Dual hydrogen production from electrocatalytic water reduction coupled with formaldehyde oxidation via a copper-silver electrocatalyst.

The broad employment of water electrolysis for hydrogen (H 2 ) production is restricted by its large voltage requirement and low energy conversion efficiency because of the sluggish oxygen evolution reaction (OER). Herein, we report a strategy to replace OER with a thermodynamically more favorable reaction, the partial oxidation of formaldehyde to formate under alkaline conditions, using a Cu 3 Ag 7 electrocatalyst. Such a strategy not only produces more valuable anodic product than O 2 but also releases H 2 at the anode with a small voltage input. Density functional theory studies indicate the H 2 C(OH)O intermediate from formaldehyde hydration can be better stabilized on Cu 3 Ag 7 than on Cu or Ag, leading to a lower C-H cleavage barrier. A two-electrode electrolyzer employing an electrocatalyst of Cu 3 Ag 7 (+)||Ni 3 N/Ni(-) can produce H 2 at both anode and cathode simultaneously with an apparent 200% Faradaic efficiency, reaching a current density of 500 mA/cm 2 with a cell voltage of only 0.60 V.