The present invention is directed to novel membrane electrode assemblies, and devices and systems incorporating them. Representative membrane electrode assemblies comprise (a) a first, porous electrode; (b) a buffer layer optionally comprising an aqueous solution comprising a pH buffer; (c) a membrane; and (d) a second, porous electrode comprising a catalyst for the generation of oxygen (O2); wherein the membrane is interposed between the first electrode and the second electrode, and the buffer layer is interposed between the membrane and the first electrode.