heroku config:set just sets an environment variable on heroku.
There is no default value for S3_BUCKET_NAME. So, if you have overwritten a previous value and want to get back to it, you will have to find from some other source what was the value and set it using heroku config:set
If you want to remove current environmental variable (undo your command), you need to do
heroku config:unset S3_BUCKET_NAME