Article Dans Une Revue Journal of Materials Chemistry A Année : 2026

From cluster halides to catalysts: nanostructured molybdenum carbides for efficient hydrogen evolution reaction

Résumé

An original synthesis route for tailoring the hydrogen evolution reaction (HER) activity of α-Mo2C-based catalysts is reported using soluble and air-stable halide precursors built from nanosized [Mo6Cl14]2− cluster units, namely (H3O)2[Mo6Cl14]·7H2O and ((n-C4H9)4N)2[Mo6Cl14], combined with sucrose as a biosourced carbon source. The resulting catalysts consist of nanosized α-Mo2C crystallites embedded in residual carbon, with molybdenum preserved in the +2 oxidation state from the halide precursor to the final material. The chemical nature of the precursor strongly influences the phase composition, homogeneity, specific surface area, and morphology of the resulting α-Mo2C powders. Among the synthesized materials, the catalyst derived from ((n-C4H9)4N)2[Mo6Cl14] exhibits the highest HER performance in alkaline media, characterized by the lowest overpotential at 10 mA cm−2, the largest electrochemical surface area, and the smallest Tafel slope. Long-term electrochemical testing also reveals surface activation during operation, enhancing both activity and stability. These findings indicate that the catalytic behavior of α-Mo2C cannot be attributed solely to nanostructuring effects but arises from a subtle interplay between crystallite size, porosity, and surface chemistry. The use of Mo6 cluster-based precursors thus provides an effective and versatile approach to control the composition and molybdenum oxidation state of molybdenum carbides, enabling the design of advanced powder materials with optimized surface and electrocatalytic properties.

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hal-05540121 , version 1 (06-03-2026)

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Guillaume Dubois, Sébastien Mathivet, Noee Dumait, Ludivine Rault, Stéphane Cordier, et al.. From cluster halides to catalysts: nanostructured molybdenum carbides for efficient hydrogen evolution reaction. Journal of Materials Chemistry A, 2026, ⟨10.1039/d5ta09668e⟩. ⟨hal-05540121⟩
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