Rational Construction of 3D Self‐Supported MOF‐Derived Cobalt Phosphide‐Based Hollow Nanowall Arrays for Efficient Overall Water Splitting At large Current Density

Abstract Developing efficient nonprecious bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) in the same electrolyte with a low overpotential and large current density presents an appealing yet challenging goal for large‐scale water electrolysis. Herein, a unique 3D self‐branched hierarchical nanostructure composed of ultra‐small cobalt phosphide (CoP) nanoparticles embedded into N, P‐codoped carbon nanotubes knitted hollow nanowall arrays (CoPʘNPCNTs HNWAs) on carbon textiles (CTs) through a carbonization‐phosphatization process is presented. Benefiting from the uniform protrusion distributions of CoP nanoparticles, the optimum CoPʘNPCNTs HNWAs composites with high abundant porosity exhibit superior electrocatalytic activity and excellent stability for OER in alkaline conditions, as well as for HER in both acidic and alkaline electrolytes, even under large current densities. Furthermore, the assembled CoPʘNPCNTs/CTs||CoPʘNPCNTs/CTs electrolyzer demonstrates exceptional performance, requiring an ultralow cell voltage of 1.50 V to deliver the current density of 10 mA cm −2 for overall water splitting (OWS) with favorable stability, even achieving a large current density of 200 mA cm −2 at a low cell voltage of 1.78 V. Density functional theory (DFT) calculation further reveals that all the C atoms between N and P atoms in CoPʘNPCNTs/CTs act as the most efficient active sites, significantly enhancing the electrocatalytic properties. This strategy, utilizing 2D MOF arrays as a structural and compositional material to create multifunctional composites/hybrids, opens new avenues for the exploration of highly efficient and robust non‐noble‐metal catalysts for energy‐conversion reactions.