Keplerate polyoxomolybdate nanoball mediated controllable preparation of metal-doped molybdenum disulfide for electrocatalytic hydrogen evolution in acidic and alkaline media

Rationally designed novel cost-effective hydrogen evolution reaction (HER) electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance. Polyoxometalates (POMs) with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts. Herein, a series of transition metal-doped MoS2 materials with different surface engineered structures (Fe, Cr, V doping and S vacancies) (M-MoS2/CC, M = Fe, Cr and V) were fabricated by a simple hydrothermal-vulcanization strategy using Keplerate polyoxomolybdate nanoball ({Mo72Fe30}, {Mo72Cr30}, {Mo72V30}, {Mo132}) as precursors. The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS2/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media. The optimized Fe-MoS2/CC afford current densities of 10 and 50 mA/cm2 at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H2SO4 and 1.0 mol/L KOH aqueous solution, respectively, outperforming most of reported typical transition metal sulfide-based catalysts. This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.