Dual Doping Induced Interfacial Engineering of Fe2N/Fe3N Hybrids with Favorable d‐Band towards Efficient Overall Water Splitting

Interfacial engineering and electronic modulation are some of the main components for enhancing the catalytic activity of electrocatalysts towards achieving efficient water splitting. Iron nitrides exhibit mediocre oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) due to their unsuitable d‐band energy level. In this work, we strongly boost the HER and OER catalytic performance of Fe2N for the first time by doping Co and Al, which could not only induce the formation of Fe2N/Fe3N hybrid interface but also tune the d‐band center position. The CoAl−Fe2N/Fe3N nanoparticles display HER and OER overpotential of 145 and 307 mV at 10 mA/cm2. XPS and DFT calculations confirm that tailoring the d‐band center position and interfacial engineering facilitates strong electronic interactions between Fe2N and Fe3N, synergistically optimize the electronic structure, which enriches H and H2O adsorption energy and oxygen‐containing intermediates. An alkaline electrolyzer based on CoAl−Fe2N/Fe3N requires an overall potential of 1.67 V at 10 mA/cm2, demonstrating the use of iron nitrides as a bifunctional electrocatalyst for water splitting activity. Electrocatalysis: Fe2N is endows with enhanced HER and OER catalytic activities not only by tuning the d‐band center positions but also formation of Fe2N/Fe3N interface as a result of dual doping with Co and Al. The dual‐doped Fe2N/Fe3N display HER and OER overpotential of 145 and 307 mV at 10 mA/cm2 and significantly better than Fe2N (461 and 451 mV) and individual Co‐ and Al‐doped Fe nitride catalysts.