skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

According to the article, 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.

Authors:
ORCiD logo; ; ORCiD logo; ; ; ; ; ; ORCiD logo; ; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1565754
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 18; Journal Issue: 9; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Materials Science; Physics

Citation Formats

Yang, Juan, Zeng, Zhiyuan, Kang, Jun, Betzler, Sophia, Czarnik, Cory, Zhang, Xiaowei, Ophus, Colin, Yu, Chang, Bustillo, Karen, Pan, Ming, Qiu, Jieshan, Wang, Lin-Wang, and Zheng, Haimei. Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates. United States: N. p., 2019. Web. doi:10.1038/s41563-019-0415-3.
Yang, Juan, Zeng, Zhiyuan, Kang, Jun, Betzler, Sophia, Czarnik, Cory, Zhang, Xiaowei, Ophus, Colin, Yu, Chang, Bustillo, Karen, Pan, Ming, Qiu, Jieshan, Wang, Lin-Wang, & Zheng, Haimei. Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates. United States. doi:10.1038/s41563-019-0415-3.
Yang, Juan, Zeng, Zhiyuan, Kang, Jun, Betzler, Sophia, Czarnik, Cory, Zhang, Xiaowei, Ophus, Colin, Yu, Chang, Bustillo, Karen, Pan, Ming, Qiu, Jieshan, Wang, Lin-Wang, and Zheng, Haimei. Mon . "Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates". United States. doi:10.1038/s41563-019-0415-3.
@article{osti_1565754,
title = {Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates},
author = {Yang, Juan and Zeng, Zhiyuan and Kang, Jun and Betzler, Sophia and Czarnik, Cory and Zhang, Xiaowei and Ophus, Colin and Yu, Chang and Bustillo, Karen and Pan, Ming and Qiu, Jieshan and Wang, Lin-Wang and Zheng, Haimei},
abstractNote = {According to the article, 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.},
doi = {10.1038/s41563-019-0415-3},
journal = {Nature Materials},
issn = {1476-1122},
number = 9,
volume = 18,
place = {United States},
year = {2019},
month = {7}
}

Works referenced in this record:

Catalysis with two-dimensional materials and their heterostructures
journal, March 2016

  • Deng, Dehui; Novoselov, K. S.; Fu, Qiang
  • Nature Nanotechnology, Vol. 11, Issue 3
  • DOI: 10.1038/nnano.2015.340

Photodetectors based on graphene, other two-dimensional materials and hybrid systems
journal, October 2014

  • Koppens, F. H. L.; Mueller, T.; Avouris, Ph.
  • Nature Nanotechnology, Vol. 9, Issue 10
  • DOI: 10.1038/nnano.2014.215

Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide
journal, September 2013


Fine Structure Constant Defines Visual Transparency of Graphene
journal, June 2008


Transition Metal Dichalcogenides and Beyond: Synthesis, Properties, and Applications of Single- and Few-Layer Nanosheets
journal, December 2014

  • Lv, Ruitao; Robinson, Joshua A.; Schaak, Raymond E.
  • Accounts of Chemical Research, Vol. 48, Issue 1
  • DOI: 10.1021/ar5002846

Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials
journal, February 2011


The rise of graphene
journal, March 2007

  • Geim, A. K.; Novoselov, K. S.
  • Nature Materials, Vol. 6, Issue 3, p. 183-191
  • DOI: 10.1038/nmat1849

General Insights into Structural Evolution of Layered Double Hydroxide: Underlying Aspects in Topochemical Transformation from Brucite to Layered Double Hydroxide
journal, November 2012

  • Ma, Renzhi; Liang, Jianbo; Liu, Xiaohe
  • Journal of the American Chemical Society, Vol. 134, Issue 48
  • DOI: 10.1021/ja310246r

Ultrathin Two-Dimensional Inorganic Materials: New Opportunities for Solid State Nanochemistry
journal, December 2014

  • Sun, Yongfu; Gao, Shan; Lei, Fengcai
  • Accounts of Chemical Research, Vol. 48, Issue 1
  • DOI: 10.1021/ar500164g

Recent Advances in the Synthesis and Application of Layered Double Hydroxide (LDH) Nanosheets
journal, March 2012

  • Wang, Qiang; O’Hare, Dermot
  • Chemical Reviews, Vol. 112, Issue 7
  • DOI: 10.1021/cr200434v

Two-Dimensional Oxide and Hydroxide Nanosheets: Controllable High-Quality Exfoliation, Molecular Assembly, and Exploration of Functionality
journal, December 2014

  • Ma, Renzhi; Sasaki, Takayoshi
  • Accounts of Chemical Research, Vol. 48, Issue 1
  • DOI: 10.1021/ar500311w

Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets
journal, March 2017

  • Jeon, Mi Young; Kim, Donghun; Kumar, Prashant
  • Nature, Vol. 543, Issue 7647
  • DOI: 10.1038/nature21421

Intercalation Complexes of Lewis Bases and Layered Sulfides: A Large Class of New Superconductors
journal, October 1971


Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel
journal, January 2016


Freestanding palladium nanosheets with plasmonic and catalytic properties
journal, December 2010

  • Huang, Xiaoqing; Tang, Shaoheng; Mu, Xiaoliang
  • Nature Nanotechnology, Vol. 6, Issue 1
  • DOI: 10.1038/nnano.2010.235

Novel polymer-free iridescent lamellar hydrogel for two-dimensional confined growth of ultrathin gold membranes
journal, February 2014

  • Niu, Jian; Wang, Dong; Qin, Haili
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4313

Ultrathin Pt–Cu Nanosheets and Nanocones
journal, November 2013

  • Saleem, Faisal; Zhang, Zhicheng; Xu, Biao
  • Journal of the American Chemical Society, Vol. 135, Issue 49
  • DOI: 10.1021/ja4101968

Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets
journal, May 2014

  • Sun, Ziqi; Liao, Ting; Dou, Yuhai
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4813

Unique Excavated Rhombic Dodecahedral PtCu 3 Alloy Nanocrystals Constructed with Ultrathin Nanosheets of High-Energy {110} Facets
journal, February 2014

  • Jia, Yanyan; Jiang, Yaqi; Zhang, Jiawei
  • Journal of the American Chemical Society, Vol. 136, Issue 10
  • DOI: 10.1021/ja413209q

Size/Shape-Controlled Synthesis of Colloidal CdSe Quantum Disks: Ligand and Temperature Effects
journal, May 2011

  • Li, Zheng; Peng, Xiaogang
  • Journal of the American Chemical Society, Vol. 133, Issue 17
  • DOI: 10.1021/ja108145c

Ultrathin PbS Sheets by Two-Dimensional Oriented Attachment
journal, July 2010


Large-Scale Soft Colloidal Template Synthesis of 1.4 nm Thick CdSe Nanosheets
journal, September 2009

  • Son, Jae Sung; Wen, Xiao-Dong; Joo, Jin
  • Angewandte Chemie International Edition, Vol. 48, Issue 37
  • DOI: 10.1002/anie.200902791

Facet development during platinum nanocube growth
journal, August 2014


High-Resolution EM of Colloidal Nanocrystal Growth Using Graphene Liquid Cells
journal, April 2012


Direction-Specific Interactions Control Crystal Growth by Oriented Attachment
journal, May 2012


Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
journal, March 2002


Synthesis of Tetrahexahedral Platinum Nanocrystals with High-Index Facets and High Electro-Oxidation Activity
journal, May 2007


Self-Assembly of PbTe Quantum Dots into Nanocrystal Superlattices and Glassy Films
journal, March 2006

  • Urban, Jeffrey J.; Talapin, Dmitri V.; Shevchenko, Elena V.
  • Journal of the American Chemical Society, Vol. 128, Issue 10
  • DOI: 10.1021/ja058269b

Imperfect Oriented Attachment: Dislocation Generation in Defect-Free Nanocrystals
journal, August 1998


Ultrahigh Energy Density Realized by a Single-Layer β-Co(OH) 2 All-Solid-State Asymmetric Supercapacitor
journal, September 2014

  • Gao, Shan; Sun, Yongfu; Lei, Fengcai
  • Angewandte Chemie International Edition, Vol. 53, Issue 47
  • DOI: 10.1002/anie.201407836

Monodisperse MFe 2 O 4 (M = Fe, Co, Mn) Nanoparticles
journal, January 2004

  • Sun, Shouheng; Zeng, Hao; Robinson, David B.
  • Journal of the American Chemical Society, Vol. 126, Issue 1
  • DOI: 10.1021/ja0380852

Synthesis of hcp-Co Nanodisks
journal, October 2002

  • Puntes, Victor F.; Zanchet, Daniela; Erdonmez, Can K.
  • Journal of the American Chemical Society, Vol. 124, Issue 43
  • DOI: 10.1021/ja027262g

An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets
journal, April 2017

  • Riedinger, Andreas; Ott, Florian D.; Mule, Aniket
  • Nature Materials, Vol. 16, Issue 7
  • DOI: 10.1038/nmat4889

In Situ Study of Spinel Ferrite Nanocrystal Growth Using Liquid Cell Transmission Electron Microscopy
journal, November 2015


Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
  • Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
  • DOI: 10.1002/anie.200802248

Projector augmented-wave method
journal, December 1994


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Cobaltous Oxide with the Zinc Blende/Wurtzite-type Crystal Structure
journal, March 1962

  • Redman, M. J.; Steward, E. G.
  • Nature, Vol. 193, Issue 4818
  • DOI: 10.1038/193867a0

Origin of antiferromagnetism in CoO: A density functional theory study
journal, April 2010

  • Deng, Hui-Xiong; Li, Jingbo; Li, Shu-Shen
  • Applied Physics Letters, Vol. 96, Issue 16
  • DOI: 10.1063/1.3402772

Electronic structure of CoO, Li-doped CoO, and LiCoO 2
journal, September 1991


Influence of on-site Coulomb interaction U on properties of MnO(001)2 × 1 and NiO(001)2 × 1 surfaces
journal, February 2013