About SiO2 NPs gives the working electrode enhance the redox current peaks of ionic in electrolytes, but i think SiO2 in micro size can be protected the working electrode and make insulate layer in the solution.
the modified working electrode with MW SiO2 become insulate electrode because SiO2 insulate materials which isolated the electrode. The thickness of SiO2 can said multi wall of material on the surface of electrode (MWSiO2/AuE).
If you are using sio2 layer in electrolysis reaction for protecting gold, it will act as an insulator and protect it. Silica will not participate in the reaction.