Yes you will need to remove the wheel first. Go buy yourself a wire brush like this: Trojan 4x15 Row Brass Wire Brush - Bunnings Australia
You can also get wire brushes that attach to your drill. Once you have cleaned the rust off the hubs, then clean it up with some brake clean to remove any dust and any oils etc and then give it a spray paint with either silver or black (or whatever colour you desire) to stop the rust coming back.
I always paint the hubs on my cars because the rust looks horrible. Refer the pics below of the process on my car:
Before:
After using wire brush:
After a coat of satin black paint:
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