Multiple-Strategy Design of MOF-Derived N, P Co-Doped MoS₂ Electrocatalysts Toward Efficient Alkaline Hydrogen...

The multiple strategy design is crucial for enhancing the efficiency of nonprecious electrocatalysts in hydrogen evolution reaction (HER). In this work, we successfully synthesized N, P-codoped MoS₂ nanosheets as highly efficient catalysts by integrating doping effects and phase engineering using a porous metal-organic framework (MOF) template. The electrocatalysts exhibit excellent bifunctional activity and stability in alkaline media. The N, P codoping induces electron redistribution to enhance conductivity and promote the intrinsic activity of the electrocatalysts. It optimizes the H* adsorption free energy and the dissociative adsorption energy, resulting in significant enhancement of HER activity. Moreover, the porous MOF structure exposes a large number of electrochemically active sites and facilitates the diffusion of ions and gases, which improve charge transfer efficiency and structural stability. Specifically, at a current density of 10 mA cm^-2, the overpotential of the HER is only 32 mV, with a Tafel slope of 47 mV dec^-1 and Faradaic efficiency as high as 98.51% (at 100 mA cm^-2). Only a 338 mV overpotential is required to achieve a current density of 50 mA cm^-2 for oxygen evolution reaction (OER), and a potential of 1.49 V (at 10 mA cm^-2) is sufficient to drive overall water splitting. Further experimental measurements and first-principles calculations evidence that the exceptional performance is primarily attributed to the dual functionality of N and P dopants, which not only activate additional S sites but also initialize the phase transition of 2H to 1T-MoS₂ to facilitate the rapid charge transfer. Through in-depth exploration of the combined design of multiple strategies for efficient catalysts, our work paves a new way for the development of future efficient nonprecious metal catalysts.