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SCIENCE CHINA Materials, Volume 63 , Issue 10 : 2079-2085(2020) https://doi.org/10.1007/s40843-020-1416-0

Intercalator-assisted plasma-liquid technology: an efficient exfoliation method for few-layer two-dimensional materials

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  • ReceivedMar 24, 2020
  • AcceptedMay 31, 2020
  • PublishedAug 5, 2020

Abstract

本工作提出了一种插层剂辅助的等离子体液相技术用于高效地剥离高质量少层二维材料. 采用氯化锂为插层剂可快速剥离石墨纸, 形成具有小D峰/G峰比(0.02)以及大碳氧比(31.5)的石墨烯产物. 并且, 这种方法可以拓展至高质量少层2H相二硫化钼的制备. 和传统的插层剂辅助电化学方法相比, 等离子体诱导产生的大量活性粒子以及快速的电子转移, 使得插层剂辅助的等离子体液相技术剥离的产物缺陷少且不会引入额外的基团. 这种可控的快速剥离方法在制备其他各种类型的高质量二维材料方面都具有巨大潜力.


Funded by

the National Natural Science Foundation of China(21975280)

Shenzhen Science and Technology Research Funding(JCYJ20180507182530279)

the Frontier Science Key Programs of Chinese Academy of Sciences(QYZDB-SSW-SLH034)

Guangdong Special Support Program(2017TX04C096)

the Leading Talents of Guangdong Province Program(00201520)

and the City University of Hong Kong Strategic Research Grants(SRG,7005105,7005264)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21975280), Shenzhen Science and Technology Research Funding (JCYJ20180507182530279), the Frontier Science Key Programs of Chinese Academy of Sciences (QYZDB-SSW-SLH034), Guangdong Special Support Program (2017TX04C096), the Leading Talents of Guangdong Province Program (00201520), and the City University of Hong Kong Strategic Research Grants (SRG, 7005105 and 7005264).


Interest statement

The authors declare no conflict of interest.


Contributions statement

Huang H and Gao M conducted the experiments and measurements; Wang J, Chu PK, Huang Y discussed the data and provided suggestions; Yu XF supervised and directed the project; All authors participated the general discussion.


Author information

Hao Huang received his BSc degree from the University of Electronic Science and Technology of China (2012) and MSc degree from Wuhan University (2015). Now, he is a PhD candidate at Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, China. His interests focus on the synthesis and applications of nanomaterials and 2D materials.


Ming Gao received his MSc degree from Donghua University (2012), and now he is a PhD candidate at Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, China. His interests focus on the preparation and surface modification of materials with low-temperature plasma technology.


Yifan Huang received his BSc and PhD degrees from Zhejiang University, China in 2005 and 2010 respectively. Then, he joined Zhejiang University as an assistant professor, and now he is a full professor at Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences. His research interest includes non-thermal plasma generation and application.


Xue-Feng Yu received his PhD degree in optics from Wuhan University (2008). He has been a senior research associate in the Department of Physics and Materials of City University of Hongkong. He is currently a professor at Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, China. His interests focus on the applied materials and interfaces including the synthesis of functional materials, materials interfaces, biochips.


Supplement

Supplementary information

Experimental details and supporting data are available in the online version of the paper.


References

[1] Novoselov KS, Geim AK, Morozov SV, et al. Electric field effect in atomically thin carbon films. Science, 2004, 306: 666-669 CrossRef ADS arXiv Google Scholar

[2] Mounet N, Gibertini M, Schwaller P, et al. Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds. Nat Nanotech, 2018, 13: 246-252 CrossRef ADS Google Scholar

[3] Bonaccorso F, Colombo L, Yu G, et al. Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science, 2015, 347: 1246501-41 CrossRef ADS Google Scholar

[4] Yi Y, Yu XF, Zhou W, et al. Two-dimensional black phosphorus: Synthesis, modification, properties, and applications. Mater Sci Eng-R-Rep, 2017, 120: 1-33 CrossRef Google Scholar

[5] Kang J, Sangwan VK, Wood JD, et al. Solution-based processing of monodisperse two-dimensional nanomaterials. Acc Chem Res, 2017, 50: 943-951 CrossRef Google Scholar

[6] Park S, Ruoff RS. Chemical methods for the production of graphenes. Nat Nanotech, 2009, 4: 217-224 CrossRef ADS Google Scholar

[7] Pei S, Cheng HM. The reduction of graphene oxide. Carbon, 2012, 50: 3210-3228 CrossRef Google Scholar

[8] Shi D, Yang M, Chang B, et al. Ultrasonic-ball milling: A novel strategy to prepare large-size ultrathin 2D materials. Small, 2020, 16: 1906734 CrossRef Google Scholar

[9] Zhang C, Tan J, Pan Y, et al. Mass production of 2D materials by intermediate-assisted grinding exfoliation. Natl Sci Rev, 2020, 7: 324-332 CrossRef Google Scholar

[10] Su CY, Lu AY, Xu Y, et al. High-quality thin graphene films from fast electrochemical exfoliation. ACS Nano, 2011, 5: 2332-2339 CrossRef Google Scholar

[11] Zeng Z, Yin Z, Huang X, et al. Single-layer semiconducting nanosheets: high-yield preparation and device fabrication. Angew Chem Int Ed, 2011, 50: 11093-11097 CrossRef Google Scholar

[12] Wu W, Zhang C, Hou S. Electrochemical exfoliation of graphene and graphene-analogous 2D nanosheets. J Mater Sci, 2017, 52: 10649-10660 CrossRef ADS Google Scholar

[13] Huang Z, Hou H, Zhang Y, et al. Layer-tunable phosphorene modulated by the cation insertion rate as a sodium-storage anode. Adv Mater, 2017, 29: 1702372 CrossRef Google Scholar

[14] Cao J, He P, Mohammed MA, et al. Two-step electrochemical intercalation and oxidation of graphite for the mass production of graphene oxide. J Am Chem Soc, 2017, 139: 17446-17456 CrossRef Google Scholar

[15] Yang S, Brüller S, Wu ZS, et al. Organic radical-assisted electrochemical exfoliation for the scalable production of high-quality graphene. J Am Chem Soc, 2015, 137: 13927-13932 CrossRef Google Scholar

[16] Liu N, Kim P, Kim JH, et al. Large-area atomically thin MoS2 nanosheets prepared using electrochemical exfoliation. ACS Nano, 2014, 8: 6902-6910 CrossRef Google Scholar

[17] Wang C, He Q, Halim U, et al. Monolayer atomic crystal molecular superlattices. Nature, 2018, 555: 231-236 CrossRef ADS Google Scholar

[18] Wang J, Manga KK, Bao Q, et al. High-yield synthesis of few-layer graphene flakes through electrochemical expansion of graphite in propylene carbonate electrolyte. J Am Chem Soc, 2011, 133: 8888-8891 CrossRef Google Scholar

[19] Neyts EC, Ostrikov KK, Sunkara MK, et al. Plasma catalysis: synergistic effects at the nanoscale. Chem Rev, 2015, 115: 13408-13446 CrossRef Google Scholar

[20] Huang H, Gao M, Kang Y, et al. Rapid and scalable production of high-quality phosphorene by plasma–liquid technology. Chem Commun, 2020, 56: 221-224 CrossRef Google Scholar

[21] Li M, Liu D, Wei D, et al. Controllable synthesis of graphene by plasma-enhanced chemical vapor deposition and its related applications. Adv Sci, 2016, 3: 1600003 CrossRef Google Scholar

[22] Wang Y, Zhang Y, Liu Z, et al. Layered double hydroxide nanosheets with multiple vacancies obtained by dry exfoliation as highly efficient oxygen evolution electrocatalysts. Angew Chem Int Ed, 2017, 56: 5867-5871 CrossRef Google Scholar

[23] Zhang Y, Rawat RS, Fan HJ. Plasma for rapid conversion reactions and surface modification of electrode materials. Small Methods, 2017, 1: 1700164 CrossRef Google Scholar

[24] Richmonds C, Sankaran RM. Plasma-liquid electrochemistry: Rapid synthesis of colloidal metal nanoparticles by microplasma reduction of aqueous cations. Appl Phys Lett, 2008, 93: 131501 CrossRef ADS Google Scholar

[25] Yen PJ, Ting CC, Chiu YC, et al. Facile production of graphene nanosheets comprising nitrogen-doping through in situ cathodic plasma formation during electrochemical exfoliation. J Mater Chem C, 2017, 5: 2597-2602 CrossRef Google Scholar

[26] Yang S, Ricciardulli AG, Liu S, et al. Ultrafast delamination of graphite into high-quality graphene using alternating currents. Angew Chem Int Ed, 2017, 56: 6669-6675 CrossRef Google Scholar

[27] Hernandez Y, Nicolosi V, Lotya M, et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotech, 2008, 3: 563-568 CrossRef ADS arXiv Google Scholar

[28] Wu W, Liu M, Gu Y, et al. Fast chemical exfoliation of graphite to few-layer graphene with high quality and large size via a two-step microwave-assisted process. Chem Eng J, 2020, 381: 122592 CrossRef Google Scholar

[29] Paton KR, Varrla E, Backes C, et al. Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids. Nat Mater, 2014, 13: 624-630 CrossRef ADS Google Scholar

[30] Cooper AJ, Wilson NR, Kinloch IA, et al. Single stage electrochemical exfoliation method for the production of few-layer graphene via intercalation of tetraalkylammonium cations. Carbon, 2014, 66: 340-350 CrossRef Google Scholar

[31] Wu L, Li W, Li P, et al. Powder, paper and foam of few-layer graphene prepared in high yield by electrochemical intercalation exfoliation of expanded graphite. Small, 2014, 10: 1421-1429 CrossRef Google Scholar

[32] Abdelkader AM, Cooper AJ, Dryfe RAW, et al. How to get between the sheets: a review of recent works on the electrochemical exfoliation of graphene materials from bulk graphite. Nanoscale, 2015, 7: 6944-6956 CrossRef ADS Google Scholar

[33] Eda G, Yamaguchi H, Voiry D, et al. Photoluminescence from chemically exfoliated MoS2. Nano Lett, 2011, 11: 5111-5116 CrossRef ADS Google Scholar

[34] Zheng J, Zhang H, Dong S, et al. High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide. Nat Commun, 2014, 5: 2995 CrossRef ADS Google Scholar

[35] Lin Z, Liu Y, Halim U, et al. Solution-processable 2D semiconductors for high-performance large-area electronics. Nature, 2018, 562: 254-258 CrossRef ADS Google Scholar

[36] Splendiani A, Sun L, Zhang Y, et al. Emerging photoluminescence in monolayer MoS2. Nano Lett, 2010, 10: 1271-1275 CrossRef ADS Google Scholar

  • Figure 1

    Characterization of the IA-PLT-exfoliated graphene: (a) photographs of the graphene-DMF dispersions; (b) AFM images and thickness distribution of graphene (at least 100 sheets were measured); (c) TEM image and HR-TEM image (inset); (d) Raman scattering spectrum; (e, f) XPS survey and C 1s spectra.

  • Figure 2

    (a–c) Cross-section SEM images, inset photographs and (d) XRD spectra and enlarged specific region of the graphite paper in different expansion degrees.

  • Figure 3

    Schematic of the IA-PLT exfoliation process in graphite paper.

  • Figure 4

    Characterization of the IA-PLT-exfoliated MoS2 sheets: (a) photographs showing the IA-PLT exfoliation process and the MoS2 sheets-IPA dispersions; (b) TEM image and HR-TEM image (inset); (c) absorbance spectrum of the MoS2 sheets-IPA dispersions; (d) PL spectrum of one representative MoS2 sheet.