Our system is at -1V SCE/+1V in 3.5% neutral solution. We think this could be due to the geomentries of the electrode. In our case we use a cylindrical copper electrode as the working electrode.
It is the ovoervoltage on copper for the both reactions -- for hydrogen evolution reaction copper has high overvoltage
Copper is a mid way for the discharge of hydrogen. The best is platinum and Iridium. See on the volcano curve where you have the highest current exchange for hydrogen discharge connected to the force of the bond Me-H. In this link you can get a lot of information.
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422005000600023&lng=es&nrm=iso&tlng=es
In galvanic chemistry the resistence to hydrogen discharge is called overpotential. High overpotential of hydrogen means no or very little discharge of this gas; low means that the dicharge of hydrogen is competing with the plating of the metal (that is a problem in our case).
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