Phosphorous Vacancy and Built‐In Electric Field Effect of Co‐Doped MoP@MXene Heterostructures to Tune Catalytic Activity for Efficient Overall Water Splitting

Developing cost-effective, durable bifunctional electrocatalysts is crucial but remains challenging due to slow hydrogen/oxygen evolution reaction (HER/OER) kinetics in water electrolysis. Herein, a combined engineering strategy of phosphorous vacancy (V_p) and spontaneous built-in electric field (BIEF) is proposed to design novel highly-conductive Co-doped MoP@MXene heterostructures with phosphorous vacancy (V_p-Co-MoP@MXene). Wherein, Co doping regulates the surface electronic structure and charge re-distribution of MoP, V_p induces more defects and active sites, while BIEF accelerates the interfacial charge transfer rate between V_p-Co-MoP and MXene. Therefore, the synergistic integration of V_p-Co-MoP/MXene efficiently decreases activation energy and kinetic barrier, thus promoting its intrinsically catalytic activity and structural stability. Consequently, the V_p-Co-MoP@MXene catalyst displays low overpotentials of 102.3/196.5 and 265.0/320.0 mV at 10/50 mA cm^-2 for HER and OER, respectively. Notably, two-electrode electrolyzers with the V_p-Co-MoP@MXene bifunctional catalysts to achieve 10/50 mA cm^-2, only need low-cell voltages of 1.57/1.64 V in alkaline media. Besides, experimental and theoretical results confirm that the hetero-structure effectively reduces hydrogen adsorption free energy and rate-determining-step energy barrier of OER intermediates, thereby greatly boosting its intrinsically catalytic activity. This work verifies an effective strategy to fabricate efficient non-precious bifunctional electro-catalysts for water splitting via combination engineering of phosphorous vacancy, cation doping, and BIEF.