Ultrastable and highly active Co-vacancies-enriched IrCo bifunctional nanoalloys for proton exchange membrane water electrolysis.

[Display omitted] • IrCo 0.13 nanoalloy is prepared by chemical reduction and electrochemical treatment. • Abundant Co vacancies and atomic heterostructure facilitate OER and HER. • Strong interaction of Ir and Co contributes to remarkable stability and activity. • IrCo 0.13 exhibits an overpotential of 238 (OER) and 18.6 mV (HER)@10 mA cm−2, respectively. • Bifunctional IrCo 0.13 as both anode and cathode displays 1.68 V@1 A cm−2 in PEMWE. Exploring the electrocatalysts with high intrinsic activity and stability for both anode and cathode to tolerate the extremely acidic condition in proton exchange membrane water electrolyzer (PEMWE) is crucial for widespread industrial application. Herein, we constructed the bifunctional IrCo x nanoalloys with abundant metal vacancies via the combination of chemical reduction and electrochemical treatment for overall water splitting. The developed IrCo 0.13 exhibits ultra-low overpotentials of 238 mV for OER and 18.6 mV for HER at 10 mA cm−2 in 0.1 M HClO 4 , and achieves the exceptional stability of 1000 h for OER and 100 h for HER at 10 mA cm−2. Further, the cell voltage is only 1.68 V to reach a high current density of 1 A cm−2 in PEMWE with IrCo 0.13 as the both cathode and anode catalytic layer, and it shows excellent corrosion resistance in acidic environment, evidenced by 415 h stable operation at 1 A cm−2. The strong electronic interactions in the Ir-Co atomic heterostructure and the in-situ generation of Co vacancies by electrochemical oxidation synergistically contribute to the enhanced activity and stability via optimizing the electronic structure of adjacent Ir active sites, enhancing the conductivity and electrochemical active surface area of the catalyst, accelerating charge transfer and kinetics. This work provides a new perspective for designing bifunctional catalysts for practical application in PEMWE. [ABSTRACT FROM AUTHOR]