I recently came across this post here:http://www.sciencemadness.org/talk/viewthread.php?tid=28467
The logic seems sound. H2 gas is bubbled over the cathode in a divded cell and hydride anions are formed. Those Hydride anions then react with the substrate to reduce and hydrogenate it. Simultaneously the substrate can be reduced at the cathode and react with gaeous H2 to become hydrogenated.
This is very interesting... and would have a lot of implications. The flow of electrons in the solution would balance out by natural push of the voltage in the electrochemical cell, thus creating an extremely reductive atmosphere in the catholyte.
If this works this could possibly have a great many industrial applications.
Apparently the usefulness of molecular H2 gas is based off this study in 2003 that found that toluene can be indirectly electrooxidized if molecular O2 bubbled over the cathode in an electrochemical cell with PTC CTAB and V5/V4 redox couple. The molecular O2 gas being the primary source of oxygen to oxidize toluene to form benzaldehyde. Here is the LINK