Pretty much this. I'm a bit stuck on getting a decent bake my first time and want to clear the slate and start fresh. 
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Kevin Alexander James Nugent
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The 0 next to the material indicates it has no users, aka an orphan. Putting the outliner in "Orphan Data" mode and hitting the purge button will remove all but Material.003 – batFINGER Dec 15 '19 at 03:34
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https://blender.stackexchange.com/questions/5300/how-can-i-remove-all-unused-materials-from-a-blend-file – batFINGER Dec 16 '19 at 13:01
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I don't think that there is a way to clear this list without a script. If you don't want to use a script, save your objects individually, and re-load the Blender start-up file. Then import your objects, and make new shaders.
Nate_Sycro27
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Select the material you want to remove and press the little X to the right of it
Halloweenharen
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