Bulk CrCoNiFe alloy with high conductivity and density of grain boundaries for oxygen evolution reaction and urea oxidation reaction.

Multiple-principal-element alloys (MPEAs) with maximized configurational entropy show high catalytic activities for oxygen evolution reaction (OER) and urea oxidation reaction (UOR). However, the accurate relationship between their complex components (i.e., elements, phase structure, grain boundary density) and intrinsic catalytic activity is still unclear. Herein, a series of bulk MPEAs with face-centered cubic (FCC) phase structures were fabricated by the arc-melting method under an argon atmosphere. Compared to the CrCoNi and CrCoNiFeMn, the CrCoNiFe affords a higher UOR performance with the lowest overpotential of 331 mV at 10 mA·cm in 1 M KOH with 0.33 M urea, due to excellent conductivity and high density of grain boundaries. The urea electrolyzer using CrCoNiFe as anode and Pt as cathode shows a low voltage of 1.622 V at 10 mA cm and long-term stability of 60 h at 20 mA cm (4.08% decrease). These findings offer a facile strategy for designing bulk MPEAs electrodes for energy conversion.