[spidermclovin]

I've been trying to get a desulfurization reaction to work under a reductive potential (E= -1.0 V) with NaCl as the electrolyte.
After 24 hours, there are large pH changes from pH 7.2 to pH 10/11. I have tried using PBS buffer but this doesnt seem to help.
Any ideas?   

[chenbeier]

During electrolysis of NaCl solution you create on cathode side hydrogen and NaOH. Buffers are useless in this case. On anode side depending on the electrode material chlorine and/ or corrosion of electrode.

[spidermclovin]

How do you avoid this, use a less reductive potential?
Or a different electrolyte? 
I'm using carbon electrodes. 

[chenbeier]

Only acid or a metal salt, would work. Acid only develop hydrogen, metal salt like coppersulfate would give metal precipitation on the cathode.

[kriggy]

Can you try different electrolyte?  I recall Baran group among others having some papers about synthetic electrochemistry so you might want to look in there to see what electrolytes they are using.