Since Confluence is a collaborative tool just the users are able to change their own pictures.
What you as admin can do is reset a user password, access Confluence using the user credentials and then change the picture.
Another possibility is to change the default profile picture in the database, but in that case all the users will use the same picture:
UPDATE OS_PROPERTYENTRY SET string_val='/images/pathToTheNewImage/image.png' WHERE entity_key='confluence.user.profile.picture';
Hope it helps!
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