Hi Paul,
If you have O365 subscription Encryption is available by default to encrypt messages in Outlook.com, however if it is a standard account you can use the existing Certificate if it supports the algorithm to encrypt messages. As not all Certificates are for encryption, when the certificates are issued they are via the templates for specific requirements such as Web server SSL, Domain Controllers LDAPS etc.
Check the article over here for detailed process - https://www.ablebits.com/office-addins-blog/email-encryption-outlook/
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