Layered intercalation compounds: Mechanisms, new methodologies, and advanced applications

https://doi.org/10.1016/j.pmatsci.2019.100631Get rights and content

Abstract

The structural characteristics of two-dimensional (2-D) materials result in unique physical, electronic, chemical, and optical properties, making them potentially useful in a wide range of applications. These unique properties can be fine-tuned and enhanced via intercalation, expanding the applications of various 2-D intercalation compounds to a much wider scope. This article aims to provide an overview of innovations in the field of intercalation chemistry of 2-D intercalation materials, as well as to highlight their leading applications. A brief perspective on the intercalation of 2-D layered compounds is provided, focusing on mechanisms, approaches, and influential factors involving intercalation. Insights into the potential applications, challenges, and future opportunities of 2-D intercalated materials are discussed.

Introduction

Two-dimensional (2-D) layered materials such as graphene are currently a topic of intense interest because of their extraordinary physical and chemical properties [1], [2], [3], [4], [5]. 2-D layered materials share similar overall planar-like structures, with different sheet composition and crystal structure as the distinguishing features. The materials are in general characterized by strong intralayer bonding and weak interlayer interactions. The layers may be electrically neutral, or may be positively or negatively charged [6], [7], [8], [9], [10]. For neutral layered compounds, including graphite and some metal chalcogenides, metal oxides, and metal halides, the layers are held together via Van der Waals, π-stacking, or other noncovalent interactions, and the interlayer space is a network of empty lattice sites [11], [12]. For positively charged (such as layered double hydroxides (LDHs)) or negatively charged (such as metal phosphates, phosphonates, and silicates) layered materials, the layers are primarily held together by electrostatic forces and the interlayer space is filled by counter ions or by a combination of ions and solvent molecules such as water [13], [14]. Among the various 2-D materials, those with an intercalated structure have dominated the research due to their potential to offer unique properties through the combination of distinct features of guests (i.e., the intercalants) and hosts (i.e., the layers) within a single composite [15], [16]. Additionally, the interactions between guest and host may lead to new or enhanced phenomena, e.g., enhanced electronic, photonic and optoelectronic, thermal and thermoelectric, magnetic, and catalytic properties [1], [17], [18], [19], [20], [21]. Over the past few decades, there have been significant advancements in the understanding of intercalation chemistry [15], as well as the applications of intercalation materials, including, but not limited to, energy conversion and storage [22], [23], [24], [25], medical applications [26], [27], catalysis [1], [15], [28], sensors [29], display systems [15], nuclear waste treatment [30], and environmental remediation [13], [31], [32], [33].

The phenomenon of intercalation was first discovered ca. 600–700 CE in China [34]. At that time, Chinese researchers intercalated alkali metal ions into natural minerals, such as kaolin, to make porcelain [35]. The first intercalation phenomenon was reported in the literature in 1840 by Schafhäutl [36], in which it was attempted to dissolve graphite in sulfuric acid [36]. The modern era of intercalation research was initiated by a paper in 1926 by Fredenhagen et al., in which the uptake of potassium vapor into graphite was reported [37]. Since then, intercalation reactions have continued to fascinate chemists and material scientists.

To date, various approaches to achieve intercalation have been developed based on different physical and chemical reaction/interaction mechanisms [15], [16]. In addition, several key factors that influence the intercalation process have been verified, such as interlayer spacing and its regularity [38], [39]. The growing knowledge of intercalation mechanisms and influential factors has led to the attainment of intercalations at various interfaces, including solid-solid, solid-liquid, and solid-gas interfaces [15], [16], [40]. In some cases, the desired intercalated structure may be achieved in a single step by directly intercalating a layered host; however, some guest species are difficult or impossible to be directly intercalated because of size mismatch and/or lack of driving force. To solve such issues, usually multiple driving forces and/or multiple steps are necessary to achieve intercalation. Some non-conventional methods, including top down layer-by-layer self-assembly and one-step co-assembly methods, as well as bottom up synthetic methods have also been developed to address some special needs [15], [41].

In this review, we first give a brief perspective on the intercalation of 2-D layered materials concerning intercalation mechanisms, methodologies, and influential factors which may be paramount in better facilitating the development of new intercalation processes and novel and unique 2-D intercalation materials. We categorize the methodologies of the intercalation of 2-D materials into three groups: conventional intercalation methods, top down, and bottom up strategies (Fig. 1). Conventional methods generally utilize diffusion, ion exchange, intermolecular forces, acid-base reaction, electrochemical and redox-reactions, and some external factors to intercalate pre-existing 2-D materials. The section on top down and bottom up approaches will focus on the non-conventional intercalation strategies of layer-by-layer self-assembly, one-step co-assembly, and in situ one-pot synthesis of intercalation materials, among others. Finally, insights into the potential applications, challenges, and future opportunities of 2-D intercalated materials will be discussed.

Section snippets

Fundamental mechanisms and the corresponding intercalation approaches

In this part, we focus on the conventional intercalation methodologies of 2-D materials (as shown in Fig. 1a). The intercalation process consists of the insertion of molecules or ions (collectively referred to as the “guests”) into the interlayer of layered solids (collectively referred to as the “hosts”), resulting in the intercalation materials. The majority of intercalations rely on reactions/interactions between the guest and the host, including ion-exchange, acid-base reaction, hydrogen

Nonconventional techniques to achieve intercalation

As described in Fig. 1b and c, in addition to conventional intercalation approaches, special strategies of top down and bottom up have also been developed to prepare hybrids with an intercalated structure. Herein, we highlight a few representative top down strategies (including layer-by-layer self-assembly and one-step co-assembly) and bottom up methods (including in situ one-pot synthesis and calcination-rehydration approach).

Factors influencing the intercalation process

Interlayer distance is by far the most critical factor influencing the intercalation process and the ultimate results, as discussed in various examples above. Apart from interlayer distance, several other factors, such as arrangement of guests in the interlayer space, regularity of interlayer space, layer rigidity, among others, play an important role in intercalation.

Applications of intercalation compounds

The structural characteristics of 2-D materials result in unique physical, chemical, electronic, and optical properties, making them promising in a wide range of applications. Furthermore, the unique properties of individual 2-D materials can be fine-tuned and enhanced via intercalation [1]. With the rapid development in intercalation chemistry, the applications of various intercalation compounds are expected to become much wider in the near future. Herein, rather than giving a comprehensive

Summary and outlook

In summary, we highlighted the intercalation chemistry of 2-D materials. Various intercalation mechanisms, approaches, and influential factors, as well as potential applications of 2-D intercalation materials are discussed. The various intercalation mechanisms and the corresponding conventional intercalation methodologies based on reactions/interactions between the guest species and the host layered materials, including ion-exchange, acid-base reaction, hydrogen bonding, redox and

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

L. Sun acknowledges the support from the National Science Foundation (CMMI-1562907). B. R. Martin acknowledges the support from the National Science Foundation (DMR-1205670). R. Zhu acknowledges the support from the National Natural Science Foundation of China (41572031). M. Laipan thanks the National Natural Science Foundation of China (41902039), the China Postdoctoral Science Foundation (2018M640832), and the China Scholarship Council (CSC) for financial support. The authors thank Anna Marie

References (278)

  • R. Zhu et al.

    Structure of surfactant-clay complexes and their sorptive characteristics toward HOCs

    Sep Purif Technol

    (2008)
  • R. Zhu et al.

    Structure of cetyltrimethylammonium intercalated hydrobiotite

    Appl Clay Sci

    (2008)
  • J. Zhu et al.

    Superior thermal stability of Keggin-Al-30 pillared montmorillonite: a comparative study with Keggin-Al-13 pillared montmorillonite

    Microporous Mesoporous Mater

    (2018)
  • H. He et al.

    Synthesis of organoclays: a critical review and some unresolved issues

    Appl Clay Sci

    (2014)
  • A. Kimouche et al.

    Modulating charge density and inelastic optical response in graphene by atmospheric pressure localized intercalation through wrinkles

    Carbon

    (2014)
  • S. Omwoma et al.

    Recent advances on polyoxometalates intercalated layered double hydroxides: from synthetic approaches to functional material applications

    Coord Chem Rev

    (2014)
  • R. Zhao et al.

    Tetramethyl ammonium cation intercalated layered birnessite manganese dioxide for high-performance intercalation pseudocapacitor

    J Power Sources

    (2017)
  • H. He et al.

    Organoclays prepared from montmorillonites with different cation exchange capacity and surfactant configuration

    Appl Clay Sci

    (2010)
  • R. Zhu et al.

    Structural and sorptive characteristics of the cetyltrimethylammonium and polyacrylamide modified bentonite

    Chem Eng J

    (2010)
  • J. Zhu et al.

    Novel polymer/surfactant modified montmorillonite hybrids and the implications for the treatment of hydrophobic organic compounds in wastewaters

    Appl Clay Sci

    (2011)
  • J. Zhu et al.

    Expansion characteristics of organo montmorillonites during the intercalation, aging, drying and rehydration processes: effect of surfactant/CEC ratio

    Colloids Surf A

    (2011)
  • J. Zhu et al.

    Keggin-Al 30 pillared montmorillonite

    Microporous Mesoporous Mater

    (2017)
  • L. Li et al.

    Photophysical properties of donor-∏-acceptor azoic chromophores adsorbed and intercalated into Mg Al LDH

    J Solid State Chem

    (2013)
  • J.-J. Lin et al.

    Hydrogen-bond driven intercalation of synthetic fluorinated mica by poly(oxypropylene)-amidoamine salts

    Colloids Surf A

    (2007)
  • J. Zhu et al.

    Novel intercalation mechanism of zwitterionic surfactant modified montmorillonites

    Appl Clay Sci

    (2017)
  • H. Hongping et al.

    Infrared study of HDTMA+ intercalated montmorillonite

    Spectrochim Acta Part A

    (2004)
  • Y. Xi et al.

    Infrared spectroscopy of organoclays synthesized with the surfactant octadecyltrimethylammonium bromide

    Spectrochim Acta Part A

    (2005)
  • A. Clearfield et al.

    On the mechanism of ion exchange in zirconium phosphates—XXI intercalation of amines by α-zirconium phosphate

    J Inorg Nucl Chem

    (1979)
  • Q. Wang et al.

    Studies in surface science and catalysis

  • C. Depege et al.

    Synthesis and characterization of new copper-chromium layered double hydroxides pillared with polyoxovanadates

    J Solid State Chem

    (1996)
  • M. Li et al.

    Acid leaching of black shale for the extraction of vanadium

    Int J Miner Process

    (2010)
  • X. Li et al.

    Methoxy-grafted kaolinite preparation by intercalation of methanol: Mechanism of its structural variability

    Appl Clay Sci

    (2017)
  • J. Hooley et al.

    The effect of sample shape on the bromination of graphite

    Carbon

    (1965)
  • J. Wan et al.

    Tuning two-dimensional nanomaterials by intercalation: materials, properties and applications

    Chem Soc Rev

    (2016)
  • M. Laipan et al.

    Functionalized layered double hydroxides for innovative applications

    Mater Horizons

    (2020)
  • T. Smith et al.

    properties and applications of graphene oxide/reduced graphene oxide and their nanocomposites. Nano

    Mater Sci

    (2019)
  • W. Wang et al.

    One-pot facile synthesis of graphene quantum dots from rice husks for Fe3+ sensing

    Ind Eng Chem Res

    (2018)
  • Z. Yang et al.

    Engineering the exciton dissociation in quantum-confined 2D CsPbBr 3 nanosheet films

    Adv Funct Mater

    (2018)
  • F. Shayeganfar et al.

    Electro- and opto-mutable properties of MgO nanoclusters adsorbed on mono- and double-layer graphene

    Nanoscale

    (2017)
  • D. Zhou et al.

    Clay particles destabilize engineered nanoparticles in aqueous environments

    Environ Sci Technol

    (2012)
  • J. Yu et al.

    Synthesis of layered double hydroxide single-layer nanosheets in formamide

    Inorg Chem

    (2016)
  • K. Novoselov et al.

    2D materials and van der Waals heterostructures

    Science

    (2016)
  • Y. Liu et al.

    Van der Waals heterostructures and devices

    Nat Rev Mater

    (2016)
  • L. Ma et al.

    Highly selective and efficient removal of heavy metals by layered double hydroxide intercalated with the MoS42–Ion

    J Am Chem Soc

    (2016)
  • Q.-S. Yao et al.

    Corrosion resistance of Mg (OH) 2/Mg–Al-layered double hydroxide coatings on magnesium alloy AZ31: influence of hydrolysis degree of silane

    Rare Met

    (2019)
  • A. Clearfield

    Progress in intercalation research

  • D. O'Hare

    Inorganic intercalation compounds

  • D.B. Mitzi

    Thin-film deposition of organic-inorganic hybrid materials

    Chem Mater

    (2001)
  • T. Xu et al.

    Ag3PO4 immobilized on hydroxy-metal pillared montmorillonite for the visible light driven degradation of acid red 18

    Catal Sci Technol

    (2016)
  • Y. Zhou et al.

    Covalently immobilized ionic liquids on single layer nanosheets for heterogeneous catalysis applications

    Dalton Trans

    (2017)
  • Cited by (0)

    1

    These authors contributed equally to this work.

    View full text