Your question has a broad scope, in the way you posed it. Therefore, a clear answer might be elusive at this stage. Are you working with a molecular analyte dissolved in the electrolyte solution or a material/molecule immobilized on the electrode surface itself? Answering this first point can surely lead to more detailed further answers.
I am using 1 M KOH electrolyte to electrochemically characterize binary metal sulfide on nickel foam electrode in three electrode assembly. The counter and reference electrodes are plantinum wire and Hg/HgO.