Production of monolayer-rich gold-decorated 2H–WS2 nanosheets by defect engineering
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Abstract
Abstract Chemical functionalization of low-dimensional nanostructures has evolved as powerful tool to tailor the materials’ properties on demand. For two-dimensional transition metal dichalcogenides, functionalization strategies are mostly limited to the metallic 1T-polytype with only few examples showing a successful derivatization of the semiconducting 2H-polytype. Here, we describe that liquid-exfoliated WS2 undergoes a spontaneous redox reaction with AuCl3. We propose that thiol groups at edges and defects sites reduce the AuCl3 to Au0 and are in turn oxidized to disulfides. As a result of the reaction, Au nanoparticles nucleate predominantly at edges with tuneable nanoparticle size and density. The drastic changes in nanosheet mass obtained after high loading with Au nanoparticles can be exploited to enrich the dispersions in laterally large, monolayered nanosheets by simple centrifugation. The optical properties (for example photoluminescence) of the monolayers remain pristine, while the electrocatalytic activity towards the hydrogen evolution reaction is significantly improved.
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Research context
OpenAlex topics: 2D Materials and Applications · Quantum Dots Synthesis And Properties · Advanced Photocatalysis Techniques
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References (50)
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1. 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 8, 1102–1120 (2014).10.1021/nn500064s ↗
2. Mak, K. F. & Shan, J. Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides. Nat. Photon-. 10, 216–226 (2016).10.1038/nphoton.2015.282 ↗
3. Buscema, M. et al. Photocurrent generation with two-dimensional van der Waals semiconductors. Chem. Soc. Rev. 44, 3691–3718 (2015).10.1039/C5CS00106D ↗
4. Voiry, D., Yang, J. & Chhowalla, M. Recent strategies for improving the catalytic activity of 2D TMD nanosheets toward the hydrogen evolution reaction. Adv. Mater. 28, 6197–6206 (2016).10.1002/adma.201505597 ↗
5. Li, B. L. et al. Low-dimensional transition metal dichalcogenide nanostructures based sensors. Adv. Funct. Mater. 26, 7034–7056 (2016).10.1002/adfm.201602136 ↗
6. Tao, H. et al. Two-dimensional nanosheets for electrocatalysis in energy generation and conversion. J. Mater. Chem. C 16, 7257–7284 (2017).10.1039/C7TA00075H ↗
7. Pumera, M., Sofer, Z. & Ambrosi, A. Layered transition metal dichalcogenides for electrochemical energy generation and storage. J. Mater. Chem. C. 2, 8981–8987 (2014).10.1039/C4TA00652F ↗
8. Mendoza-Sánchez, B. & Gogotsi, Y. Synthesis of two-dimensional materials for capacitive energy storage. Adv. Mater. 28, 6104–6135 (2016).10.1002/adma.201506133 ↗
9. Tan, C. et al. Recent advances in ultrathin two-dimensional nanomaterials. Chem. Rev. 117, 6225–6331 (2017).10.1021/acs.chemrev.6b00558 ↗
10. Lu, Q., Yu, Y., Ma, Q., Chen, B. & Zhang, H. 2D transition-metal-dichalcogenide-nanosheet-based composites for photocatalytic and electrocatalytic hydrogen evolution reactions. Adv. Mater. 28, 1917–1933 (2016).10.1002/adma.201503270 ↗
11. Bonaccorso, F., Bartolotta, A., Coleman, J. N. & Backes, C. 2D-crystal-based functional inks. Adv. Mater. 28, 6136–6166 (2016).10.1002/adma.201506410 ↗
12. Nicolosi, V., Chhowalla, M., Kanatzidis, M. G., Strano, M. S. & Coleman, J. N. Liquid exfoliation of layered materials. Science 340, 1420 (2013).10.1126/science.1226419 ↗
13. Tao, H. et al. Scalable exfoliation and dispersion of two-dimensional materials - an update. Phys. Chem. Chem. Phys. 19, 921–960 (2017).10.1039/C6CP06813H ↗
14. Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).10.1038/nchem.1589 ↗
15. Kelly, A. G. et al. All-printed thin-film transistors from networks of liquid-exfoliated nanosheets. Science 356, 69–73 (2017).10.1126/science.aal4062 ↗
16. McManus, D. et al. Water-based and biocompatible 2D crystal inks for all-inkjet-printed heterostructures. Nat. Nano. 12, 343–350 (2017).10.1038/nnano.2016.281 ↗
17. Kang, J. et al. Thickness sorting of two-dimensional transition metal dichalcogenides via copolymer-assisted density gradient ultracentrifugation. Nat. Commun. 5, 5478 (2014).10.1038/ncomms6478 ↗
18. Backes, C. et al. Production of highly monolayer enriched dispersions of liquid-exfoliated nanosheets by liquid cascade centrifugation. ACS Nano 10, 1589–1601 (2016).10.1021/acsnano.5b07228 ↗
19. Kang, J., Sangwan, V. K., Wood, J. D. & Hersam, M. C. Solution-based processing of monodisperse two-dimensional nanomaterials. Acc. Chem. Res. 50, 943–951 (2017).10.1021/acs.accounts.6b00643 ↗
20. Chen, X. & McDonald, A. R. Functionalization of two-dimensional transition-metal dichalcogenides. Adv. Mater. 28, 5738–5746 (2016).10.1002/adma.201505345 ↗
21. Presolski, S. & Pumera, M. Covalent functionalization of MoS2. Mater. Today 19, 140–145 (2016).10.1016/j.mattod.2015.08.019 ↗
22. Hirsch, A. & Hauke, F. Post graphene 2D chemistry: the emerging field of molybdenum disulfide and black phosphorus functionalization. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.201708211 (2017).10.1002/anie.201708211 ↗
23. Backes, C. et al. Functionalization of liquid-exfoliated two-dimensional 2H-MoS2. Angew. Chem. Int. Ed. 54, 2638–2642 (2015).10.1002/anie.201409412 ↗
24. Chen, X., Berner, N. C., Backes, C., Duesberg, G. S. & McDonald, A. R. Functionalization of two-dimensional MoS2: on the reaction between MoS2 and organic thiols. Angew. Chem. Int. Ed. 55, 5803–5808 (2016).10.1002/anie.201510219 ↗
25. Kim, J., Byun, S., Smith, A. J., Yu, J. & Huang, J. Enhanced electrocatalytic properties of transition-metal dichalcogenides sheets by spontaneous gold nanoparticle decoration. J. Phys. Chem. Lett. 4, 1227–1232 (2013).10.1021/jz400507t ↗
26. Shi, Y. et al. Selective decoration of Au nanoparticles on monolayer MoS2 single crystals. Sci. Rep. 3, 1839 (2013).10.1038/srep01839 ↗
27. Zhang, P. et al. MoS2 nanosheets decorated with gold nanoparticles for rechargeable Li-O2batteries. J. Mater. Chem. C. 3, 14562–14566 (2015).10.1039/C5TA02945G ↗
28. Topolovsek, P. et al. Thiol click chemistry on gold-decorated MoS2: elastomer composites and structural phase transitions. Nanoscale 8, 10016–10020 (2016).10.1039/C6NR01490A ↗
29. Sun, H. et al. Gold nanoparticle-decorated MoS2 nanosheets for simultaneous detection of ascorbic acid, dopamine and uric acid. RSC Adv. 4, 27625–27629 (2014).10.1039/c4ra04046e ↗
30. Su, S. et al. Direct electrochemistry of glucose oxidase and a biosensor for glucose based on a glass carbon electrode modified with MoS2 nanosheets decorated with gold nanoparticles. Microchim. Acta 181, 1497–1503 (2014).10.1007/s00604-014-1178-9 ↗
31. Forcherio, G. T. & Roper, D. K. Spectral characteristics of noble metal nanoparticle–molybdenum disulfide heterostructures. Adv. Opt. Mater. 4, 1288–1294 (2016).10.1002/adom.201600219 ↗
32. Forcherio, G. T., Benamara, M. & Roper, D. K. Electron energy loss spectroscopy of hot electron transport between gold nanoantennas and molybdenum disulfide by plasmon excitation. Adv. Opt. Mater. 5, 1600572 (2017).10.1002/adom.201600572 ↗
33. Lin, J., Li, H., Zhang, H. & Chen, W. Plasmonic enhancement of photocurrent in MoS2 field-effect-transistor. Appl. Phys. Lett. 102, 203109 (2013).10.1063/1.4807658 ↗
34. Yin, Z. et al. Au nanoparticle-modified MoS2 nanosheet-based photoelectrochemical cells for water splitting. Small 10, 3537–3543 (2014).10.1002/smll.201400124 ↗
35. Kang, Y. et al. Plasmonic hot electron enhanced MoS2 photocatalysis in hydrogen evolution. Nanoscale 7, 4482–4488 (2015).10.1039/C4NR07303G ↗
36. Huang, X. et al. Solution-phase epitaxial growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide nanosheets. Nat. Commun. 4, 1444 (2013).10.1038/ncomms2472 ↗
37. Zhong, L. et al. Defect engineering of two-dimensional transition metal dichalcogenides. 2D Mater. 3, 022002 (2016).10.1088/2053-1583/3/2/022002 ↗
38. Backes, C. et al. Edge and confinement effects allow in situ measurement of size and thickness of liquid-exfoliated nanosheets. Nat. Commun. 5, 4576 (2014).10.1038/ncomms5576 ↗
39. Mie, G. Beiträge zur Optik trüber Medien, speziell kolloidaler Metallösungen. Ann. Phys. 330, 377–445 (1908).10.1002/andp.19083300302 ↗
40. Bandyopadhyay, S., Chattopadhyay, S. & Dey, A. The protonation state of thiols in self-assembled monolayers on roughened Ag/Au surfaces and nanoparticles. Phys. Chem. Chem. Phys. 17, 24866–24873 (2015).10.1039/C5CP04450B ↗
41. Battocchio, C. et al. Gold nanoparticles stabilized with aromatic thiols: interaction at the molecule–metal interface and ligand arrangement in the molecular shell investigated by SR-XPS and NEXAFS. J. Phys. Chem. C. 118, 8159–8168 (2014).10.1021/jp4126057 ↗
42. Vitale, F. et al. Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization. Nanoscale Res. Lett. 6, 103 (2011).10.1186/1556-276X-6-103 ↗
43. Gade, M. et al. Immobilization of multivalent glycoprobes on gold surfaces for sensing proteins and macrophages. Analyst 141, 2250–2258 (2016).10.1039/C5AN02336J ↗
44. Forcherio, G. T. et al. Gold nanoparticles physicochemically bonded onto tungsten disulfide nanosheet edges exhibit augmented plasmon damping. AIP Adv. 7, 075103 (2017).10.1063/1.4989774 ↗
45. Mak, K. F., Lee, C., Hone, J., Shan, J. & Heinz, T. F. Atomically thin MoS2. A new direct-gap semiconductor. Phys. Rev. Lett. 105, 136805 (2010).10.1103/PhysRevLett.105.136805 ↗
46. Mitioglu, A. A. et al. Optical manipulation of the exciton charge state in single-layer tungsten disulfide. Phys. Rev. B 88, 245403 (2013).10.1103/PhysRevB.88.245403 ↗
47. McAteer, D. et al. Thickness dependence and percolation scaling of hydrogen production rate in MoS2 nanosheet and nanosheet-carbon nanotube composite catalytic electrodes. ACS Nano 10, 672–683 (2016).10.1021/acsnano.5b05907 ↗
48. Gholamvand, Z. et al. Comparison of liquid exfoliated transition metal dichalcogenides reveals MoSe2 to be the most effective hydrogen evolution catalyst. Nanoscale 8, 5737–5749 (2016).10.1039/C5NR08553E ↗
49. Gholamvand, Z., McAteer, D., Harvey, A., Backes, C. & Coleman, J. N. Electrochemical applications of two-dimensional nanosheets: the effect of nanosheet length and thickness. Chem. Mater. 28, 2641–2651 (2016).10.1021/acs.chemmater.6b00009 ↗
50. Higgins, T. M. & Coleman, J. N. Avoiding resistance limitations in high-performance transparent supercapacitor electrodes based on large-area, high-conductivity PEDOT:PSS films. ACS Appl. Mater. Interfaces 7, 16495–16506 (2015).10.1021/acsami.5b03882 ↗