Three-dimensional Nitrogen-Doped Graphene Supported Molybdenum Disulfide Nanoparticles as an Advanced Catalyst for Hydrogen Evolution Reaction

Scientific Reports - Tập 5 Số 1
Haifeng Dong1, Conghui Liu1, Haitao Ye2, Linping Hu3, Bunshi Fugetsu4, Wenhao Dai1, Yu Cao1, Xueqiang Qi3, Huiting Lu1, Xueji Zhang1
1Beijing Key Laboratory for Bioengineering and Sensing Technology, School of Chemistry & Biological Engineering, University of Science & Technology Beijing, Beijing, 100083, P.R. China
2School of Engineering and Applied Science, Aston University, Birmingham B4 7ET, United Kingdom
3Chemistry and Chemical Engineering, Chongqing University, No. 174 Shazhengjie, Shaping Ba, 400044, Chongqing, P.R. China
4Japan Policy Alternative Research Institute, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-0032, Tokyo, Japan

Tóm tắt

AbstractAn efficient three-dimensional (3D) hybrid material of nitrogen-doped graphene sheets (N-RGO) supporting molybdenum disulfide (MoS2) nanoparticles with high-performance electrocatalytic activity for hydrogen evolution reaction (HER) is fabricated by using a facile hydrothermal route. Comprehensive microscopic and spectroscopic characterizations confirm the resulting hybrid material possesses a 3D crumpled few-layered graphene network structure decorated with MoS2 nanoparticles. Electrochemical characterization analysis reveals that the resulting hybrid material exhibits efficient electrocatalytic activity toward HER under acidic conditions with a low onset potential of 112 mV and a small Tafel slope of 44 mV per decade. The enhanced mechanism of electrocatalytic activity has been investigated in detail by controlling the elemental composition, electrical conductance and surface morphology of the 3D hybrid as well as Density Functional Theory (DFT) calculations. This demonstrates that the abundance of exposed active sulfur edge sites in the MoS2 and nitrogen active functional moieties in N-RGO are synergistically responsible for the catalytic activity, whilst the distinguished and coherent interface in MoS2/N-RGO facilitates the electron transfer during electrocatalysis. Our study gives insights into the physical/chemical mechanism of enhanced HER performance in MoS2/N-RGO hybrids and illustrates how to design and construct a 3D hybrid to maximize the catalytic efficiency.

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Tài liệu tham khảo

Joshi, A. S., Dincer, I. & Reddy, B. V. Exergetic assessment of solar hydrogen production methods. Int. J. Hydrogen Energy 35, 4901–4908 (2010).

Jiao, Y., Zheng, Y., Jaroniec, M. & Qiao, S. Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 44, 2060–2086 (2015).

Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).

Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).

Faber, M. S. & Jin, S. Earth-Abundant inorganic electrocatalysts and their nanostructures for energy conversion applications. Energy Environ. Sci. 7, 3519–3542 (2014).

Xu, S., Li, D. & Wu, P. One‐pot, facile and versatile synthesis of monolayer MoS2/WS2 quantum dots as bioimaging probes and efficient electrocatalysts for hydrogen evolution reaction. Adv. Funct. Mater. 25, 1127–1136 (2015).

Norskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nature Chem. 1, 37–46 (2009).

Du, P. & Eisenberg, R. Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: recent progress and future challenges. Energy Environ. Sci. 5, 6012–6021 (2012).

Huang, Z. et al. Cobalt phosphide nanorods as an efficient electrocatalyst for the hydrogen evolution reaction. Nano Energ. 9, 373–382 (2014).

Mellmann, D. et al. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights. Chem.-Eur. J. 20, 13589–13602 (2014).

Borg, S. J. et al. Electron transfer at a dithiolate-bridged diiron assembly: electrocatalytic hydrogen evolution. J. Am. Chem. Soc. 126, 16988–16999 (2004).

Dempsey, J. L., Brunschwig, B. S., Winkler, J. R. & Gray, H. B. Hydrogen evolution catalyzed by cobaloximes. Accounts. Chem. Res. 42, 1995–2004 (2009).

Zheng, Y. et al. Hydrogen evolution by a metal-free electrocatalyst. Nat. Commun. 5, 1–8 (2014).

Deng, J. et al. Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction. Energy Environ. Sci. 7, 1919–1923 (2014).

Morales-Guio, C. G., Stern, L.-A. & Hu, X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 43, 6555–6569 (2014).

Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).

Lukowski, M. A. et al. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem.Soc. 135, 10274–10277 (2013).

Voiry, D. et al. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Letters 13, 6222–6227 (2013).

Yan, Y., Xia, B., Xu, Z. & Wang, X. Recent development of molybdenum sulfides as advanced electrocatalysts for hydrogen evolution reaction. ACS Catal. 4, 1693–1705 (2014).

Li, D. J. et al. Molybdenum sulfide/N-doped CNT forest hybrid catalysts for high-performance hydrogen evolution reaction. Nano Lett. 14, 1228–1233 (2014).

Chen, S., Duan, J., Tang, Y., Jin, B. & Qiao, S. Z. Molybdenum sulfide clusters-nitrogen-doped graphene hybrid hydrogel film as an efficient three-dimensional hydrogen evolution electrocatalyst. Nano Energ. 11, 11–18 (2015).

Pumera, M., Ambrosi, A. & Chng, E. L. K. Impurities in graphenes and carbon nanotubes and their influence on the redox properties. Chem. Sci. 3, 3347–3355 (2012).

Bian, X. et al. Nanocomposite of MoS2 on ordered mesoporous carbon nanospheres: a highly active catalyst for electrochemical hydrogen evolution. Electrochem. Commun. 22, 128–132 (2012).

Fang, Y. et al. A low-concentration hydrothermal synthesis of biocompatible ordered mesoporous carbon nanospheres with tunable and uniform size. Angew. Chem., Int. Ed. 49, 7987–7991 (2010).

Li, Y. G. et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 133, 7296–7299 (2011).

Wang, Y. & Jiang, X. Facile preparation of porous carbon nanosheets without template and their excellent electrocatalytic property. ACS Appl. Mater. Inter. 5, 11597–11602 (2013).

Wang, H., Maiyalagan, T. & Wang, X. Review on recent progress in nitrogen-doped graphene: synthesis, characterization and its potential applications. ACS Catal. 2, 781–794 (2012).

Duan, J., Chen, S., Jaroniec, M. & Qiao, S. Z. Porous C3N4 Nanolayers@ N-Graphene Films as Catalyst Electrodes for Highly Efficient Hydrogen Evolution. ACS Nano 9, 931–940 (2015).

Maitra, U. et al. Highly effective visible-light-induced H2 generation by single-layer 1T-MoS2 and a nanocomposite of few-layer 2H-MoS2 with heavily nitrogenated graphene. Angew Chem. Int Ed 125, 13295–13299 (2013).

Hou, Y. et al. A 3D hybrid of layered MoS2/nitrogen-doped graphene nanosheet aerogels: an effective catalyst for hydrogen evolution in microbial electrolysis cells. J. Mater. Chem. A 2, 13795–13800 (2014).

Qu, L., Liu, Y., Baek, J.-B. & Dai, L. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4, 1321–1326 (2010).

Wang, Y., Shao, Y., Matson, D. W., Li, J. & Lin, Y. Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano 4, 1790–1798 (2010).

Jeong, H. M. et al. Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett. 11, 2472–2477 (2011).

Koroteev, V. O. et al. Charge transfer in the MoS2/carbon nanotube composite. J. Phys.Chem. C 115, 21199–21204 (2011).

Stankovich, S. et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45, 1558–1565 (2007).

Zalan, Z., Lazar, L. & Fulop, F. Chemistry of hydrazinoalcohols and their heterocyclic derivatives. part 1. synthesis of hydrazinoalcohols. Curr. Org. Chem. 9, 357–376 (2005).

Long, D. et al. Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide. Langmuir. 26, 16096–16102 (2010).

Wu, Z. S. et al. 3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction. J. Am. Chem. Soc. 134, 9082–9085 (2012).

Zheng, X. et al. Space-confined growth of MoS2 nanosheets within graphite: the layered hybrid of MoS2 and graphene as an active catalyst for hydrogen evolution reaction. Chem. Mater. 26, 2344–2353 (2014).

Zhao, X., Zhua, H. & Yang, X. Amorphous carbon supported MoS2 nanosheets as effective catalysts for electrocatalytic hydrogen evolution. Nanoscale 6, 10680–10685 (2014).

Zhu, H. et al. Probing the unexpected behavior of aunps migrating through nanofibers: a new strategy for the fabrication of carbon nanofiber-noble metal nanocrystal hybrid nanostructures. J. Mater. Chem. A 2, 11728–11741 (2014).

Zhan, Y., Liu, Z., Najmaei, S., Ajayan, P. M. & Lou, J. Large-area vapor-phase growth and characterization of MoS2 atomic layers on a SiO2 substrate. Small 8, 966–971 (2012).

Benck, J. D., Chen, Z., Kuritzky, L. Y., Forman, A. J. & Jaramillo, T. F. Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: insights into the origin of their catalytic activity. ACS Catal. 2, 1916–1923 (2012).

Zhou, W. et al. MoO2 nanobelts@nitrogen self-doped MoS2 nanosheets as effective electrocatalysts for hydrogen evolution reaction. J. Mater. Chem. A 2, 11358–11364 (2014).

Tao, Y. S., Kanoh, H., Abrams, L. & Kaneko, K. Mesopore-modified zeolites: preparation, characterization and applications. Chem. Rev. 106, 896–910 (2006).

Liang, H. W., Wei, W., Wu, Z. S., Feng, X. & Mullen, K. Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction. J. Am. Chem. Soc. 135, 16002–16005 (2013).

Pachfule, P., Dhavale, V. M., Kandambeth, S., Kurungot, S. & Banerjee, R. Porous-organic-framework-templated nitrogen-rich porous carbon as a more proficient electrocatalyst than Pt/C for the electrochemical reduction of oxygen. Chem.-Eur. J. 19, 974–980 (2013).

Chen, L.F. et al. Synthesis of nitrogen-doped porous carbon nanofibers as an efficient electrode material for supercapacitors. ACS Nano 6, 7092–7102 (2012).

Liu, G., Li, X., Ganesan, P. & Popov, B. N. Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on n-doped ordered porous carbon. Appl. Catal. B-Environ. 93, 156–165 (2009).

Zeng, Z. et al. Single-layer semiconducting nanosheets: high-yield preparation and device fabrication. Ange. Chem., Int. Ed. 50, 11093–11097 (2011).

Matte, H. S. S. R. et al. MoS2 and WS2 analogues of graphene. Ange. Chem., Int. Ed. 49, 4059–4062 (2010).

Lin, Z., Waller, G., Liu, Y., Liu, M. & Wong, C.-P. Facile synthesis of nitrogen-doped graphene via pyrolysis of graphene oxide and urea and its electrocatalytic activity toward the oxygen-reduction reaction. Adv. Energy Mater. 2, 884–888 (2012).

Kong, D. et al. Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett. 13, 1341–1347 (2013).

Hou, Y., Zuo, F., Dagg, A. P., Liu, J. & Feng, P. Branched WO3 nanosheet array with layered C3N4 heterojunctions and CoOx nanoparticles as a flexible photoanode for efficient photoelectrochemical water oxidation. Adv. Mater. 26, 5043–5049 (2014).

Hou, Y. et al. Metal-organic framework-derived nitrogen-doped core-shell-structured porous Fe/Fe3C@C nanoboxes supported on graphene sheets for efficient oxygen reduction reactions. Adv. Energy Mater. 4, 1400337–1400344 (2014).

Yang, S., Feng, X., Ivanovici, S. & Muellen, K. Fabrication of graphene-encapsulated oxide nanoparticles: towards high-performance anode materials for lithium storage. Ange. Chem., Int. Ed. 49, 8408–8411 (2010).

Chen, D., Ji, G., Ma, Y., Lee, J. Y. & Lu, J. Graphene-encapsulated hollow Fe3O4 nanoparticle aggregates as a high-performance anode material for lithium ion batteries. ACS Appl. Mater. Inter. 3, 3078–3083 (2011).

Park, K. W. et al. New RuO2 and carbon-RuO2 composite diffusion layer for use in direct methanol fuel cells. J. Power Sources 109, 439–445 (2002).

Liang, Z. X. & Zhao, T. S. New DMFC anode structure consisting of Platinum nanowires deposited into a nafion membrane. J. Phys. Chem. C 111, 8128–8134 (2007).

Greeley, J. et al. Hydrogen evolution over bimetallic systems: understanding the trends. Chem. Phys. Chem. 7, 1032–1035 (2006).

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