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Title: Synthesis of Two-Dimensional Materials by Selective Extraction

Abstract

Two-dimensional (2D) materials have attracted much attention in the past decade. They offer high specific surface area, as well as electronic structure and properties that differ from their bulk counterparts due to the low dimensionality. Graphene is the best known and the most studied 2D material, but metal oxides and hydroxides (including clays), dichalcogenides, boron nitride (BN), and other materials that are one or several atoms thick are receiving increasing attention. They may deliver a combination of properties that cannot be provided by other materials. The most common synthesis approach in general is by reacting different elements or compounds to form a new compound. However, this approach does not necessarily work well for low-dimensional structures, since it favors formation of energetically preferred 3D (bulk) solids. Many 2D materials are produced by exfoliation of van der Waals solids, such as graphite or MoS2, breaking large particles into 2D layers. However, these approaches are not universal; for example, 2D transition metal carbides cannot be produced by any of them. An alternative but less studied way of material synthesis is the selective extraction process, which is based on the difference in reactivity and stability between the different components (elements or structural units) ofmore » the original material. It can be achieved using thermal, chemical, or electrochemical processes. Many 2D materials have been synthesized using selective extraction, such as graphene from SiC, transition metal oxides (TMO) from layered 3D salts, and transition metal carbides or carbonitrides (MXenes) from MAX phases. Selective extraction synthesis is critically important when the bonds between the building blocks of the material are too strong (e.g., in carbides) to be broken mechanically in order to form nanostructures. Unlike extractive metallurgy, where the extracted metal is the goal of the process, selective extraction of one or more elements from the precursor materials releases 2D structures. In this Account, in addition to graphene and TMO, we focused on MXenes as an example for the use of selective extraction synthesis to produce novel 2D materials. About 10 new carbides and carbonitrides of transition metals have been produced by this method in the past 3 years. They offer an unusual combination of metallic conductivity and hydrophilicity and show very attractive electrochemical properties. We hope that this Account will encourage researchers to extend the use of selective extraction to other layered material systems that in turn will result in expanding the world of nanomaterials in general and 2D materials in particular, generating new materials that cannot be produced by other means.« less

Authors:
 [1];  [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Div.
  2. Drexel Univ., Philadelphia, PA (United States). A. J. Drexel Nanomaterials Inst. and Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1185695
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 48; Journal Issue: 1; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Naguib, Michael, and Gogotsi, Yury. Synthesis of Two-Dimensional Materials by Selective Extraction. United States: N. p., 2014. Web. doi:10.1021/ar500346b.
Naguib, Michael, & Gogotsi, Yury. Synthesis of Two-Dimensional Materials by Selective Extraction. United States. https://doi.org/10.1021/ar500346b
Naguib, Michael, and Gogotsi, Yury. Tue . "Synthesis of Two-Dimensional Materials by Selective Extraction". United States. https://doi.org/10.1021/ar500346b. https://www.osti.gov/servlets/purl/1185695.
@article{osti_1185695,
title = {Synthesis of Two-Dimensional Materials by Selective Extraction},
author = {Naguib, Michael and Gogotsi, Yury},
abstractNote = {Two-dimensional (2D) materials have attracted much attention in the past decade. They offer high specific surface area, as well as electronic structure and properties that differ from their bulk counterparts due to the low dimensionality. Graphene is the best known and the most studied 2D material, but metal oxides and hydroxides (including clays), dichalcogenides, boron nitride (BN), and other materials that are one or several atoms thick are receiving increasing attention. They may deliver a combination of properties that cannot be provided by other materials. The most common synthesis approach in general is by reacting different elements or compounds to form a new compound. However, this approach does not necessarily work well for low-dimensional structures, since it favors formation of energetically preferred 3D (bulk) solids. Many 2D materials are produced by exfoliation of van der Waals solids, such as graphite or MoS2, breaking large particles into 2D layers. However, these approaches are not universal; for example, 2D transition metal carbides cannot be produced by any of them. An alternative but less studied way of material synthesis is the selective extraction process, which is based on the difference in reactivity and stability between the different components (elements or structural units) of the original material. It can be achieved using thermal, chemical, or electrochemical processes. Many 2D materials have been synthesized using selective extraction, such as graphene from SiC, transition metal oxides (TMO) from layered 3D salts, and transition metal carbides or carbonitrides (MXenes) from MAX phases. Selective extraction synthesis is critically important when the bonds between the building blocks of the material are too strong (e.g., in carbides) to be broken mechanically in order to form nanostructures. Unlike extractive metallurgy, where the extracted metal is the goal of the process, selective extraction of one or more elements from the precursor materials releases 2D structures. In this Account, in addition to graphene and TMO, we focused on MXenes as an example for the use of selective extraction synthesis to produce novel 2D materials. About 10 new carbides and carbonitrides of transition metals have been produced by this method in the past 3 years. They offer an unusual combination of metallic conductivity and hydrophilicity and show very attractive electrochemical properties. We hope that this Account will encourage researchers to extend the use of selective extraction to other layered material systems that in turn will result in expanding the world of nanomaterials in general and 2D materials in particular, generating new materials that cannot be produced by other means.},
doi = {10.1021/ar500346b},
journal = {Accounts of Chemical Research},
number = 1,
volume = 48,
place = {United States},
year = {Tue Dec 09 00:00:00 EST 2014},
month = {Tue Dec 09 00:00:00 EST 2014}
}

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  • Advanced Energy Materials, Vol. 7, Issue 23
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Simultaneous Preparation and Functionalization of 2D Materials Assisted by Amphiphilic MoS 2 Nanosheets
journal, December 2016

  • Shen, Jianfeng; Pei, Yu; Wang, Man
  • Advanced Materials Interfaces, Vol. 4, Issue 4
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Elastic properties of 2D Ti 3 C 2 T x MXene monolayers and bilayers
journal, June 2018

  • Lipatov, Alexey; Lu, Haidong; Alhabeb, Mohamed
  • Science Advances, Vol. 4, Issue 6
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Strain engineering of phonon thermal transport properties in monolayer 2H-MoTe 2
journal, January 2017

  • Shafique, Aamir; Shin, Young-Han
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 47
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Synthesis of novel nanomaterials and their application in efficient removal of radionuclides
journal, June 2019


Recent Advances in Layered Ti 3 C 2 T x MXene for Electrochemical Energy Storage
journal, February 2018


Nanoscale Elastic Changes in 2D Ti 3 C 2 T x (MXene) Pseudocapacitive Electrodes
journal, March 2016

  • Come, Jeremy; Xie, Yu; Naguib, Michael
  • Advanced Energy Materials, Vol. 6, Issue 9
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Recent Advances in Chemical Functionalization of 2D Black Phosphorous Nanosheets
journal, November 2019


Penta-graphene: A new carbon allotrope
journal, February 2015

  • Zhang, Shunhong; Zhou, Jian; Wang, Qian
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 8
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Antiferromagnetic monolayer MnC 2 with density functional theory prediction
journal, April 2018

  • Zhang, Bingwen; Zhang, Qinfang; Bai, Yujie
  • Journal of Physics: Condensed Matter, Vol. 30, Issue 17
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Fluoride‐Free Synthesis of Two‐Dimensional Titanium Carbide (MXene) Using A Binary Aqueous System
journal, November 2018

  • Yang, Sheng; Zhang, Panpan; Wang, Faxing
  • Angewandte Chemie International Edition, Vol. 57, Issue 47
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Macroporous three-dimensional MXene architectures for highly efficient solar steam generation
journal, January 2019

  • Zhao, Xing; Zha, Xiang-Jun; Pu, Jun-Hong
  • Journal of Materials Chemistry A, Vol. 7, Issue 17
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Electrochemical Reduction of TiO 2 /Al 2 O 3 /C to Ti 3 AlC 2 and Its Derived Two-Dimensional (2D) Carbides
journal, January 2018

  • Li, Shangshu; Zou, Xingli; Hu, Yong
  • Journal of The Electrochemical Society, Vol. 165, Issue 3
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Layered Orthorhombic Nb 2 O 5 @Nb 4 C 3 T x and TiO 2 @Ti 3 C 2 T x Hierarchical Composites for High Performance Li-ion Batteries
journal, May 2016

  • Zhang, Chuanfang John; Kim, Seon Joon; Ghidiu, Michael
  • Advanced Functional Materials, Vol. 26, Issue 23
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Nanoengineering of 2D MXene‐Based Materials for Energy Storage Applications
journal, July 2019


3D Metal Carbide@Mesoporous Carbon Hybrid Architecture as a New Polysulfide Reservoir for Lithium-Sulfur Batteries
journal, October 2016

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  • Advanced Functional Materials, Vol. 26, Issue 47
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Insight into In Situ Amphiphilic Functionalization of Few-Layered Transition Metal Dichalcogenide Nanosheets
journal, August 2016


Organic-Base-Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance
journal, October 2016

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  • Angewandte Chemie International Edition, Vol. 55, Issue 47
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Front-End-of-Line Integration of Graphene Oxide for Graphene-Based Electrical Platforms
journal, January 2018

  • Lu, Xiaoling; Munief, Walid-Madhat; Heib, Florian
  • Advanced Materials Technologies, Vol. 3, Issue 4
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Raman study of 2D anatase TiO 2 nanosheets
journal, January 2016

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  • Phys. Chem. Chem. Phys., Vol. 18, Issue 47
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Two‐Dimensional Electrocatalysts for Efficient Reduction of Carbon Dioxide
journal, October 2019


Configurable multi-state non-volatile memory behaviors in Ti 3 C 2 nanosheets
journal, January 2019

  • Ding, Guanglong; Zeng, Kelin; Zhou, Kui
  • Nanoscale, Vol. 11, Issue 15
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Ultrathin MXene-Micropattern-Based Field-Effect Transistor for Probing Neural Activity
journal, February 2016


Ultrathin 2D Nanomaterials for Electromagnetic Interference Shielding
journal, November 2019


Binder-free 2D titanium carbide (MXene)/carbon nanotube composites for high-performance lithium-ion capacitors
journal, January 2018


2D magnetic titanium carbide MXene for cancer theranostics
journal, January 2018

  • Liu, Zhuang; Zhao, Menglong; Lin, Han
  • Journal of Materials Chemistry B, Vol. 6, Issue 21
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2D visible-light-driven TiO2@Ti3C2/g-C3N4 ternary heterostructure for high photocatalytic activity
journal, March 2019


Two-Dimensional Nanostructured Materials for Gas Sensing
journal, August 2017

  • Liu, Xianghong; Ma, Tiantian; Pinna, Nicola
  • Advanced Functional Materials, Vol. 27, Issue 37
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Heterogeneous Nanostructures for Sodium Ion Batteries and Supercapacitors
journal, September 2015


A Cr 2 CO 2 monolayer as a promising cathode for lithium and non-lithium ion batteries: a computational exploration
journal, January 2016

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Effect of Synthesis on Quality, Electronic Properties and Environmental Stability of Individual Monolayer Ti 3 C 2 MXene Flakes
journal, November 2016

  • Lipatov, Alexey; Alhabeb, Mohamed; Lukatskaya, Maria R.
  • Advanced Electronic Materials, Vol. 2, Issue 12
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Fluoride‐Free Synthesis of Two‐Dimensional Titanium Carbide (MXene) Using A Binary Aqueous System
journal, November 2018


Interwoven MXene Nanosheet/Carbon-Nanotube Composites as Li-S Cathode Hosts
journal, November 2016

  • Liang, Xiao; Rangom, Yverick; Kwok, Chun Yuen
  • Advanced Materials, Vol. 29, Issue 3
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Layered BiOBr/Ti3C2 MXene composite with improved visible-light photocatalytic activity
journal, October 2018


A Two-Dimensional Zirconium Carbide by Selective Etching of Al 3 C 3 from Nanolaminated Zr 3 Al 3 C 5
journal, March 2016

  • Zhou, Jie; Zha, Xianhu; Chen, Fan Y.
  • Angewandte Chemie International Edition, Vol. 55, Issue 16
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Emergent Pseudocapacitance of 2D Nanomaterials
journal, February 2018


A facile method for synthesizing CuS decorated Ti 3 C 2 MXene with enhanced performance for asymmetric supercapacitors
journal, January 2019

  • Pan, Zhihu; Cao, Fa; Hu, Xing
  • Journal of Materials Chemistry A, Vol. 7, Issue 15
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Facile Solution Processing of Stable MXene Dispersions towards Conductive Composite Fibers
journal, July 2019

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  • Global Challenges, Vol. 3, Issue 10
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Nanolaminated composite materials: structure, interface role and applications
journal, January 2016

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Layered Ti 3 C 2 MXene modified two-dimensional Bi 2 WO 6 composites with enhanced visible light photocatalytic performance
journal, January 2019

  • Zhao, Danxia; Cai, Chun
  • Materials Chemistry Frontiers, Vol. 3, Issue 11
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Emerging Two‐Dimensional Nanomaterials for Cancer Therapy
journal, August 2019


Novel elastic, lattice dynamics and thermodynamic properties of metallic single-layer transition metal phosphides: 2H- M 2 P (Mo 2 P, W 2 P, Nb 2 P and Ta 2 P)
journal, March 2018

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  • Journal of Physics: Condensed Matter, Vol. 30, Issue 13
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A high-performance trace level acetone sensor using an indispensable V 4 C 3 T x MXene
journal, January 2020

  • Zhao, Wei-Na; Yun, Na; Dai, Zhen-Hua
  • RSC Advances, Vol. 10, Issue 3
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Layered ternary M n +1 AX n phases and their 2D derivative MXene: an overview from a thin-film perspective
journal, February 2017

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Penta-BxNy sheet: a density functional theory study of two-dimensional material
journal, August 2016

  • Li, Jiao; Fan, Xinyu; Wei, Yanpei
  • Scientific Reports, Vol. 6, Issue 1
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2D Ultrathin MXene-Based Drug-Delivery Nanoplatform for Synergistic Photothermal Ablation and Chemotherapy of Cancer
journal, February 2018

  • Han, Xiaoxia; Huang, Ju; Lin, Han
  • Advanced Healthcare Materials, Vol. 7, Issue 9
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Review of MXenes as new nanomaterials for energy storage/delivery and selected environmental applications
journal, October 2018


Graphene for batteries, supercapacitors and beyond
journal, May 2016


Two-Step Oxidation of Mxene in the Synthesis of Layer-Stacked Anatase Titania with Enhanced Lithium-Storage Performance
journal, April 2016


Electronic and Optical Properties of 2D Transition Metal Carbides and Nitrides (MXenes)
journal, November 2018


Pristine Titanium Carbide MXene Films with Environmentally Stable Conductivity and Superior Mechanical Strength
journal, November 2019

  • Chen, Hongwu; Wen, Yeye; Qi, Yingyi
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Surface Tension Components Based Selection of Cosolvents for Efficient Liquid Phase Exfoliation of 2D Materials
journal, April 2016


VC 2 and V 1/2 Mn 1/2 C 2 nanosheets with robust mechanical and thermal properties as promising materials for Li-ion batteries
journal, January 2019

  • Zhang, Bingwen; Zhang, Weiyi; Meng, Qiangqiang
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 3
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Synthesis and Electrochemical Properties of Two-Dimensional RGO/Ti3C2Tx Nanocomposites
journal, January 2018

  • Shen, Changjie; Wang, Libo; Zhou, Aiguo
  • Nanomaterials, Vol. 8, Issue 2
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In situ atomistic insight into the growth mechanisms of single layer 2D transition metal carbides
journal, June 2018


Recent advances in MXene: Preparation, properties, and applications
journal, June 2015


A New Family of Two‐Dimensional Topological Materials: CdX (X = F, Cl, Br, and I)
journal, January 2019

  • Yi, Xiao; Wang, Wei; Zhou, Pan
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Two‐dimensional MXenes for lithium‐sulfur batteries
journal, January 2020

  • Zhang, Chuanfang (John); Cui, Linfan; Abdolhosseinzadeh, Sina
  • InfoMat, Vol. 2, Issue 4
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Photoluminescent Ti 3 C 2 MXene Quantum Dots for Multicolor Cellular Imaging
journal, February 2017


Fluorine-Free Synthesis of High-Purity Ti 3 C 2 T x (T=OH, O) via Alkali Treatment
journal, April 2018

  • Li, Tengfei; Yao, Lulu; Liu, Qinglei
  • Angewandte Chemie International Edition, Vol. 57, Issue 21
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The strategies of advanced cathode composites for lithium-sulfur batteries
journal, January 2017

  • Zhou, Kuan; Fan, XiaoJing; Wei, XiangFeng
  • Science China Technological Sciences, Vol. 60, Issue 2
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Experimental and theoretical calculation investigation on efficient Pb( ii ) adsorption on etched Ti 3 AlC 2 nanofibers and nanosheets
journal, January 2018

  • Gu, Pengcheng; Xing, Jinlu; Wen, Tao
  • Environmental Science: Nano, Vol. 5, Issue 4
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Interfacial competition between a borophene-based cathode and electrolyte for the multiple-sulfide immobilization of a lithium sulfur battery
journal, January 2019

  • Rao, Dewei; Liu, Xiaojing; Yang, Huan
  • Journal of Materials Chemistry A, Vol. 7, Issue 12
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Front-End-of-Line Integration of Graphene Oxide for Graphene-Based Electrical Platforms
collection, January 2018

  • Lu, Xiaoling; Munief, Walid-Madhat; Heib, Florian
  • Universität des Saarlandes
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Penta-Graphene: a new Carbon Allotrope
journal, December 2015

  • Zhang, Shunhong; Zhou, Jian; Wang, Qian
  • Radioelectronics. Nanosystems. Information Technologies., Vol. 7, Issue 2
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Facile Solution Processing of Stable MXene Dispersions towards Conductive Composite Fibers
journal, July 2019

  • Seyedin, Shayan; Zhang, Jizhen; Usman, Ken Aldren S.
  • Global Challenges, Vol. 3, Issue 10
  • DOI: 10.1002/gch2.201900037

Penta-BxNy sheet: a density functional theory study of two-dimensional material
journal, August 2016

  • Li, Jiao; Fan, Xinyu; Wei, Yanpei
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep31840

Synthesis and Electrochemical Properties of Two-Dimensional RGO/Ti3C2Tx Nanocomposites
journal, January 2018

  • Shen, Changjie; Wang, Libo; Zhou, Aiguo
  • Nanomaterials, Vol. 8, Issue 2
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Electrical Properties of Two-Dimensional Materials Used in Gas Sensors
journal, March 2019