Multifunctional molybdenum-tuning porous nickel-cobalt bimetallic phosphide nanoarrays for efficient water splitting and energy-saving hydrogen production

Abstract

The sluggish kinetics of the hydrogen evolution reaction (HER) and substantial barriers in the oxygen evolution reaction (OER) significantly impede its application in hydrogen production. To address this issue and enhance energy efficiency in hydrogen generation, we explored a high-activity alkaline HER catalyst while concurrently coupling it with the urea oxidation reaction (UOR). In this work, we designed and synthesized porous molybdenum (Mo)-modulated nickel-cobalt bimetallic phosphide nanoarrays (M0.3NCP@NF). This multifunctional self-supported electrocatalyst demonstrates superior performance in HER, OER, and UOR. The introduction of Mo, in the form of CoMoO4 nanoparticles, promotes interfacial electron transfer to reduce the electron density around the cations in phosphides, enhancing the kinetics and intrinsic activity. Furthermore, the morphological changes induced by Mo accelerate both electron and mass transfer processes. Density functional theory and operando electrochemical impedance spectroscopy indicate that Mo introduction optimizes the interaction with HER intermediate H*, facilitating the conversion to a high-valent active intermediate for OER and accelerating UOR kinetics. Benefiting from dual optimization of morphology and structure, the as-prepared M0.3NCP@NF electrocatalyst demonstrates outstanding HER, OER, and UOR performances. Notably, a full urea electrolysis device powered by M0.3NCP@NF operates with a cell voltage of only 1.53 V to achieve a current density of 100 mA cm−2. which is 240 mV lower than that of conventional water electrolysis, demonstrating the competitive potential of our approach for efficient and energy-saving hydrogen production, along with simultaneous urea wastewater remediation.