Electrocatalytic water splitting has been widely recognized as a promising approach in producing clean H2. However, its broad employment is restricted by the large voltage requirement and low energy conversion efficiency because of the sluggish anodic O2 evolution reaction, whose product O2 is not of significant value. Hence, it’s highly appealing to explore other thermodynamically more favorable reactions to replace OER at the anode. We demonstrate that the low-potential oxidation of formaldehyde to formate is a feasible reaction with extremely small oxidation potential. More importantly, H2 can also be produced at the anode. By taking advantage of the excellent hydrogen adsorption into and permeation through palladium membrane electrodes, we further demonstrate that it is feasible to perform electrocatalytic dual hydrogenation of organics when another palladium membrane is also adopted as the cathode. Such a design enables electrocatalytic hydrogenation of the same substrate at both anode and cathode in two separated chambers spatially isolated from the electrochemical cell with a theoretical maximum Faradaic efficiency of 200%.

Low-potential oxidation of formaldehyde enables hydrogen evolution and hydrogenation at the anode

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