Porous Plate-like MoP Assembly as an Efficient pH-Universal Hydrogen Evolution Electrocatalyst.

Abstract

Molybdenum phosphide is one of the most potential electrocatalysts for the hydrogen evolution reaction (HER), whereas it is still challenging to achieve an efficient molybdenum phosphide-based catalyst that performs well over a wide pH range. Herein, a porous nanoplate composed of small MoP flakes confined in thin N, P, S-triple-doped carbon (MoP@NPSC) was prepared by the assembly of phosphomolybdic acid (H3PMo12O40·nH2O, {PMo12}) and egg white, followed by phosphorization. Given its small size (ca. 1 nm) in favor of deriving small particles and the oxygen-rich surface with strong coordination ability, the {PMo12} cluster was selected to combine with egg white to obtain a lamellar hybrid precursor via a hydrogen bond. Through controllable phosphating, a nanoplate organized by interconnected MoP particles was generated, accompanied by the in situ formation of the N, P, S-doped carbon thin layer and pores from the pyrolysis of egg white. The plentiful pores, thin carbon coating, and multielement doping bring about promoted electrolyte/bubble diffusion, enhanced conductivity and stability, and lowered adsorption energy of hydrogen/hydroxyl, respectively. All of the above merits endow MoP@NPSC with prominent activity with low overpotentials of 50, 76, and 71 mV at 10 mA cm-2 toward the HER in alkaline, neutral, and acid media, respectively, and nearly no attenuation after 40 h of testing. Especially, compared with commercial Pt/C, MoP@NPSC exhibits similar low onset potential and even better at large current density in 1 M KOH. The electrolyzer equipped with the MoP@NPSC cathode and the NiFe-LDH anode requires only 1.52 V to deliver 10 mA cm-2 and can be powered by a solar cell (1.524 V) charged by sunlight.