Hierarchical MoS2@NiFeCo‐Mo(doped)‐Layered Double Hydroxide Heterostructures as Efficient Alkaline Water Splitting (Photo)Electro‐catalysts

Abstract Designing cost‐effective electrocatalysts with fast reaction kinetics and high stability is an outstanding challenge in green hydrogen generation through overall water splitting (OWS). Layered double hydroxide (LDH) heterostructure materials are promising candidates to catalyze both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), the two OWS half‐cell reactions. This work develops a facile hydrothermal route to synthesiz hierarchical heterostructure MoS 2 @NiFeCo‐LDH and MoS 2 @NiFeCo‐Mo(doped)‐LDH electrocatalysts, which exhibit extremely good OER and HER performance as witnessed by their low IR‐corrected overpotentials of 156 and 61 mV with at a current density of 10 mA cm −2 under light assistance. The MoS 2 @NiFeCo‐Mo(doped)‐LDH‐MoS 2 @NiFeCo‐LDH OWS cell achieves a low cell voltage of 1.46V at 10 mA cm −2 during light‐assisted water electrolysis. Both materials exhibited exceptional stability under industrially relevant HER and OER conditions, maintaining a current density of 1 A cm −2 with minimal alterations in their potential and performance. The experimental and computational results demonstrate that doping the LDH matrix with high‐valence Mo atoms and MoS 2 quantum dots improves the electrocatalytic activity by 1) enhancing electron transfer, 2) making the electrocatalyst metallic, 3) increasing the number of active sites, 4) lowering the thermodynamic overpotential, and 5) changing the OER mechanism. Overall, this work develops a facile synthesis method to design highly active and stable MoS 2 @NiFeCo‐Mo(doped)‐LDH heterostructure electrocatalysts.