Electrocatalysis of Furfural Oxidation Coupled with H₂ Evolution via Nickel‐Based Electrocatalysts in Water

Abstract Electrocatalytic water splitting has been widely considered as a promising approach to produce clean H₂. The anodic half reaction of water splitting, the O₂ evolution reaction (OER), is the kinetic bottleneck of the overall process and its product O₂ is not of high value. Herein, we report a novel strategy to replace OER with a thermodynamically more favorable anodic reaction, furfural oxidation to 2‐furoic acid. Furfural is one of the dehydration products of biomass and its oxidation product 2‐furoic acid has many industrial applications. A bifunctional electrocatalyst of Ni₂P‐derived arrays on nickel foam (Ni₂P/Ni/NF) was developed for the integrated electrocatalysis of both furfural oxidation and H₂ production. When Ni₂P/Ni/NF acts as the electrocatalyst for both anode and cathode, nearly 100 % Faradaic efficiencies for H₂ evolution and furfural oxidation were obtained. Such an integrated electrolysis catalyzed by Ni₂P/Ni/NF required an applied voltage ≈110 mV smaller than that of pure water splitting to achieve the current density of 10 mA cm⁻², together with robust stability. Overall, our novel electrolyzer produced valuable products at both electrodes (H₂ at cathode and 2‐furoic acid at anode) and may extend to the coupling of H₂ evolution with many other valuable organic oxidation reactions.