, resource, software notify_classes = 2bounce, resource, software