First remove an existing key binding with:
xfconf-query --reset \
--channel xfce4-keyboard-shortcuts \
--property /commands/custom/'<Super>f'
Then add yours:
xfconf-query --create \
--channel xfce4-keyboard-shortcuts \
--property /commands/custom/'<Super>f' \
--type string \
--set 'exo-open --launch FileManager'
Customize these commands, and add them to any automation scripts you have!
Note: If you want to bind
<Ctrl>you have to call it<Primary>for some odd reason!