Targeted bottom-up synthesis of 1T-phase MoS2 arrays with high electrocatalytic hydrogen evolution activity by simultaneous structure and morphology engineering
Download citation
573
Views
23
Downloads
52
Crossref
N/A
WoS
49
Scopus
1
CSCD
The incorporation of small guest molecules or ions by bottom-up hydrothermal synthesis has recently emerged as a promising new way to engineer 1T-phase MoS2 with high hydrogen evolution reaction (HER) activity. However, the mechanism of the associated structural evolution remains elusive and controversial, leading to a lack of effective routes to prepare 1T-phase MoS2 with controlled structure and morphology, along with high purity and stability. Herein, urea is chosen as precursor of small molecules or ions to simultaneously engineer the phase (~16.4%, ~69.4%, and ~90.2% of 1T phase) and size (~98.8, ~151.6, and ~251.8 nm for the 90.2% 1T phase) of MoS2 nanosheets, which represent an ideal model system for investigating the structural evolution in these materials, as well as developing a new type of 1T-phase MoS2 arrays. Using reaction intermediate monitoring and theoretical calculations, we show that the oriented growth of 1T-phase MoS2 is controlled by ammonia-assisted assembly, recrystallization, and stabilization processes. A superior HER performance in acidic media is obtained, with an overpotential of only 76 mV required to achieve a stable current density of 10 mA·cm–2 for 15 h. This excellent performance is attributed to the unique array structure, involving well-dispersed, edge-terminated, and high-purity 1T-phase MoS2 nanosheets.
menu
Targeted bottom-up synthesis of 1T-phase MoS2 arrays with high electrocatalytic hydrogen evolution activity by simultaneous structure and morphology engineering
Abstract
The incorporation of small guest molecules or ions by bottom-up hydrothermal synthesis has recently emerged as a promising new way to engineer 1T-phase MoS2 with high hydrogen evolution reaction (HER) activity. However, the mechanism of the associated structural evolution remains elusive and controversial, leading to a lack of effective routes to prepare 1T-phase MoS2 with controlled structure and morphology, along with high purity and stability. Herein, urea is chosen as precursor of small molecules or ions to simultaneously engineer the phase (~16.4%, ~69.4%, and ~90.2% of 1T phase) and size (~98.8, ~151.6, and ~251.8 nm for the 90.2% 1T phase) of MoS2 nanosheets, which represent an ideal model system for investigating the structural evolution in these materials, as well as developing a new type of 1T-phase MoS2 arrays. Using reaction intermediate monitoring and theoretical calculations, we show that the oriented growth of 1T-phase MoS2 is controlled by ammonia-assisted assembly, recrystallization, and stabilization processes. A superior HER performance in acidic media is obtained, with an overpotential of only 76 mV required to achieve a stable current density of 10 mA·cm–2 for 15 h. This excellent performance is attributed to the unique array structure, involving well-dispersed, edge-terminated, and high-purity 1T-phase MoS2 nanosheets.
References(60)
Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.; Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nano 2012, 7, 699–712.
Jariwala, D.; Sangwan, V. K.; Lauhon, L. J.; Marks, T. J.; Hersam, M. C. Emerging device applications for semiconducting two-dimensional transition metal dichalcogenides. ACS Nano 2014, 8, 1102–1120.
Lu, Q. P.; Yu, Y. F.; Ma, Q. L.; Chen, B.; Zhang, H. 2D transition-metal-dichalcogenide-nanosheet-based composites for photocatalytic and electrocatalytic hydrogen evolution reactions. Adv. Mater. 2016, 28, 1917–1933.
Liu, D. B.; Xu, W. Y.; Liu, Q.; He, Q.; Haleem, Y. A.; Wang, C. D.; Xiang, T.; Zou, C. W.; Chu, W. S.; Zhong, J. et al. Unsaturated-sulfur-rich MoS2 nanosheets decorated on free-standing SWNT film: Synthesis, characterization and electrocatalytic application. Nano Res. 2016, 9, 2079–2087.
Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 2007, 317, 100–102.
Ding, Q.; Song, B.; Xu, P.; Jin, S. Efficient electrocatalytic and photoelectrochemical hydrogen generation using MoS2 and related compounds. Chem 2016, 1, 699–726.
Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. J.; Loh, K. P.; Zhang, H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263–275.
Kong, D. S.; Wang, H. T.; Cha, J. J.; Pasta, M.; Koski, K. J.; Yao, J.; Cui, Y. Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett. 2013, 13, 1341–1347.
Tan, Y. W.; Liu, P.; Chen, L. Y.; Cong, W. T.; Ito, Y.; Han, J. H.; Guo, X. W.; Tang, Z.; Fujita, T.; Hirata, A. et al. Monolayer MoS2 films supported by 3D nanoporous metals for high-efficiency electrocatalytic hydrogen production. Adv. Mater. 2014, 26, 8023–8028.
Kibsgaard, J.; Chen, Z. B.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.
Yang, L.; Hong, H.; Fu, Q.; Huang, Y. F.; Zhang, J. Y.; Cui, X. D.; Fan, Z. Y.; Liu, K. H.; Xiang, B. Single-crystal atomic-layered molybdenum disulfide nanobelts with high surface activity. ACS Nano 2015, 9, 6478–6483.
Xie, J. F.; Zhang, H.; Li, S.; Wang, R. X.; Sun, X.; Zhou, M.; Zhou, J. F.; Lou, X. W.; Xie, Y. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 2013, 25, 5807–5813.
Yu, Z. H.; Pan, Y. M.; Shen, Y. T.; Wang, Z. L.; Ong, Z. Y.; Xu, T.; Xin, R.; Pan, L. J.; Wang, B. G.; Sun, L. T. et al. Towards intrinsic charge transport in monolayer molybdenum disulfide by defect and interface engineering. Nat. Commun. 2014, 5, 5290.
Hong, J. H.; Hu, Z. X.; Probert, M.; Li, K.; Lv, D. H.; Yang, X. N.; Gu, L.; Mao, N. N.; Feng, Q. L.; Xie, L. M. et al. Exploring atomic defects in molybdenum disulphide monolayers. Nat. Commun. 2015, 6, 6293.
Li, H.; Tsai, C.; Koh, A. L.; Cai, L. L.; Contryman, A. W.; Fragapane, A. H.; Zhao, J. H.; Han, H. S.; Manoharan, H. C.; Abild-Pedersen, F. et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat. Mater. 2016, 15, 48–53.
Wang, H. T.; Tsai, C.; Kong, D. S.; Chan, H. R.; Abild-Pedersen, F.; Nørskov, J. K.; Cui, Y. Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution. Nano Res. 2015, 8, 566–575.
Voiry, D.; Yamaguchi, H.; Li, J. W.; Silva, R.; Alves, D. C. B.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 2013, 12, 850–855.
Yin, Y.; Han, J. C.; Zhang, Y. M.; Zhang, X. H.; Xu, P.; Yuan, Q.; Samad, L.; Wang, X. J.; Wang, Y.; Zhang, Z. H. et al. Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets. J. Am. Chem. Soc. 2016, 138, 7965–7972.
Voiry, D.; Salehi, M.; Silva, R.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G.; Chhowalla, M. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013, 13, 6222–6227.
Geng, X. M.; Jiao, Y. C.; Han, Y.; Mukhopadhyay, A.; Yang, L.; Zhu, H. L. Freestanding metallic 1T MoS2 with dual ion diffusion paths as high rate anode for sodium-ion batteries. Adv. Funct. Mater. 2017, 27, 1702998.
Acerce, M.; Voiry, D.; Chhowalla, M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat. Nanotechnol. 2015, 10, 313–318.
Lin, Y. C.; Dumcenco, D. O.; Huang, Y. S.; Suenaga, K. Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2. Nat. Nanotechnol. 2014, 9, 391–396.
Kang, Y. M.; Najmaei, S.; Liu, Z.; Bao, Y. J.; Wang, Y. M.; Zhu, X.; Halas, N. J.; Nordlander, P.; Ajayan, P. M.; Lou, J. et al. Plasmonic hot electron induced structural phase transition in a MoS2 monolayer. Adv. Mater. 2014, 26, 6467–6471.
Shi, Y.; Wang, J.; Wang, C.; Zhai, T. T.; Bao, W. J.; Xu, J. J.; Xia, X. H.; Chen, H. Y. Hot electron of Au nanorods activates the electrocatalysis of hydrogen evolution on MoS2 nanosheets. J. Am. Chem. Soc. 2015, 137, 7365–7370.
Sandoval, S. J.; Yang, D.; Frindt, R. F.; Irwin, J. C. Raman study and lattice dynamics of single molecular layers of MoS2. Phys. Rev. B 1991, 44, 3955–3962.
Wang, L. L.; Liu, X.; Luo, J. M.; Duan, X. D.; Crittenden, J.; Liu, C. B.; Zhang, S. Q.; Pei, Y.; Zeng, Y. X.; Duan, X. F. Self-optimization of the active site of molybdenum disulfide by an irreversible phase transition during photocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2017, 56, 7610–7614.
Geng, X. M.; Sun, W. W.; Wu, W.; Chen, B.; Al-Hilo, A.; Benamara, M.; Zhu, H. L.; Watanabe, F.; Cui, J. B.; Chen, T. P. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction. Nat. Commun. 2016, 7, 10672.
Liu, Q.; Li, X. L.; Xiao, Z. R.; Zhou, Y.; Chen, H. P.; Khalil, A.; Xiang, T.; Xu, J. Q.; Chu, W. S.; Wu, X. J. et al. Stable metallic 1T-WS2 nanoribbons intercalated with ammonia ions: The correlation between structure and electrical/optical properties. Adv. Mater. 2015, 27, 4837–4844.
Wang, D. Z.; Zhang, X. Y.; Bao, S. Y.; Zhang, Z. T.; Fei, H.; Wu, Z. Z. Phase engineering of a multiphasic 1T/2H MoS2 catalyst for highly efficient hydrogen evolution. J. Mater. Chem. A 2017, 5, 2681–2688.
Liu, Q.; Li, X. L.; He, Q.; Khalil, A.; Liu, D. B.; Xiang, T.; Wu, X. J.; Song, L. Gram-scale aqueous synthesis of stable few-layered 1T-MoS2: Applications for visible-light-driven photocatalytic hydrogen evolution. Small 2015, 11, 5556–5564.
Calandra, M. Chemically exfoliated single-layer MoS2: Stability, lattice dynamics, and catalytic adsorption from first principles. Phys. Rev. B 2013, 88, 245428.
Güller, F.; Llois, A. M.; Goniakowski, J.; Noguera, C. Prediction of structural and metal-to-semiconductor phase transitions in nanoscale MoS2, WS2, and other transition metal dichalcogenide zigzag ribbons. Phys. Rev. B 2015, 91, 075407.
Wang, J.; Zhong, H. X.; Wang, Z. L.; Meng, F. L.; Zhang, X. B. Integrated three-dimensional carbon paper/carbon tubes/cobalt-sulfide sheets as an efficient electrode for overall water splitting. ACS Nano 2016, 10, 2342–2348.
Li, D. Q.; Liao Q. Y.; Ren, B. W.; Jin, Q. Y.; Cui, H.; Wang, C. X. A 3D-composite structure of FeP nanorods supported by vertically aligned graphene for the high-performance hydrogen evolution reaction. J. Mater. Chem. A 2017, 5, 11301–11308.
Tang, C.; Zhang, R.; Lu, W. B.; He, L. B.; Jiang, X. E.; Asiri, A. M.; Sun, X. P. Fe-Doped CoP Nanoarray: A monolithic multifunctional catalyst for highly efficient hydrogen generation. Adv. Mater. 2017, 29, 1602441.
Fan, X. B.; Xu, P. T.; Zhou, D. K.; Sun, Y. F.; Li, Y. C.; Nguyen, M. A. T.; Terrones, M.; Mallouk, T. E. Fast and efficient preparation of exfoliated 2H MoS2 nanosheets by sonication-assisted lithium intercalation and infrared laser-induced 1T to 2H phase reversion. Nano. Lett. 2015, 15, 5956–5960.
Cheng, P. F.; Sun. K.; Hu, Y. H. Memristive behavior and ideal memristor of 1T phase MoS2 nanosheets. Nano Lett. 2016, 16, 572–576.
Kappera, R.; Voiry, D.; Yalcin, S. E.; Branch, B.; Gupta, G.; Mohite, A. D.; Chhowalla, M. Phase-engineered low-resistance contacts for ultrathin MoS2 transistors. Nat. Mater. 2014, 13, 1128–1134.
Chou, S. S.; Huang, Y. K.; Kim, J.; Kaehr, B.; Foley, B. M.; Lu, P.; Dykstra, C.; Hopkins, P. E.; Brinker, C. J.; Huang, J. X. et al. Controlling the metal to semiconductor transition of MoS2 and WS2 in solution. J. Am. Chem. Soc. 2015, 137, 1742–1745.
Maitra, U.; Gupta, U.; De, M.; Datta, R.; Govindaraj, A.; Rao, C. N. R. 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. 2013, 52, 13057–13061.
Ma, L.; Zhou, X. P.; Xu, L. M.; Xu, X. Y.; Zhang, L. L.; Chen, W. X. Chitosan-assisted fabrication of ultrathin MoS2/graphene heterostructures for Li-ion battery with excellent electrochemical performance. Electrochim. Acta 2015, 167, 39–47.
Hu, S.; Wang, X. Single-walled MoO3 nanotubes. J. Am. Chem. Soc. 2008, 130, 8126–8127.
Wang, P. P.; Sun, H. Y.; Ji, Y. J.; Li, W. H.; Wang, X. Three-dimensional assembly of single-layered MoS2. Adv. Mater. 2014, 26, 964–969.
Enyashin, A. N.; Yadgarov, L.; Houben, L.; Popov, I.; Weidenbach, M.; Tenne, R.; Bar-Sadan, M.; Seifert, G. New route for stabilization of 1T-WS2 and MoS2 phases. J. Phys. Chem. C 2011, 115, 24586–24591.
Cai, L.; He, J. F.; Liu, Q. H.; Yao, T.; Chen, L.; Yan, W. S.; Hu, F. C.; Jiang, Y.; Zhao, Y. D.; Hu, T. D. et al. Vacancy-induced ferromagnetism of MoS2 nanosheets. J. Am. Chem. Soc. 2015, 137, 2622–2627.
Hu, S.; Wang. X. Fullerene-like colloidal nanocrystal of nickel hydroxychloride. J. Am. Chem. Soc. 2010, 132, 9573–9575.
Tang, M. L.; Grauer, D. C.; Lassalle-Kaiser, B.; Yachandra, V. K.; Amirav, L.; Long, J. R.; Yano, J.; Alivisatos, A. P. Structural and electronic study of an amorphous MoS3 hydrogen-generation catalyst on a quantum-controlled photosensitizer. Angew. Chem., Int. Ed. 2011, 123, 10385–10389.
Vrubel, H.; Merki, D.; Hu, X. L. Hydrogen evolution catalyzed by MoS3 and MoS2 particles. Energy Environ. Sci. 2012, 5, 6136–6144.
Li, D. J.; Maiti, U. N.; Lim, J.; Choi, D. S.; Lee, W. J.; Oh, Y.; Lee, G. Y.; Kim, S. O. Molybdenum sulfide/N-doped CNT forest hybrid catalysts for high performance hydrogen evolution reaction. Nano Lett. 2014, 14, 1228–1233.
Wang, H.; Lu, Z.; Xu, S.; Kong, D.; Cha, J. J.; Zheng, G.; Hsu, P.; Yan, K.; Bradshaw, D.; Prinz, F. B. et al. Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction. Proc. Natl. Acad. Sci. USA 2013, 110, 19701–19706.
Tan, S. J. R.; Abdelwahab, I.; Ding, Z. J.; Zhao, X. X.; Yang, T. S.; Loke, G. Z. J.; Lin, H.; Verzhbitskiy, I.; Sock Mui Poh, S. M.; Xu, H. et al. Chemical stabilization of 1T' phase transition metal dichalcogenides with giant optical Kerr nonlinearity. J. Am. Chem. Soc. 2017, 139, 2504–2511.
Cook J. B.; Kim H. S.; Yan Y.; Ko J. S.; Robbennolt S.; Dunn B.; Tolbert S. H. Mesoporous MoS2 as a transition metal dichalcogenide exhibiting pseudocapacitive Li and Na-ion charge storage. Adv. Energy Mater. 2016, 6, 1501937.
Liu, K. K.; Zhang, W. J.; Lee, Y. H.; Lin, Y. C.; Chang, M. T.; Su, C. Y.; Chang, C. S.; Li, H.; Shi, Y. M.; Zhang, H. et al. Growth of large-area and highly crystalline MoS2 thin layers on insulating substrates. Nano Lett. 2012, 12, 1538–1544.
Koroteev, V. O.; Bulusheva, L. G.; Okotrub, A. V.; Yudanov, N. F.; Vyalikh, D. V. Formation of MoS2 nanoparticles on the surface of reduced graphite oxide. Phys. Stat. Solid. B 2011, 248, 2740–2743.
Liao, L.; Zhu, J.; Bian, X. J.; Zhu, L. N.; Scanlon, M. D.; Girault, H. H.; Liu, B. H. MoS2 formed on mesoporous graphene as a highly active catalyst for hydrogen evolution. Adv. Funct. Mater. 2013, 23, 5326–5333.
Lukowski, M. A.; Daniel, A. S.; Meng, F.; Forticaux, A.; Li, L. S.; Jin, S. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem. Soc. 2013, 135, 10274–10277.
Skúlason, E.; Karlberg, G. S.; Rossmeisl, J.; Bligaard, T.; Greeley, J.; Jónsson, H.; Nørskov, J. K. Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode. Phys. Chem. Chem. Phys. 2007, 9, 3241–3250.
Hinnemann, B.; Moses, P. G.; Bonde, J.; Jørgensen, K. P.; Nielsen, J. H.; Horch, S.; Chorkendorff, I.; Nørskov, J. K. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 2005, 127, 5308–5309.
Greeley, J.; Nørskov, J. K. Large-scale, density functional theory-based screening of alloys for hydrogen evolution. Surf. Sci. 2007, 601, 1590–1598.
Fan, X. L.; Yang, Y.; Xiao, P.; Lau, W. M. Site-specific catalytic activity in exfoliated MoS2 single-layer polytypes for hydrogen evolution: Basal plane and edges. J. Mater. Chem. A 2014, 2, 20545–20551.
Publication history
Copyright
Acknowledgements
This work has been financially support by the National Natural Science Foundation of China (No. 21676300), the Beijing Natural Science Foundation (No. 2184104), the Fundamental Research Funds for the Central Universities (No. 16CX06007A) and China Postdoctoral Science Foundation (No. 2017M610076).
FEEDBACK 
TOP