A Low-Temperature Synthetic Route Toward a High-Entropy 2D Hexernary Transition Metal Dichalcogenide for Hydrogen Evolution Electrocatalysis

一种用于析氢电催化的高熵二维六元过渡金属二硫化物低温合成路线

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Abstract

High-entropy (HE) metal chalcogenides are a class of materials that have great potential in applications such as thermoelectrics and electrocatalysis. Layered 2D transition-metal dichalcogenides (TMDCs) are a sub-class of high entropy metal chalcogenides that have received little attention to date as their preparation currently involves complicated, energy-intensive, or hazardous synthetic steps. To address this, a low-temperature (500 °C) and rapid (1 h) single source precursor approach is successfully adopted to synthesize the hexernary high-entropy metal disulfide (MoWReMnCr)S(2) . (MoWReMnCr)S(2) powders are characterized by powder X-ray diffraction (pXRD) and Raman spectroscopy, which confirmed that the material is comprised predominantly of a hexagonal phase. The surface oxidation states and elemental compositions are studied by X-ray photoelectron spectroscopy (XPS) whilst the bulk morphology and elemental stoichiometry with spatial distribution is determined by scanning electron microscopy (SEM) with elemental mapping information acquired from energy-dispersive X-ray (EDX) spectroscopy. The bulk, layered material is subsequently exfoliated to ultra-thin, several-layer 2D nanosheets by liquid-phase exfoliation (LPE). The resulting few-layer HE (MoWReMnCr)S(2) nanosheets are found to contain a homogeneous elemental distribution of metals at the nanoscale by high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) with EDX mapping. Finally, (MoWReMnCr)S(2) is demonstrated as a hydrogen evolution electrocatalyst and compared to 2H-MoS(2) synthesized using the molecular precursor approach. (MoWReMnCr)S(2) with 20% w/w of high-conductivity carbon black displays a low overpotential of 229 mV in 0.5 M  H(2) SO(4) to reach a current density of 10 mA cm(-2) , which is much lower than the overpotential of 362 mV for MoS(2) . From density functional theory calculations, it is hypothesised that the enhanced catalytic activity is due to activation of the basal plane upon incorporation of other elements into the 2H-MoS(2) structure, in particular, the first row TMs Cr and Mn.

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