Modular Solar-to-Fuel Electrolysis at Low Cell Potentials Enabled by Glycerol Electrooxidation and a Bipolar Membrane Separator.

Solar fuel generation through water electrolysis or electrochemical CO 2 reduction is thermodynamically limited when it is paired with oxygen evolution reaction (OER). Glycerol electrooxidation reaction (GEOR) is an alternative anodic reaction with lower anodic electrochemical potential that utilizes a renewable coproduct produced during biodiesel synthesis. We show that GEOR on an Au-Pt-Bi ternary metal electrocatalyst in a model alkaline crude glycerol solution can provide significant cell potential reductions even when paired to reduction reactions in seawater and acidic catholytes via a bipolar membrane (BPM). We showed that the combination of GEOR and a BPM separator lowers the total cell potential by 1 V at an electrolysis current of 10.0 mA cm -2 versus an anode performing anode's OER when paired with hydrogen evolution and CO 2 reduction cathodes. The observed voltage reduction was steady for periods of up to 80 h, with minimal glycerol crossover observed through the membrane. These results motivate new, high-performance cell designs for photoelectrochemical solar fuel integrated systems based on glycerol electrooxidation.