This option is available in Configuration details, Application settings tab, when you click a "..." icon to the right of the application.
By using the "Key code" field, you can assign a key to run the application.
This option mostly used on Android TV boxes using a remote control.
The list of key codes is available in the official Android documentation:
https://developer.android.com/reference/android/view/KeyEvent (click the KEYCODE_* link, and use the constant value in that field, for example, use 23 for KEYCODE_DPAD_CENTER).