You can set a hotkey for almost any function in OBS Studio. While this is said, it is not suggested that you bind "start stream" or "stop stream" as you could accidentally go live.
If you'd like to use hotkeys, simply left click in the box to the right of the type of hotkey you'd like and enter in the key you will be using to use the hotkey.
Be sure to click the "Apply" button at the bottom to ensure that your settings have saved