Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates

Abstract

Two-dimensional (2D) materials have attracted significant interest because of their large surface-to-volume ratios and electron confinement. Compared to common 2D materials such as graphene or metal hydroxides, with their intrinsic layered atomic structures, the formation mechanisms of 2D metal oxides with a rocksalt structure are not well understood. Here, we report the formation process for 2D cobalt oxide and cobalt nickel oxide nanosheets, after analysis by in situ liquid-phase transmission electron microscopy. Our observations reveal that three-dimensional (3D) nanoparticles are initially formed from the molecular precursor solution and then transform into 2D nanosheets. Ab initio calculations show that a small nanocrystal is dominated by positive edge energy, but when it grows to a certain size, the negative surface energy becomes dominant, driving the transformation of the 3D nanocrystal into a 2D structure. Uncovering these growth pathways, including the 3D-to-2D transition, provides opportunities for future material design and synthesis in solution.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Growth and transformations of cobalt oxide and cobalt nickel oxide nanocrystals into 2D nanosheets.
Fig. 2: Tracking of cobalt oxide nanosheet development with high resolution.
Fig. 3: The interaction and attachments between two cobalt oxide nanosheets.
Fig. 4: Sequential images show the growth of nickel oxide nanocrystals.
Fig. 5: Energy evolution of cobalt oxide during the 3D-to-2D transition.

Data availability

Data are available in the online version of this paper. Data that support the findings of this study are available from corresponding authors upon reasonable request.

Code availability

Computer codes for theoretical calculations in this work are available upon request from the corresponding authors.

References

  1. 1.

    Deng, D. et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotechnol. 11, 218–230 (2016).

  2. 2.

    Koppens, F. H. L. et al. Photodetectors based on graphene, other two-dimensional materials and hybrid systems. Nat. Nanotechnol. 9, 780–793 (2014).

  3. 3.

    Lukatskaya, M. R. et al. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 341, 1502–1505 (2013).

  4. 4.

    Nair, R. R. et al. Fine structure constant defines visual transparency of graphene. Science 320, 1308 (2008).

  5. 5.

    Lv, R. et al. Transition metal dichalcogenides and beyond: synthesis, properties and applications of single- and few-layer nanosheets. Acc. Chem. Res. 48, 56–64 (2015).

  6. 6.

    Gao, L. et al. Face-to-face transfer of wafer-scale graphene films. Nature 505, 190–194 (2014).

  7. 7.

    Coleman, J. N. et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 331, 568–571 (2011).

  8. 8.

    Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater. 6, 183–191 (2007).

  9. 9.

    Ma, R., Liang, J., Liu, X. & Sasaki, T. General insights into structural evolution of layered double hydroxide: underlying aspects in topochemical transformation from brucite to layered double hydroxide. J. Am. Chem. Soc. 134, 19915–19921 (2012).

  10. 10.

    Sun, Y., Gao, S., Lei, F., Xiao, C. & Xie, Y. Ultrathin two-dimensional inorganic materials: new opportunities for solid state nanochemistry. Acc. Chem. Res. 48, 3–12 (2015).

  11. 11.

    Wang, Q. & O’Hare, D. Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets. Chem. Rev. 112, 4124–4155 (2012).

  12. 12.

    Ma, R. & Sasaki, T. Two-dimensional oxide and hydroxide nanosheets: controllable high-quality exfoliation, molecular assembly and exploration of functionality. Acc. Chem. Res. 48, 136–143 (2015).

  13. 13.

    Jeon, M. Y. et al. Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets. Nature 543, 690–694 (2017).

  14. 14.

    Gamble, F. R. et al. Intercalation complexes of Lewis bases and layered sulfides: a large class of new superconductors. Science 174, 493–497 (1971).

  15. 15.

    Ha, B., Char, K. & Jeon, H. S. Intercalation mechanism and interlayer structure of hexadecylamines in the confined space of layered α-zirconium phosphates. J. Phys. Chem. B 109, 24434–24440 (2005).

  16. 16.

    Jang, J. et al. Ultrathin zirconium disulfide nanodiscs. J. Am. Chem. Soc. 133, 7636–7639 (2011).

  17. 17.

    Manna, L., Wang, Cingolani, R. & Alivisatos, A. P. First-principles modeling of unpassivated and surfactant-passivated bulk facets of wurtzite CdSe: a model system for studying the anisotropic growth of CdSe nanocrystals. J. Phys. Chem. B 109, 6183–6192 (2005).

  18. 18.

    Gao, S. et al. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 529, 68–71 (2016).

  19. 19.

    Huang, X. et al. Freestanding palladium nanosheets with plasmonic and catalytic properties. Nat. Nanotechnol. 6, 28–32 (2011).

  20. 20.

    Niu, J. et al. Novel polymer-free iridescent lamellar hydrogel for two-dimensional confined growth of ultrathin gold membranes. Nat. Commun. 5, 3313 (2014).

  21. 21.

    Saleem, F. et al. Ultrathin Pt–Cu nanosheets and nanocones. J. Am. Chem. Soc. 135, 18304–18307 (2013).

  22. 22.

    Sun, Z. et al. Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets. Nat. Commun. 5, 3813 (2014).

  23. 23.

    Jia, Y. et al. Unique excavated rhombic dodecahedral PtCu3 alloy nanocrystals constructed with ultrathin nanosheets of high-energy {110} facets. J. Am. Chem. Soc. 136, 3748–3751 (2014).

  24. 24.

    Li, Z. & Peng, X. Size/shape-controlled synthesis of colloidal CdSe quantum disks: ligand and temperature effects. J. Am. Chem. Soc. 133, 6578–6586 (2011).

  25. 25.

    Schliehe, C. et al. Ultrathin PbS sheets by two-dimensional oriented attachment. Science 329, 550–553 (2010).

  26. 26.

    Son, J. S. et al. Large-scale soft colloidal template synthesis of 1.4-nm-thick CdSe nanosheets. Angew. Chem. Int. Ed. 48, 6861–6864 (2009).

  27. 27.

    Liao, H. G. et al. Facet development during platinum nanocube growth. Science 345, 916–919 (2014).

  28. 28.

    Yuk, J. M. et al. High-resolution EM of colloidal nanocrystal growth using graphene liquid cells. Science 336, 61–64 (2012).

  29. 29.

    Li, D. et al. Direction-specific interactions control crystal growth by oriented attachment. Science 336, 1014–1018 (2012).

  30. 30.

    Hansen, P. L. et al. Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals. Science 295, 2053–2055 (2002).

  31. 31.

    Tian, N., Zhou, Z. Y., Sun, S.-G., Ding, Y. & Wang, Z. L. Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 316, 732–735 (2007).

  32. 32.

    Urban, J. J., Talapin, D. V., Shevchenko, E. V. & Murray, C. B. Self-assembly of PbTe quantum dots into nanocrystal superlattices and glassy films. J. Am. Chem. Soc. 128, 3248–3255 (2006).

  33. 33.

    Penn, R. L. & Banfield, J. F. Imperfect oriented attachment: dislocation generation in defect-free nanocrystals. Science 281, 969–971 (1998).

  34. 34.

    Gao, S. et al. Ultrahigh energy density realized by a single-layer beta-Co(OH)2 all-solid-state asymmetric supercapacitor. Angew. Chem. Int. Ed. 53, 12789–12793 (2014).

  35. 35.

    Sun, S. et al. Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles. J. Am. Chem. Soc. 126, 273–279 (2004).

  36. 36.

    Son, J. S. et al. Colloidal synthesis of ultrathin two-dimensional semiconductor nanocrystals. Adv. Mater. 23, 3214–3219 (2011).

  37. 37.

    Puntes, V. F., Zanchet, D., Erdonmez, C. K. & Alivisatos, A. P. Synthesis of hcp-Co nanodisks. J. Am. Chem. Soc. 124, 12874–12880 (2002).

  38. 38.

    Riedinger, A. et al. An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets. Nat. Mater. 16, 743–748 (2017).

  39. 39.

    Liang, W. I. et al. In situ study of spinel ferrite nanocrystal growth using liquid cell transmission electron microscopy. Chem. Mater. 27, 8146–8152 (2015).

  40. 40.

    Xia, Y. N., Xiong, Y. J., Lim, B. & Skrabalak, S. E. Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? Angew. Chem. Int. Ed. 48, 60–103 (2009).

  41. 41.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

  42. 42.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

  43. 43.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

  44. 44.

    Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006).

  45. 45.

    Redman, M. J. & Steward, E. G. Cobaltous oxide with the zinc blende/wurtzite-type crystal structure. Nature 193, 867 (1962).

  46. 46.

    Deng, H. X. et al. Origin of antiferromagnetism in CoO: a density functional theory study. Appl. Phys. Lett. 96, 162508–162510 (2010).

  47. 47.

    Imada, S. & Jo, T. Magnetic states of cobalt oxide and ferrites and magnetic dichroism in 2p-3d X-ray absorption spectroscopy. J. Magn. Magn. Mater. 104, 2001–2002 (1992).

  48. 48.

    van Elp, J. et al. Electronic structure of CoO, Li-doped CoO and LiCoO2. Phys. Rev. B 44, 6090–6103 (1991).

  49. 49.

    Schrön, A., Granovskij, M. & Bechstedt, F. Influence of on-site Coulomb interaction U on properties of MnO(001) 2 × 1 and NiO(001) 2 × 1 surfaces. J. Phys. Condens. Matter 25, 094006–094015 (2013).

Download references

Acknowledgements

This work was funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05-CH11231 within the in situ TEM programme (KC22ZH). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. J.Y. and J.Q. acknowledge funding support from the Natural Science Foundation of China (nos 51802251 and U1508201). J.Y. also acknowledges funding support from the China Scholarship Council (201506060073) and China Postdoctoral Science Foundation (2018M631168). This work used resources of the National Energy Research Scientific Computing Center and the Oak Ridge Leadership Computing Facility through the INCITE project. The authors thank D. Zherebetskyy (L.-W.W.'s group) for useful discussions.

Author information

J.Y. designed and performed the experiments and analysed the experimental data. J.K. and L.-W.W. performed the DFT calculations. Z.Z., X.Z. and C.Y. provided reagents and analysed data. S.B. carried out the measurements and calibration of liquid thickness in the liquid cells. C.C. and M.P. provided part of the TEM characterization. C.O. and K.B. helped with image processing and materials structure analyses. J.Y. and H.Z. wrote the manuscript. All authors contributed to the overall scientific interpretation and editing of the manuscript. J.Q. supervised part of the experimental work. L.-W.W. supervised the theory part of this work. All work was carried out under the supervision of H.Z.

Correspondence to Jieshan Qiu or Lin-Wang Wang or Haimei Zheng.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–24 Supplementary Tables 1–2 Supplementary video legends 1–8

Supplementary video 1

Shape evolution and the attachment of cobalt nickel oxide nanocrystals from abundant nanoparticles to the large nanosheets. The video plays 15 times faster than real time. The play rate is 3 frames s−1

Supplementary video 2

Shape evolution of cobalt nickel oxide nanocrystals from 3D nanoparticles to a 2D nanosheet. The video plays 15 times faster than real time. The play rate is 15 frames s−1.

Supplementary video 3

Shape evolution of cobalt oxide nanocrystals from 3D nanoparticles to a 2D nanosheet. The video plays 15 times faster than real time. The play rate is 15 frames s−1.

Supplementary video 4

The growth trajectories of the cobalt oxide nanosheet viewed along the [002] axis. The original video was recorded at 400 frames s−1 using a K2 IS camera. The sample drift in the original image sequence was corrected using custom developed MatLab scripts. The video plays in real time with a play rate of 10 frames s−1.

Supplementary video 5

Growth trajectories of the cobalt oxide nanosheet recorded at 400 frames s−1 using a K2 IS camera. The sample drift in the original image sequence was corrected using custom developed MatLab scripts. The video plays in real time with a play rate of 5 frames s−1.

Supplementary video 6

Growth trajectories of a cobalt oxide nanosheet viewed along the [002] axis when there is an adjacent nanocrystal. The original video was recorded at 400 frames s−1 using a K2 IS camera. The sample drift in the original image sequence was corrected using custom developed MatLab scripts. The video plays in real time with a play rate of 10 frames s−1.

Supplementary video 7

The attachment process of two cobalt oxide nanosheets recorded at 400 frames s−1 using a K2 IS camera. The sample drift in the original image sequence was corrected using custom developed MatLab scripts. The video plays in real time with a play rate of 6 frames s−1.

Supplementary video 8

The growth process of nickel oxide nanocrystals. The video plays in real time with a play rate of 5 frames s−1. The full frame is about 40 nm × 40 nm, and the cropped and enlarged region has a width of 7.5 nm.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark