Structural Approaches to Control Interlayer Interactions in 2D Covalent Organic Frameworks

The ability to design and synthesize monomers can affect fundamental aspects in 2D covalent organic frameworks, such as dimensionality, topology, and pore size. Besides this, the structure of the monomers can also affect interlayer interactions, which provide an additional means to influence crystallinity, layer arrangement, interlayer distances, and exfoliability. Herein, some of the effects that the structure of monomers can have on the interlayer interactions in 2D covalent organic frameworks and related materials are illustrated.     

Interface Characterization and Control of 2D Materials and Heterostructures

2D materials and heterostructures have attracted significant attention for a variety of nanoelectronic and optoelectronic applications. At the atomically thin limit, the material characteristics and functionalities are dominated by surface chemistry and interface coupling. Therefore, methods for comprehensively characterizing and precisely controlling surfaces and interfaces are required to realize the full technological potential of 2D materials. Here, the surface and interface properties that govern the performance of 2D materials are introduced. Then the experimental approaches that resolve surface and interface phenomena down to the atomic scale, as well as strategies that allow tuning and optimization of interfacial interactions in van der Waals heterostructures, are systematically reviewed. Finally, a future outlook that delineates the remaining challenges and opportunities for 2D material interface characterization and control is presented.     

Nanoscale Assembly of 2D Materials for Energy and Environmental Applications

Rational design of 2D materials is crucial for the realization of their profound implications in energy and environmental fields. The past decade has witnessed significant developments in 2D material research, yet a number of critical challenges remain for real-world applications. Nanoscale assembly, precise control over the orientational and positional ordering, and complex interfaces among 2D layers are essential for the continued progress of 2D materials, especially for energy storage and conversion and environmental remediation. Herein, recent progress, the status, future prospects, and challenges associated with nanoscopic assembly of 2D materials are highlighted, specifically targeting energy and environmental applications. Geometric dimensional diversity of 2D material assembly is focused on, based on novel assembly mechanisms, including 1D fibers from the colloidal liquid crystalline phase, 2D films by interfacial tension (Marangoni effect), and 3D nanoarchitecture assembly by electrochemical processes. Relevant critical advantages of 2D material assembly are highlighted for application fields, including secondary batteries, supercapacitors, catalysts, gas sensors, desalination, and water decontamination.     

2D Organic Materials for Optoelectronic Applications

The remarkable merits of 2D materials with atomically thin structures and optoelectronic attributes have inspired great interest in integrating 2D materials into electronics and optoelectronics. Moreover, as an emerging field in the 2D‐materials family, assembly of organic nanostructures into 2D forms offers the advantages of molecular diversity, intrinsic flexibility, ease of processing, light weight, and so on, providing an exciting prospect for optoelectronic applications. Herein, the applications of organic 2D materials for optoelectronic devices are a main focus. Material examples include 2D, organic, crystalline, small molecules, polymers, self‐assembly monolayers, and covalent organic frameworks. The protocols for 2D‐organic‐crystal‐fabrication and ‐patterning techniques are briefly discussed, then applications in optoelectronic devices are introduced in detail. Overall, an introduction to what is known and suggestions for the potential of many exciting developments are presented.     

Polymeric Materials: Patterned Polymer Carpets (Small 5/2011)

For the development of polymer carpets as active devices for micro‐ and nanotechnology, a control of the polymer carpet morphology and especially control of the stimulus responsive polymer brush is needed. Here, we report on the first example for the fabrication of patterned polymer carpets. On a two‐dimensional framework of fully crosslinked and chemically patterned nanosheets, polymer brushes of styrene and 4‐vinyl pyridine were grafted by self‐initiated surface photopolymerization and photografting (SIPGP). It was found that polymer grafting by SIPGP occurred over the entire nanosheets but with a preferred grafting on the amino functionalized nanosheet areas. This results in continuous polymer carpets with an intact nanosheet framework but with amplification of the chemical patterning into a three dimensional topography of the grafted polymer brush. In the case of negative patterned nanosheets, the patterned carpet could be prepared as freestanding ultrathin membranes. Furthermore, swelling experiments with poly(4‐vinyl pyridine) carpets showed that the patterns induces a directional buckling of the flexible polymer carpet. This may open the possibility of the development of micro‐ or nanoactuator devices with anisotropic responds upon environmental changes.     

Protonation‐Assisted Exfoliation of N‐Containing 2D Conjugated Polymers

Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar‐to‐chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid‐phase protonation‐assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N‐containing conjugated polymers such as g‐C₃N₄, C₂N, and aza‐CMP. The exfoliation yields are only 2–15% in pure water whereas they can be substantially improved to 41–56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N‐containing conjugated polymer nanosheets for future solar energy conversion.     

Controllable Synthesis of 2D Materials by Electrochemical Exfoliation for Energy Storage and Conversion Application

2D materials have captured much recent research interest in a broad range of areas, including electronics, biology, sensors, energy storage, and others. In particular, preparing 2D nanosheets with high quality and high yield is crucial for the important applications in energy storage and conversion. Compared with other prevailing synthetic strategies, the electrochemical exfoliation of layered starting materials is regarded as one of the most promising and convenient methods for the large-scale production of uniform 2D nanosheets. Here, recent developments in electrochemical delamination are reviewed, including protocols, categories, principles, and operating conditions. State-of-the-art methods for obtaining 2D materials with small numbers of layers—including graphene, black phosphorene, transition metal dichalcogenides and MXene—are also summarized and discussed in detail. The applications of electrochemically exfoliated 2D materials in energy storage and conversion are systematically reviewed. Drawing upon current progress, perspectives on emerging trends, existing challenges, and future research directions of electrochemical delamination are also offered.     

Surface Tension Components Based Selection of Cosolvents for Efficient Liquid Phase Exfoliation of 2D Materials

A proper design of direct liquid phase exfoliation (LPE) for 2D materials as graphene, MoS₂, WS₂, h‐BN, Bi₂Se₃, MoSe₂, SnS₂, and TaS₂ with common cosolvents is carried out based on considering the polar and dispersive components of surface tensions of various cosolvents and 2D materials. It has been found that the exfoliation efficiency is enhanced by matching the ratio of surface tension components of cosolvents to that of the targeted 2D materials, based on which common cosolvents composed of IPA/water, THF/water, and acetone/water can be designed for sufficient LPE process. In this context, the library of low‐toxic and low‐cost solvents with low boiling points for LPE is infinitely enlarged when extending to common cosolvents. Polymer‐based composites reinforced with a series of different 2D materials are compared with each other. It is demonstrated that the incorporation of cosolvents‐exfoliated 2D materials can substantially improve the mechanical and thermal properties of polymer matrices. Typically, with the addition of 0.5 wt% of such 2D material as MoS₂ nanosheets, the tensile strength and Young's modulus increased up to 74.85% and 136.97%, respectively. The different enhancement effect of 2D materials is corresponded to the intrinsic properties and LPE capacity of 2D materials.     

Layer-Controlled Perovskite 2D Nanosheet Interlayer for the Energy Storage Performance of Nanocomposites

Polymer-based nanocomposites are desirable materials for next-generation dielectric capacitors. 2D dielectric nanosheets have received significant attention as a filler. However, randomly spreading the 2D filler causes residual stresses and agglomerated defect sites in the polymer matrix, which leads to the growth of an electric tree, resulting in a more premature breakdown than expected. Therefore, realizing a well-aligned 2D nanosheet layer with a small amount is a key challenge; it can inhibit the growth of conduction paths without degrading the performance of the material. Here, an ultrathin Sr_1.8Bi_0.2Nb₃O₁₀ (SBNO) nanosheet filler is added as a layer into poly(vinylidene fluoride) (PVDF) films via the Langmuir–Blodgett method. The structural properties, breakdown strength, and energy storage capacity of a PVDF and multilayer PVDF/SBNO/PVDF composites as a function of the thickness-controlled SBNO layer are examined. The seven-layered (only 14 nm) SBNO nanosheets thin film can sufficiently prevent the electrical path in the PVDF/SBNO/PVDF composite and shows a high energy density of 12.8 J cm⁻³ at 508 MV m⁻¹, which is significantly higher than that of the bare PVDF film (9.2 J cm⁻³ at 439 MV m⁻¹). At present, this composite has the highest energy density among the polymer-based nanocomposites under the filler of thin thickness.     

A High‐Performance Lithium‐Ion Capacitor Based on 2D Nanosheet Materials

Lithium‐ion capacitors (LICs) are promising electrical energy storage systems for mid‐to‐large‐scale applications due to the high energy and large power output without sacrificing long cycle stability. However, due to the different energy storage mechanisms between anode and cathode, the energy densities of LICs often degrade noticeably at high power density, because of the sluggish kinetics limitation at the battery‐type anode side. Herein, a high‐performance LIC by well‐defined ZnMn₂O₄‐graphene hybrid nanosheets anode and N‐doped carbon nanosheets cathode is presented. The 2D nanomaterials offer high specific surface areas in favor of a fast ion transport and storage with shortened ion diffusion length, enabling fast charge and discharge. The fabricated LIC delivers a high specific energy of 202.8 Wh kg^?1 at specific power of 180 W kg^?1, and the specific energy remains 98 Wh kg^?1 even when the specific power achieves as high as 21 kW kg^?1.     

Strain Engineering of 2D Materials: Issues and Opportunities at the Interface

Triggered by the growing needs of developing semiconductor devices at ever‐decreasing scales, strain engineering of 2D materials has recently seen a surge of interest. The goal of this principle is to exploit mechanical strain to tune the electronic and photonic performance of 2D materials and to ultimately achieve high‐performance 2D‐material‐based devices. Although strain engineering has been well studied for traditional semiconductor materials and is now routinely used in their manufacturing, recent experiments on strain engineering of 2D materials have shown new opportunities for fundamental physics and exciting applications, along with new challenges, due to the atomic nature of 2D materials. Here, recent advances in the application of mechanical strain into 2D materials are reviewed. These developments are categorized by the deformation modes of the 2D material–substrate system: in‐plane mode and out‐of‐plane mode. Recent state‐of‐the‐art characterization of the interface mechanics for these 2D material–substrate systems is also summarized. These advances highlight how the strain or strain‐coupled applications of 2D materials rely on the interfacial properties, essentially shear and adhesion, and finally offer direct guidelines for deterministic design of mechanical strains into 2D materials for ultrathin semiconductor applications.     

Layer Dependence and Light Tuning Surface Potential of 2D MoS2 on Various Substrates

Here surface potential of chemical vapor deposition (CVD) grown 2D MoS₂ with various layers is reported, and the effect of adherent substrate and light illumination on surface potential of monolayer MoS₂ are investigated. The surface potential of MoS₂ on Si/SiO₂ substrate decreases from 4.93 to 4.84 eV with the increase in the number of layer from 1 to 4 or more. Especially, the surface potentials of monolayer MoS₂ are strongly dependent on its adherent substrate, which are determined to be 4.55, 4.88, 4.93, 5.10, and 5.50 eV on Ag, graphene, Si/SiO₂, Au, and Pt substrates, respectively. Light irradiation is introduced to tuning the surface potential of monolayer MoS₂, with the increase in light intensity, the surface potential of MoS₂ on Si/SiO₂ substrate decreases from 4.93 to 4.74 eV, while increases from 5.50 to 5.56 eV on Pt substrate. The I–V curves on vertical of monolayer MoS₂/Pt heterojunction show the decrease in current with the increase of light intensity, and Schottky barrier height at MoS₂/Pt junctions increases from 0.302 to 0.342 eV. The changed surface potential can be explained by trapped charges on surface, photoinduced carriers, charge transfer, and local electric field.