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Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

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Abstract

Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13]2− building blocks. Of the three terminal disulfide (S22−) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum.

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Figure 1: Structures of molybdenum sulfide materials.
Figure 2: Spectroscopic characterization of a-MoSx catalyst.
Figure 3: HAADF-STEM analysis.
Figure 4: Electrochemical properties of a-MoSx electrodes.
Figure 5: Proposed catalytic pathway for H2 evolution.
Figure 6: DFT-calculated potential catalytic intermediates.

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Acknowledgements

P.D.T. and J.B. acknowledge the Energy Research Institute @ Nanyang Technological University (ERI@N) and the Singapore-Berkeley Research Initiative for Sustainable Energy (SinBeRISE) CREATE for financial and facilities supports. P.D.T. acknowledges University of Science and Technology of Hanoi for startup funding support (project USTH PECH2). Q.D.T. and I.H. acknowledge the Japan Society for Promotion of Science for financial support (Grant No. P13070). This work was supported by the French National Research Agency (Labex program, ARCANE, ANR-11-LABX-0003-01) and the European Research Council under the European Union’s Seventh Framework Programme (FP/2007–2013)/ERC Grant Agreement n.306398. J. Pérard is gratefully acknowledged for his help during ICP-AES measurements.

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P.D.T. and V.A. designed research and performed material synthesis and electrochemical studies. T.V.T. performed resonance Raman analysis. Q.D.T., K.N., Y.S. and I.H. performed and analysed STEM studies. S.Y.C. and R.Y. performed XPS studies. S.T. and V.A. performed and analysed EPR studies. M.O. performed DFT calculations. P.D.T., V.A. and J.B. wrote the paper.

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Correspondence to Phong D. Tran or Vincent Artero.

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Tran, P., Tran, T., Orio, M. et al. Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide. Nature Mater 15, 640–646 (2016). https://doi.org/10.1038/nmat4588

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