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

• Published in: Advanced science 2023-05, Vol.10 (14), p.e2204488-n/a
• Main Authors: Qu, Jie, Elgendy, Amr, Cai, Rongsheng, Buckingham, Mark A., Papaderakis, Athanasios A., Latour, Hugo, Hazeldine, Kerry, Whitehead, George F. S., Alam, Firoz, Smith, Charles T., Binks, David J., Walton, Alex, Skelton, Jonathan M., Dryfe, Robert A. W., Haigh, Sarah J., Lewis, David J.
• Format: Article
• Language: English
• Subjects: 2D material; Decomposition; Electrocatalysis; Fluorides; Graphene; high‐entropy disulfide; hydrogen evolution reaction electrocatalysis; Metal oxides; Metals; Microscopy; Nanomaterials; Oxidation; single source precursor; Spectrum analysis; Sulfur content
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202204488

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)S2. (MoWReMnCr)S2 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)S2 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)S2 is demonstrated as a hydrogen evolution electrocatalyst and compared to 2H‐MoS2 synthesized using the molecular precursor approach. (MoWReMnCr)S2 with 20% w/w of high‐conductivity carbon black displays a low overpotential of 229 mV in 0.5 M  H2SO4 to reach a current density of 10 mA cm−2, which is much lower than the overpotential of 362 mV for MoS2. 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‐MoS2 structure, in particular, the first row TMs Cr and Mn. A novel high entropy sulfide (MoWReMnCr)S2 is synthesized by facile thermal decomposition of a cocktail of five individual molecular precursors at a relatively low temperature of 500 °C for 1 h. The performance of the exfoliated 2D nanosheets derived from these high entropy layered materials are measured for electrocatalytic activity in the hydrogen evolution reaction (HER) and the results