Where are you trying to highlight the skill or potion with the mouse cursor? You need to do so in the icon bar that pops up when you click on either the skill or potion button in the interface at the bottom of the screen, and then hit a function key. For example, if you open the potion bar and highlight the icon for minor restoration potions, then hit F1, there should be an 'F1' shown in the corner of the icon, and after that hitting F1 will use a minor restoration potion (as long as there is one in your inventory).

Once you have that working, you can get more elaborate, if you wish;
Tutorial-Changing F1-F12 hotkeys to different keys


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