Are you using SendMail or SMTP? If the latter, your email service might have caps. If you are doing it all on the server, check your admin settings.
Oh, I thought you were talking about XF admin.Do you use a control panel, such as cPanel or Plesk? Settings may be found there.
Options --> E-Mail Options
Default will be using sendmail, or SMTP will be configured separately.
But that's not where email caps would be set.
But is it active for your forum mail? If you're not certain what to do, ask your host about the proper settings. It may be easier than to go into Plesk, which is not my personal cup of tea or realm of expertise.
Do any e-mails get sent from the forum? I'd have thought that if it's set to default, then it will be using sendmail via php on the server to send the mails. I have mine set up to send via SMTP, which if you were using google to send the mails, this would need to be set via the ACP?
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