Heterostructured MoO3 Anchored Defect‐Rich NiFe‐LDH/NF as a Robust Self‐Supporting Electrocatalyst for Overall Water Splitting

Abstract The rational design of inexpensive metal electrocatalysts with exciting catalytic activity for overall water splitting (OWS) remains a significant challenge. Heterostructures of NiFe layered double hydroxides (NiFe‐LDHs) with abundant oxygen defects and tunable electronic properties have garnered considerable attention. Here, a self‐supporting heterostructured catalyst (named MoO 3 /NiFe‐NF) is synthesized via a hydrothermal method to grow NiFe‐LDH with oxygen vacancies (O V ) in situ on inexpensive nickel foam (NF). Subsequently, MoO 3 is anchored and grown on the surface of NiFe‐LDH by electrodeposition. The obtained catalysts achieved outstanding oxygen/hydrogen evolution reaction (OER/HER, 212 mV/85 mV@10 mA cm −2 ) performance in 1 m KOH. Additionally, when MoO 3 /NiFe‐NF is utilized as the cathode and anode in OWS, a current density of 10 mA cm −2 can be obtained as an ultralow battery voltage of 1.43 V, a significantly lower value compared to the commercial electrolyzer incorporating Pt/C and IrO 2 electrode materials. Finally, density functional theory (DFT) calculations and advanced spectroscopy technology are conducted to reveal the effects of heterojunctions and O V on the internal electronic structure of the electrical catalysts. Mainly, the present study provides a novel tactic for the rational design of remarkable, low‐cost NiFe‐LDH electrocatalysts with heterostructures for OWS.