Electrochemical systems and methods for producing hydrogen. Generally, the systems and methods involve providing an electrochemical cell that includes an anolyte compartment holding an anode in contact with an anolyte, wherein the anolyte includes an oxidizable substance having a higher standard oxidation potential than water. The cell further comprises a catholyte compartment holding a cathode in contact with a catholyte that includes a substance that reduces to form hydrogen. Additionally, the cell includes an alkali cation conductive membrane that separates the anolyte compartment from the catholyte compartment. As an electrical potential passes between the anode and cathode, the reducible substance reduces to form hydrogen and the oxidizable substance oxidizes to form an oxidized product. The pH within the catholyte compartment may be controlled and maintained to a value in the range of 6 to 8. Apparatus and methods to regenerate the oxidizable substance are disclosed.