When you freeze/cancel one of your Payouts.com cards, this will prevent any and all future transactions made on this card from going through.
However, if you have any card transactions in PENDING status when you freeze/cancel said card, you may still see these transactions go through. This is because a card transaction in PENDING has already been approved by Payouts.com and is now waiting for the merchant to authorize said payment, which they have 7 business days to do. If the merchant approves one of these transactions, it will go through even though your card has been deactivated, as the transaction no longer sits with Payouts.com.