Abstract

Combining the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) within an integrated electrolytic system may offer the advantages of enhanced kinetics of the anode, reduced energy consumption, and the production of high-purity hydrogen. Herein, it is reported the construction of Ni─MoN nanorod arrays supported on a nickel foam substrate (Ni─MoN/NF) as a bifunctional electrocatalyst for electrocatalytic hydrogen production and selective methanol oxidation to formate. Remarkably, The optimal Ni─MoN/NF catalyst displays exceptional HER performance with an overpotential of only 49mV to attain 10mAcm-2 in acid, and exhibits a high activity for MOR to achieve 100mAcm-2 at 1.48V in alkali. A hybrid acid/base electrolytic cell with Ni─MoN/NF electrode as anode and cathode is further developed for an integrated HER-MOR cell, which only requires a voltage of 0.56V at 10mAcm-2 , significantly lower than that of the HER-OER system (0.70V). The density functional theory studies reveal that the incorporation of Ni effectively modulates the electronic structure of MoN, thereby resulting in enhanced catalytic activity. The unique combination of high electrocatalytic activity and excellent stability make the Ni─MoN/NF catalyst a promising candidate for practical applications in electrocatalytic hydrogen production and methanol oxidation.

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