Corresponding Author

Sheng-li CHEN(slchen@whu.edu.cn)


Molybdenum disulfide (MoS2) has been acknowledged to play important roles in hydrogen evolution reaction (HER) for hydrogen energy technology. Both computational and experimental results have suggested that the promising catalytic activity of MoS2 for the HER could be attributed to the sulfur edges of two-dimensional nanosheets, while their basal planes were catalytically inert. In order to verify this conclusion, we prepared single MoS2 sheet electrodes which were made of individual MoS2 sheets attached on the self-assembly monolayers (SAM) of SH(CH2)15COOH at Au ultramicroelectrodes (Au/SAM/MoS2). The single MoS2 sheet electrodes were prepared by dipping the SAM-modified Au ultramicroelectrodes in dilute solutions of MoS2 sheets whose sizes were similar to or slightly smaller than the Au/SAM electrodes. The electrocatalytic properties of the as-prepared single MoS2sheet electrodes with different sizes for HER were investigated in 0.5 mol·L-1 H2SO4. It is shown that the nanoscale MoS2 sheets exhibited superior HER activity over the microsize MoS2 sheets. This is because of the abundantly exposed active sites on the nanoscale MoS2 and the individual nanosheet could reflect its intrinsic reactivity more exactly. It directly proved that the active sites of MoS2 in HER were at the edges.

Graphical Abstract


MoS2, edges, nanoelectrodes, hydrogen evolution reaction.

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[1] Bard A J, Fox M A. Artificial photosynthesis: solar splitting of water to hydrogen and oxygen[J]. Accounts of Chemical Research, 1995, 28(3): 141-145.

[2] Dresselhaus M, Thomas I. Alternative energy technologies[J]. Nature, 2001, 414: 332-337.

[3] Walter M G, Warren M L, McKone J R, et al. Solar water splitting cells[J]. Chemical reviews, 2010, 110(11): 6446-6473.

[4] Lewis N S, Nocera D G. Powering the planet: Chemical challenges in solar energy utilization[J]. Proceedings of the National Academy of Sciences, 2006, 103(43):15729-15735.

[5] Turner J A. Sustainable hydrogen production[J]. Science, 2004, 305(5686):972-974.

[6] Trasatti S. Electrocatalysis of hydrogen evolution: progress in cathode activation[J]. Advances in electrochemical science and engineering, 1992, 2: 1-85.

[7] McKone J R, Warren E L, Bierman M J, et al. Evaluation of Pt, Ni, and Ni€“Mo electrocatalysts for hydrogen evolution on crystalline Si electrodes[J]. Energy & Environmental Science, 2011, 4:3573-3583.

[8] Chianelli R R, Siadati M H, Rosa M P, et al. Catalytic properties of single layers of transition metal sulfide catalytic materials[J]. Catalysis Reviews, 2006, 48(1):1-41.

[9] Laursen A B, Kegnæs S, Dahl S, et al. Molybdenum sulfides-efficient and viable materials for electro- and photoelectrocatalytic hydrogen evolution[J]. Energy & Environmental Science, 2012, 5: 5577-5591.

[10] Lukowski M A, Daniel A S, Meng F, et al. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets[J]. Journal of the American Chemical Society, 2013, 135(28):10274-10277.

[11] Zhao Y F, Xie X Q, Zhang J Q, et al. MoS2 Nanosheets Supported on 3D Graphene Aerogel as a Highly Efficient Catalyst for Hydrogen Evolution[J]. Chemistry-A European Journal, 2015, 21: 15908-15913.

[12] Chen Z B, Kibsgaard J, Jaramillo T. Nanostructuring MoS2 for photoelectrochemical water splitting[J]. Proc. SPIE, Solar Hydrogen and Nano technology V, 2010, 7770(77700K):1-7.

[13] Nørskov J K, Bligaard T, Logadottir A, et al. Trends in the exchange current for hydrogen ev- olution[J]. Journal of The Electrochemical Society, 2005, 152(3):J23-J26.

[14] Nørskov J K, Bligaard T, Rossmeisl J, et al. Towards the computational design of solid cata- lysts[J]. Nature chemistry, 2009, 1:37-46.

[15] Chhowalla M, Shin H S, Eda G. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets[J]. Nature chemistry, 2013, 5,(4): 263-275.

[16] Karunadasa H I, Montalvo E, Sun Y J, et al. A Molecular MoS2 edge site mimic for catalytic hydrogen generation[J]. Science, 2012, 335(6069): 698 -702.

[17] Li Y G, Wang H L, Xie L M, et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction[J]. Journal of the American Chemical Society, 2011, 133(19):7296-7299.

[18] Jaramillo T F, Jørgensen K P, Bonde J, et al. Identification of active edge sites for electro- chemical H2 evolution from MoS2 nanocatalysts [J]. science, 2007, 317(5834):100-102.

[19] Bonde J, Moses P G, Jaramillo T F, et al. Hydrogen evolution on nanoparticulate transition metal sulfides[J]. Faraday discussions, 2009, 140:219-231.

[20] Hinnemann B, Moses P G, Bond J, et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution[J]. Journal of the American Chemical Society, 2005, 127(15):5308-5309.

[21] Jaramillo T F, Bonde J, Zhang J D, et al. Hydrogen evolution on supported incomplete cubane-type [Mo3S4]4+ electrocatalysts[J]. The Journal of Physical Chemistry C, 2008, 112(45): 17492-17498.

[22] Lauritsen J V, Kibsgaard J, Helveg S, et al. Size-dependent structure of MoS2 Nanocrystals [J]. nature nanotechnology, 2007, 2(1): 53-58.

[23] Tremiliosi-Filho G, Dall€™Antonia L H, Jerkiewicz G. Growth of surface oxides on gold electrodes under well-defined potential, time and temperature conditions[J.] Journal of Electro- analytical Chemistry, 2005, 578(1): 1€“8.

[24] Burke L D, Hurley L M, Lodge V E. The effect of severe thermal pretreatment on the redox behaviour of gold in aqueous acid solution[J]. Journal of Solid State Electrochemistry, 2001, 5:250-260.

[25] Brett C M?A, Kresak S, Hianik T, et al. Studies on Self-Assembled Alkanethiol Monolayers Formed at Applied Potential on Polycrystalline Gold Electrodes[J]. Electroanalysis, 2003, 15(5-6): 557-565.

[26] Ulman A. Formation and structure of self- assembled monolayers[J]. Chemical reviews, 1996, 96(4): 1533-1554.

[27] Huang J, Hemminger J C. Photooxidation of thiols in self-assembled monolayers on gold[J]. Journal of the American Chemical Society, 1993, 115(8): 3342-3343.

[28] Laibinis P E, Whitesides G M, Allara D L, et al. Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, copper, silver, and gold[J]. Journal of the American Chemical Society, 1991, 113(19):7152-7167.

[29] Voiry D, Salehi M, Silva R, et al. Conducting MoS2 Nanosheets as Catalysts for Hydrogen Evolution Reaction[J]. Nano Letters, 2013, 13(12):6222-6227.



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