Rational Manipulation of Active CNT Encapsulated Fe Doped NiCoP Nanoparticles In Situ Grown in Hierarchically Carbonized Wood for High‐Current‐Density Water Splitting

Abstract Precise morphology design and electronic structure regulation are critically significant to promote catalytic activity and stability for electrochemical hydrogen production at high current density. Herein, the carbon nanotube (CNT) encapsulated Fe‐doped NiCoP nanoparticles is in‐situ grown in hierarchical carbonized wood (NCF 0.5 P@CNT/CW) for water splitting. Coupling merits of porous carbonized wood (CW) substrate, CNT encapsulating and Fe doping, the NCF 0.5 P@CNT/CW features remarkable and durable electrocatalytic activity. The overpotentials of NCF 0.5 P@CNT/CW at 50 mA cm −2 mV and 205 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) and features high current density of 800 mA cm −2 within 300 mV for both OER and HER. Moreover, NCF 0.5 P@CNT/CW displays outstanding overall water splitting performance (η 50 = 1.62 V and η 100 = 1.67 V), outperforming Pt/C║RuO 2 (η 50 = 1.74 V), and can achieve the current density of 700 mA cm −2 at a lower cell voltage of 1.78 V. Overpotential is only 4.0 % decay after 120 h measurement at 50 mA cm −2 . Density functional theory (DFT) calculations reveals Fe doping optimizes the binding energy and Gibbs free energy of intermediates, and regulates d‐band center of NCF 0.5 P@CNT/CW. Such synergistic strategy of morphology manipulation and electronic structure optimization provides a spark for developing effective and robust bifunctional catalysts.