二维材料插层改性方法研究进展

二维材料凭借其独特的电学、光学、磁学等性质引起了广泛关注,如何处理二维材料使其改性是目前的研究热点。 插层方法是目前调控二维材料性质的主要方法之一。 插层过程中,客体粒子插入主体材料的范德华层间,造成二维材料物理与化学性质的变化。 气相、液相、固相插层均可以使二维材料的性质得到提升。 本文主要介绍二维材料插层方法,分析其不同优势和限制条件,并展望如何综合应用插层方法更好地提升二维材料电学、光学等性能。     

二维材料范德华间隙的利用

Since their discovery, two-dimensional (2D) materials have attracted significant research attention owing to their excellent and controllable physical and chemical properties. These materials have emerged rapidly as important material system owing to their unique properties such as electricity, optics, quantum properties, and catalytic properties. 2D materials are mostly bonded by strong ionic or covalent bonds within the layers, and the layers are stacked together by van der Waals forces, thereby making it possible to peel off 2D materials with few or single layers. The weak interaction between the layers of 2D materials also enables the use of van der Waals gaps for regulating the electronic structure of the system and further optimizing the material properties. The introduction of guest atoms can significantly change the interlayer spacing of the original material and coupling strength between the layers. Also, interaction between the guest and host atom also has the potential to change the electronic structure of the original material, thereby affecting the material properties. For example, the electron structure of a host can be modified by interlayer guest atoms, and characteristics such as carrier concentration, optical transmittance, conductivity, and band gap can be tuned. Organic cations intercalated between the layers of 2D materials can produce stable superlattices, which have great potential for developing new electronic and optoelectronic devices. This method enables the modulation of the electrical, magnetic, and optical properties of the original materials, thereby establishing a family of 2D materials with widely adjustable electrical and optical properties. It is also possible to introduce some new properties to the 2D materials, such as magnetic properties and catalytic properties, by the intercalation of guest atoms. Interlayer storage, represented by lithium-ion batteries, is also an important application of 2D van der Waals gap utilization in energy storage, which has also attracted significant research attention. Herein, we review the studies conducted in recent years from the following aspects: (1) changing the layer spacing to change the interlayer coupling; (2) introducing the interaction between guest and host atoms to change the physico-chemical properties of raw materials; (3) introducing the guest substances to obtain new properties; and (4) interlayer energy storage. We systematically describe various interlayer optimization methods of 2D van der Waals gaps and their effects on the physical and chemical properties of synthetic materials, and suggest the direction of further development and utilization of 2D van der Waals gaps.     

Intercalation of Two-dimensional Layered Materials

Two-dimensional(2D) layered materials have attracted great attention due to their unique electrical, optical, thermal and mechanical properties. 2D layered materials have unique van der Waals gaps, thus the foreign substance, such as atoms, molecules and ions, can be inserted into the gaps to change the physical and chemical properties of 2D layered materials, which is conducive to realize their multi-functional application. Herein, we present a critical review of recent research progress of 2D intercalated materials, including the synthesizing methods, theoretical calculation, characterization and multifunctional application. Finally, we will summarize the current challenges and future opportunities in the development of 2D intercalated materials.     

From two-dimensional materials to heterostructures

Graphene, hexagonal boron nitride, molybdenum disulphide, and layered transition metal dichalcogenides (TMDCs) represent a class of two-dimensional (2D) atomic crystals with unique properties due to reduced dimensionality. Stacking these materials on top of each other in a controlled fashion can create heterostructures with tailored properties that offers another promising approach to design and fabricate novel electronic devices. In this report, we attempt to review this rapidly developing field of hybrid materials. We summarize the fabrication methods for different 2D materials, the layer-by-layer growth of various vertical heterostructures and their electronic properties. Particular interests are given to in-situ stack aforementioned 2D materials in controlled sequences, and the TMDCs heterostructures.     

Exfoliation of 2D Materials for Energy and Environmental Applications

The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.     

缺陷位工程在二维材料电催化析氢反应中的研究进展

面对不可再生资源的快速消耗和环境污染的日益加重,寻找清洁可再生能源势在必行.氢能是一种清洁可再生的能源,是目前最有希望替代化石燃料的一种能源.电化学水分解可用来产生高纯氢气,其中析氢催化剂起着至关重要的作用.尽管贵金属铂基催化剂表现出优异的析氢性能,然而稀缺性和高成本限制了其大规模应用.因此,开发高效和地球存量丰富的电...     

Advances in two-dimensional heterostructures by mono-element intercalation underneath epitaxial graphene

Two-dimensional (2D) materials have displayed many remarkable physical properties, including 2D superconductivity, magnetism, and layer-dependent bandgaps. However, it is difficult for a single 2D material to meet complex practical requirements. Heterostructures obtained by vertically stacking different kinds of 2D materials have extensively attracted researchers’ attention because of their rich electronic features. With heterostructures, the constraints of lattice matching can be overcome. Meanwhile, high application potential has been explored for electronic and optoelectronic devices, including tunneling transistors, flexible electronics, and photodetectors. Specifically, graphene-based van der Waals heterostructures (vdWHs) by intercalation are emerging to realize various functional heterostructures-based electronic devices. Intercalating atoms under epitaxial graphene can efficiently decouple graphene from the substrate, and is expected to realize rich novel electronic properties in graphene. In this study, we systematically review the progress of the mono-element intercalation in graphene-based vdWHs, including the intercalation mechanism, intercalation-modified electronic properties, and the practical applications of 2D intercalated heterostructures. This work would inspire edge-cutting ideas in the scientific frontiers of 2D materials.     

液态金属催化剂:二维材料的点金石

由于石墨烯等二维材料具有独特的结构与优异的性能,其在众多新型电子器件的构建中具有重要的应用前景。然而,其可控生长仍然存在诸多挑战性的问题,这也是制约这类明星材料真正迈向应用的瓶颈所在。化学气相沉积法(CVD)是目前可控制备高质量石墨烯最有效的方法,其中催化基底的设计尤为重要,这将直接决定CVD最为核心的两个过程:催化和传质。相较于改变催化剂的化学组成,近年来我们发现改变催化剂的物态——由固态到液态,对石墨烯等二维材料的CVD过程有质的改变和提升。与固态基底相比,液态基底具有更松散的原子排列、更剧烈的原子迁移,使得液面平滑而各向同性,液相可流动且可包埋异质原子。这使得液态金属在催化石墨烯等二维材料及其异质结生长时表现出很多独特的行为,比如层数严格自限制、超快的生长速度、晶粒拼接平滑等。更重要的是,基底的液态特性给二维材料的自组装和转移带来了突破,实乃二维材料的点金石。本文将梳理液态金属催化剂上二维材料的生长、组装与转移行为,这些关键技术的突破将为二维材料迈向真正应用奠定坚实的基础。     

Rapid development in two-dimensional layered perovskite materials and their application in solar cells

This review summarized recent research progresses of two-dimensional layered organic-inorganic hybrid perovskite materials and their photovoltaic performances in 2D perovskite solar cells.     

Unlocking the Electrocatalytic Activity of Antimony for CO2 Reduction by Two‐Dimensional Engineering of the Bulk Material

Two‐dimensional (2D) materials are known to be useful in catalysis. Engineering 3D bulk materials into the 2D form can enhance the exposure of the active edge sites, which are believed to be the origin of the high catalytic activity. Reported herein is the production of 2D “few‐layer” antimony (Sb) nanosheets by cathodic exfoliation. Application of this 2D engineering method turns Sb, an inactive material for CO₂ reduction in its bulk form, into an active 2D electrocatalyst for reduction of CO₂ to formate with high efficiency. The high activity is attributed to the exposure of a large number of catalytically active edge sites. Moreover, this cathodic exfoliation process can be coupled with the anodic exfoliation of graphite in a single‐compartment cell for in situ production of a few‐layer Sb nanosheets and graphene composite. The observed increased activity of this composite is attributed to the strong electronic interaction between graphene and Sb.     

Quasi-one-dimensional materials: polymers and chains

Results of density-functional calculations on materials that can be considered being quasi-1D are reported. The materials include some based on carbon (fullerene nanotubes and a polyyne), chains of metal atoms (Pb, Au, and Ag), and charged chains as building blocks of crystals (PtS₂ chains surrounded by K atoms and NiN chains separated by Ca atoms). In many cases it is found that 2D or 3D behaviors can be recognized, but in some cases the smaller changes due to the change from true 3D or 2D to quasi-1D have profound effects.     

Smart Organic Two‐Dimensional Materials Based on a Rational Combination of Non‐covalent Interactions

Rational design of organic 2D (O2D) materials has made some progress, but it is still in its infancy. A class of self‐assembling small molecules is presented that form nano/microscale supramolecular 2D materials in aqueous media. A judicial combination of four different intermolecular interactions forms the basis for the robust formation of these ultrathin assemblies. These assemblies can be programmed to disassemble in response to a specific protein and release its non‐covalently bound guest molecules.     

Development prospects of metal-based two-dimensional nanomaterials in lithium-sulfur batteries

A lithium-sulfur(Li-S) system is an important candidate for future lithium-ion system due to its low cost and high specific theoretical capacity(1675 m Ah/g, 2600 Wh/kg), which is greatly hindered by the poor conductivity of sulfur, large volume change and dissolution of lithium polysulfides. Two-dimensional(2D)materials with monolayers or few-layers usually have peculiar structures and physical/chemical properties, which can resolve the critical issues in Li-S batteries. Especially, the metal-b...     

Two-dimensional transition metal chalcogenide nanomaterials for cancer diagnosis and treatment

For more than a decade, the exfoliation of graphene and other layered materials has led to a tremendous amount of research in two-dimensional (2D) materials, among which 2D transition metal chalcogenides (TMCs) nanomaterials have attracted much attention in a wide range of applications including photoelectric devices, lithium-ion batteries, catalysis, and energy conversion and storage owing to their unique photoelectric physical properties. With such large specific surface area, strong near-infrared (NIR) absorption and abundant chemical element composition, 2D TMCs nanomaterials have become good candidates in biomedical imaging and cancer treatment. This review systematically summarizes recent progress on 2D TMCs nanomaterials, which includes their synthesis methods and applications in cancer treatment. At the end of this review, we also highlight the future prospects and challenges of 2D TMCs nanomaterials. It is expected that this work can provide the readers with a detailed overview of the synthesis of 2D TMCs and inspire more novel functional biomaterials based on 2D TMCs for cancer treatment in the future.     

PEEM/LEEM技术在两维原子晶体表面物理化学研究中的应用

光发射电子显微镜(PEEM)/低能电子显微镜(LEEM)技术能够原位实时对表面结构、表面电子态和表面化学进行动态成像研究,在催化、能源、纳米、材料等领域有着重要的应用。本文着重介绍这两种技术的新进展,以及该技术在两维原子晶体的表面物理化学研究中的应用;包括原位研究两维原子晶体(石墨烯、氮化硼等)的生长、异质结构的形成、两维原子晶体表面下的插层反应和限域催化反应;将表面原位成像、微区低能电子衍射(μ-LEED)、图像亮度随电子束能量变化(I－V)曲线研究与其它表面表征技术相结合,能够有效理解两维层状材料表面以及层状材料与衬底界面上的动态过程。     

Bridging the Gap between Structurally Distinct 2D Lamellar Zeolitic Precursors through a 3D Germanosilicate Intermediate

There is broad scientific interest in lamellar zeolitic materials for a large variety of technological applications. The traditional synthetic methods towards two‐dimensional (2D) zeolitic precursors have made a great impact in the construction of families of related zeolites; however, the connection between structurally distinct 2D zeolitic precursors is much less investigated in comparison, thereby resulting in a synthetic obstacle that theoretically limits the types of zeolites that can be constructed from each layer. Herein, we report a Ge‐recycling strategy for the topotactic conversion between different 2D zeolitic precursors through a three‐dimensional (3D) germanosilicate. Specifically, the intermediate germanosilicate can be constructed within 150 min by taking advantage of its structural similarity with the parent lamellar precursor. This process enables the conversion of one 2D zeolite structure into another distinct structure, thus overcoming the synthetic obstacle between two families of zeolitic materials.     

A C−N Coupling Polymerization on Ice-Surface towards Decimeter-Sized 2D Covalent Materials with High Catalytic Activity for Water-Splitting

Compared to other solid templates (metal, ceramic, carbon, etc.), polymerization on ice-surface has many advantages. However, the popularity of this method has been impeded by the lack of appropriate polymerization reactions. To date, only few oxidation polymerizations have been reported to occur on ice-surface, and unfortunately they can only produce supramolecular films rather than fully covalent films. Herein for the first time, 2D covalent materials have been created on ice-surface even at −16 °C through a C−N coupling polymerization, and two free-standing 2D polyarylamines ( 2DPA )s were synthesized. Both 2DPA s have decimeter-size and nanometer thickness. This study provides the first polymerization reaction to synthesize 2D covalent materials on ice-surface, which can be used to fabricate materials/tools/robots with specific 2D structure by copying ice morphologies. Furthermore, both 2DPA s exhibit higher hydrogen evolution reaction activity than many metal-free catalysts and even some metal-based catalysts, so this study also provides further insight for the development of metal-free catalysts for water-splitting.     

A review on two-dimensional (2D) and 2D-3D multidimensional perovskite solar cells: Perovskites structures,stability, and photovoltaic performances

Perovskite solar cells (PSCs) fabricated with two-dimensional (2D) halide and 2D-3D mixed-halide materials are remarkable for their optoelectronic properties. The 2D perovskite structures are extremely stable but show limited charge transport and large bandgap for solar cell applications. To overcome these challenges, multidimensional 2D-3D perovskite materials are used to maintain simultaneously, a long-term stability, and high performance. In this review, we discuss the recent progress and the advantages of 2D and 2D-3D perovskite materials as absorber for solar cell applications. First, we discuss the structure and the unique properties of 2D and multidimensional 2D-3D perovskites materials. Second, the stability of 2D and 2D-3D mixed perovskites and the perspects of PSCs are hashed out.     

Lead‐ and Iodide‐Deficient (CH3NH3)PbI3 (d‐MAPI): The Bridge between 2D and 3D Hybrid Perovskites

3D and 2D hybrid perovskites, which have been known for more than 20 years, have emerged recently as promising materials for optoelectronic applications, particularly the 3D compound (CH₃NH₃)PbI₃ (MAPI). The discovery of a new family of hybrid perovskites called d ‐MAPI is reported: the association of PbI₂ with both methyl ammonium (MA⁺) and hydroxyethyl ammonium (HEA⁺) cations leads to a series of five compounds with general formulation (MA)_1−2.48x(HEA)_3.48x[Pb_1−xI_3−x]. These materials, which are lead‐ and iodide‐deficient compared to MAPI while retaining 3D architecture, can be considered as a bridge between the 2D and 3D materials. Moreover, they can be prepared as crystallized thin films by spin‐coating. These new 3D materials appear very promising for optoelectronic applications, not only because of their reduced lead content, but also in account of the large flexibility of their chemical composition through potential substitutions of MA⁺, HEA⁺, Pb²⁺ and I⁻ ions.     

Recent advances in electron tomography: TEM and HAADF-STEM tomography for materials science and semiconductor applications.

Electron tomography is a well-established technique for three-dimensional structure determination of (almost) amorphous specimens in life sciences applications. With the recent advances in nanotechnology and the semiconductor industry, there is also an increasing need for high-resolution three-dimensional (3D) structural information in physical sciences. In this article, we evaluate the capabilities and limitations of transmission electron microscopy (TEM) and high-angle-annular-dark-field scanning transmission electron microscopy (HAADF-STEM) tomography for the 3D structural characterization of partially crystalline to highly crystalline materials. Our analysis of catalysts, a hydrogen storage material, and different semiconductor devices shows that features with a diameter as small as 1-2 nm can be resolved in three dimensions by electron tomography. For partially crystalline materials with small single crystalline domains, bright-field TEM tomography provides reliable 3D structural information. HAADF-STEM tomography is more versatile and can also be used for high-resolution 3D imaging of highly crystalline materials such as semiconductor devices.