Deciphering the Electrocatalytic Potential of Ni‐Metal–Organic Framework: A Synergistic Approach to Electrocatalysis and Theoretical Analysis

Abstract Hydrogen stands at the forefront of next‐generation clean energy solutions. Specifically, electrochemical water splitting represents a cutting‐edge, environmentally benign approach for sustainable green hydrogen generation. The development of next‐generation highly efficient electrocatalysts with high efficiency and durability is pivotal to overcome the intrinsic kinetic limitations of both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Contextually, metal–organic frameworks (MOFs), owing to their ultrahigh surface area, tuneable nanostructures, and exceptional porosity, have emerged as a versatile class of materials for designing advanced bifunctional electrocatalysts. Herein, a nickel‐metal complex ( NMC ) and a nickel‐metal–organic framework ( NMF ) was rationally synthesized. Electrochemical analyses revealed that the NMF exhibited superior bifunctional activity, with low overpotentials of 144 mV for HER and 347 mV for OER at the current density of 10 mA cm −2 in alkaline media. Remarkably, the NMF || NMF catalyst delivered a low overall water splitting cell voltage of 1.647 V at 10 mA cm −2 , along with outstanding long‐term stability. Comprehensive experimental and in silico insights confirm that NMF dramatically lowers the energy barrier for hydrogen adsorption. These findings highlight the NMF as a state‐of‐the‐art electrocatalyst, underscoring its potential to enable next‐generation, advanced water electrolysis techniques for green hydrogen production.