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 MoS_(2)materials with different surface engineered structures(Fe,Cr,V doping and S vacancies)(M-MoS_(2)/CC,M=Fe,Cr and V)were fabricated by a simple hydrothermalvulcanization strategy using Keplerate polyoxomolybdate nanoball({Mo_(72)Fe_(30)},{Mo_(72)Cr_(30)},{Mo_(72)V_(30)},{Mo_(132)})as precursors.The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS_(2)/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media.The optimized Fe-MoS_(2)/CC afford current densities of 10 and 50 mA/cm^(2)at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H_(2)SO_(4)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.