Big to Small: Ultrafine Mo₂C Particles Derived from Giant Polyoxomolybdate Clusters for Hydrogen Evolution Reaction

Abstract

Due to its electronic structure, similar to platinum, molybdenum carbides (Mo₂C) hold great promise as a cost-effective catalyst platform. However, the realization of high-performance Mo₂C catalysts is still limited because controlling their particle size and catalytic activity is challenging with current synthesis methods. Here, the synthesis of ultrafine β-Mo₂C nanoparticles with narrow size distribution (2.5 ± 0.7 nm) and high mass loading (up to 27.5 wt%) on graphene substrate using a giant Mo-based polyoxomolybdate cluster, Mo₁₂₃ ((NH₄)₄₂ [Mo₁₂₃O₃₇₂(CH₃COO)₃₀(H₂O)₇₂]·10CH₃COONH₄ ·300H₂O) is demonstrated. Moreover, a nitrogen-containing polymeric binder (polyethyleneimine) is used to create Mo—N bonds between Mo₂C nanoparticles and nitrogen-doped graphene layers, which significantly enhance the catalytic activity of Mo₂C for the hydrogen evolution reaction, as is revealed by X-ray photoelectron spectroscopy and density functional theory calculations. The optimal Mo₂C catalyst shows a large exchange current density of 1.19 mA cm–² , a high turnover frequency of 0.70 s–¹ as well as excellent durability. The demonstrated new strategy opens up the possibility of developing practical platinum substitutes based on Mo₂C for various catalytic applications.