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Small. 2019 Mar;15(11):e1900358. doi: 10.1002/smll.201900358. Epub 2019 Feb 8.

Big to Small: Ultrafine Mo2 C Particles Derived from Giant Polyoxomolybdate Clusters for Hydrogen Evolution Reaction.

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School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, New South Wales, 2006, Australia.
School of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, China.
Department of Chemistry and the Institute for Computational and Engineering Sciences, The University of Texas at Austin, 105 E. 24th Street, Stop A5300, Austin, TX, 78712, USA.
Faculty of Engineering, The University of Tokyo, Yayoi, Bunkyo-Ku, Tokyo, 113-00, Japan.
School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney, Sydney, New South Wales, 2006, Australia.
School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, 637459, Singapore.


Due to its electronic structure, similar to platinum, molybdenum carbides (Mo2 C) hold great promise as a cost-effective catalyst platform. However, the realization of high-performance Mo2 C catalysts is still limited because controlling their particle size and catalytic activity is challenging with current synthesis methods. Here, the synthesis of ultrafine β-Mo2 C 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, Mo132 ((NH4 )42 [Mo132 O372 (CH3 COO)30 (H2 O)72 ]·10CH3 COONH4 ·300H2 O) is demonstrated. Moreover, a nitrogen-containing polymeric binder (polyethyleneimine) is used to create MoN bonds between Mo2 C nanoparticles and nitrogen-doped graphene layers, which significantly enhance the catalytic activity of Mo2 C for the hydrogen evolution reaction, as is revealed by X-ray photoelectron spectroscopy and density functional theory calculations. The optimal Mo2 C 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 Mo2 C for various catalytic applications.


graphene; hydrogen evolution reaction; molybdenum carbide; polyoxomolybdate


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