Phase Engineering of Two‐Dimensional Transition Metal Dichalcogenides

Transition metal dichalcogenides (TMDs) possess a large number of two‐dimensional (2D) materials with novel physical and chemical properties and hold great potential applications in electronic devices, optical devices as well as catalysts. TMDs usually have poly‐phases, such as 2H, 3R and 1T. Chemical and physical properties, including electrical conductivity, superconductivity, magnetism and catalytic activity, are different for different phases of TMDs. Therefore, great efforts have been made to obtain a specific pure phase of 2D TMD materials. Here, we review the recent phase engineering research for 2D TMDs, including ion insertion, alloying, temperature, defects, strain and electric field.     

Designed Synthesis of van der Waals Heterostructures: The Power of Kinetic Control

Selecting specific 2D building blocks and specific layering sequences of van der Waals heterostructures should allow the formation of new materials with designed properties for specific applications. Unfortunately, the synthetic ability to prepare such structures at will, especially in a manner that can be manufactured, does not exist. Herein, we report the targeted synthesis of new metal–semiconductor heterostructures using the modulated elemental‐reactant technique to nucleate specific 2D building blocks, control their thickness, and avoid epitaxial structures with long‐range order. The building blocks, VSe₂ and GeSe₂, have different crystal structures, which inhibits cation intermixing. The precise control of this approach enabled us to synthesize heterostructures containing GeSe₂ monolayers alternating with VSe₂ structural units with specific sequences. The transport properties systematically change with nanoarchitecture and a charge‐density wave‐like transition is observed.     

Recent progress in MXene and graphene based nanocomposites for microwave absorption and electromagnetic interference shielding

There is widespread use of telecommunication and microwave technology in modern society, and raised the electromagnetic interference (EMI) issue to alarming situation due to apprehensive demand and growth of 5G technology undesirably disturbing the human health. The two dimensional (2D) materials including graphene and MXenes are already been used for variety of electronic devices due to their exceptional electrical, mechanical, optical, chemical, and thermal properties. MXene is composed of metal carbides, in which mainly metals are the building blocks for dielectrics, semiconductors, or semimetals. However, the strong interfaces with electromagnetic waves (EM) are variable from terahertz (THz) to gigahertz (GHz) frequency levels and are widely used in EMI and Microwave absorption (MA) for mobile networks and communication technologies. The use of different organic materials with metal, organic, inorganic fillers, polymers nanocomposite and MXene as a novel material has been studied to address the recent advancement and challenges in the microwave absorption mechanism of 2D materials and their nanocomposites. In this concern, various techniques and materials has been reported for the improvement of shielding effectiveness (SE), and theoretical aspects of EMI shielding performance, as well stability of 2D materials particularly MXene, graphene and its nanocomposites. Consequently, various materials including polymers, conducting polymers, and metal–organic frameworks (MOF) have also been discussed by introducing various strategies for improved MA and control of EMI shieling. Here in this comprehensive review, we summarized the recent developments on material synthesis and fabrication of MXene based nanocomposites for EMI shielding and MA. This research work is a comprehensive review majorly focuses on the fundamentals of EMI/MA.  The recent developments and challenges of the MXene and graphene based various structures with different polymeric composites are described in a broader perspective.     

Malonic acid: a multi-modal bridging ligand for new architectures and properties on molecule-based magnets

In this work, we show how the design of one-, two- and three-dimensional materials can strongly benefit from the use of crystal engineering techniques, which can give rise to structures of different shapes, and how these differences can give rise to different properties. We will focus on the networks constructed by assembling malonate ligands and metal centres. The idea of using malonate (dianion of propanedioic acid, H₂mal) is that they can give rise to different coordination modes with the metal ions bind. Extended magnetic networks of dimensionalities 1 (1D), 2 (2D) and 3 (3D) can be chemically constructed from malonato-bridged metallic complexes. These coordination polymers behave as ferro-, ferri- or canted antiferromagnets. The control of the spatial arrangement of the magnetic building blocks is of paramount importance in determining the strength of the magnetic interaction. It depends on the coordination bond between the metal ion and the ligands, and on supramolecular interactions such as stacking interactions or hydrogen bonds.     

Synthetic Two-dimensional Organic Structures

Synthetic two-dimensional(2 D) polymers have totally different topology structures compared with traditional linear or branched polymers. The peculiar 2 D structures bring superior properties. Although, from linear to 2 D polymers, the study of these new materials is still in its infancy, they already show potential applications especially in optoelectronics, membranes, energy storage and catalysis, etc. In this review, we summarize the recent progress of the 2 D materials from three respects:(1) Chemistry—different types of polymerization reactions or supramolecular assembly to construct the 2 D networks were described;(2) Preparation methods—surface science, crystal engineering approaches and solution synthesis were introduced;(3) Functionalization and some early applications.     

Metal–Organic Organopolymeric Hybrid Framework by Reversible [2+2] Cycloaddition Reaction

Organic polymers are usually amorphous or possess very low crystallinity. The metal complexes of organic polymeric ligands are also difficult to crystallize by traditional methods because of their poor solubilities and their 3D structures can not be determined by single‐crystal X‐ray crystallography owing to a lack of single crystals. Herein, we report the crystal structure of a 1D Zn^II coordination polymer fused with an organic polymer ligand made in situ by a [2+2] cycloaddition reaction of a six‐fold interpenetrated metal–organic framework. It is also shown that this organic polymer ligand can be depolymerized in a single‐crystal‐to‐single‐crystal (SCSC) fashion by heating. This strategy could potentially be extended to make a range of monocrystalline metal organopolymeric complexes and metal–organic organopolymeric hybrid materials. Such monocrystalline metal complexes of organic polymers have hitherto been inaccessible for materials researchers.     

Deuterium structural effects in inorganic and bioinorganic aggregates

Deuterium kinetic isotope effects are widely used in chemical and biological research. Deuterium thermodynamic effects on the aqueous synthesis of inorganic materials, however, seem not to have been recognized. Here we report that the simple replacement of H(2)O with D(2)O in the synthesis of a solid-state manganese complex results in a new structurally and magnetically distinct phase. When iron oxides are synthesized, the relative amount of the mineral phases obtained in H(2)O vs D(2)O is different. The morphology and magnetic properties of the iron core of the iron storage protein ferritin are likewise different when mineralization is carried out in heavy water. The formation of extra inorganic solids, change in the ratio of two phases or alteration of a single phase morphology in D(2)O suggest that new inorganic and bioinorganic metal complexes might be obtained by using the thermodynamic isotope effect.     

Two-dimensional Covalent Organic Frameworks: Tessellation by Synthetic Art

Covalent organic frameworks(COFs) featuring designable nanoporous structures exhibit many fascinating properties and have attracted great attention in recent years for their intriguing application potential in sensing, catalysis, gas storage and separation, optoelectronics, etc. Rational design of twodimensional(2D) COFs through judiciously selecting chemical building blocks is critical to acquiring predetermined skeleton and pore structures. In this perspective, we review the reticular synthesis of 2D COFs with different topologies, highlighting the important role of various characterization techniques in crystal structure determination. 2D COFs with simple tessellations have been widely investigated, while the synthesis of complex tessellated COFs is still a great challenge. Some recent examples of 2D COFs with novel topological structures are also surveyed.     

Three-dimensional architectures constructed using two-dimensional nanosheets

Two-dimensional(2D) nanomaterials such as transition metal dichalcogenides(TMDs) and graphene have attracted extensive interest as emergent materials, owing to their excellent properties that favor their future use in electronic devices, catalysis, optics, and biological- or energy-relevant areas. However, 2D nanosheets tend to easily restack and condense, which weakens their performance in many of these applications. Assembling these 2D nanosheets as building blocks for three-dimensional(3D) architectures not only maintains the intrinsic performances of the 2D nanostructures but also synergistically makes use of the advantages of the 3D microstructures to improve the overall material properties. In this critical review, we will highlight recent developments of sundry 2D nanosheet-assembled 3D architectures, including their design, synthesis, and potential applications. Their controllable syntheses, novel structures, and potential applications will be systematically explained, analyzed, and summarized. In the end, we will offer some perspective on the challenges facing future advancement of this field.     

基于二维材料及其范德瓦尔斯异质结的光电探测器

近些年来,石墨烯、黑磷和过渡金属二硫化物以及其他二维材料受到了越来越多的关注。凭借其独特的结构和优异的电学、光学特性,这些二维材料在光电器件中得到了广泛应用,具有良好的发展潜力。本文概述了二维材料在光电探测器领域的最新研究进展,介绍了一些常见的二维材料及其制备方法,阐述了光电探测器件的基本原理和评价参数,以及回顾了二维材料及其异质结构在光电探测器中的应用,最后总结了该领域仍然面临的挑战并对其未来的发展方向进行了展望。     

Metal organic framework (MOF) liquid crystals. 1D, 2D and 3D ionic coordination polymer structures in the thermotropic mesophases of metal soaps,including alkaline earth,transition metal and lanthanide soaps

Taken together, the body of existing literature on metal soap crystal structures and mesophases supports the view that much is to be gained by treating the soaps as metal organic frameworks (MOF's) when relating their structure and liquid crystallinity.We argue that metal soaps mesophases often consist of disordered metal organic (carboxylate) frameworks (MOF's). Metal atoms are linked by bridging carboxylates, and the metal–oxygen networks form semi-flexible rods, chains and sheets of M–O polyhedra within their co-bonded, mesotructured, self-assemblies of lipidic chains. The packing of the molten hydrocarbon chains allows otherwise unconnected MOF networks to coexist as spatially isolated units in the same unit cell. For instance the lamellar phases are true 2D MOF's or layers of 1-D MOF's. The phase transitions can then be regarded as coupled disordering/re-ordering transitions involving rotational and conformational disordering of the hydrocarbon chains balanced with disordering of MOF symmetries, MOF topological transformations, depolymerizations and dimensionality reductions ultimately leading to anisotropic melts.By way of demonstration, thermotropic phase transitions of homologous series of lanthanide soaps are systematically studied using a variety of experimental methods, and the data are used in a topological model for testing the consistency with the MOF concept of metal soap crystal structures and thermotropic mesophases. Finally, an interpenetrating bicontinuous MOF comprised of SrO₆ polyhedral rods is presented as an atomically resolved model for the network topology of the cubic mesophase of strontium soaps.Metal soaps are therefore shown to afford a bridge between liquid crystals and metal organic framework (MOF) materials.     

Perturbation of Spin Crossover Behavior by Covalent Post‐Synthetic Modification of a Porous Metal–Organic Framework

Covalent post‐synthetic modification is a versatile method for gaining high‐level synthetic control over functionality within porous metal–organic frameworks and for generating new materials not accessible through one‐step framework syntheses. Here we apply this topotactic synthetic approach to a porous spin crossover framework and show through detailed comparison of the structures and properties of the as‐synthesised and covalently modified phases that the modification reaction proceeds quantitatively by a thermally activated single‐crystal‐to‐single‐crystal transformation to yield a material with lowered spin‐switching temperature, decreased lattice cooperativity, and altered color. Structure–function relationships to emerge from this comparison show that the approach provides a new route for tuning spin crossover through control over both outer‐sphere and steric interactions.     

Novel Two‐Dimensional Porous Materials for Electrochemical Energy Storage: A Minireview

Two dimensional (2D) porous materials have great potential in electrochemical energy conversion and storage. Over the past five years, our research group has focused on Simple, Mass, Homogeneous and Repeatable Synthesis of various 2D porous materials and their applications for electrochemical energy storage especially for supercapacitors (SCs). During the experimental process, through precisely controlling the experimental parameters, such as reaction species, molar ratio of different ions, concentration, pH value of reaction solution, heating temperature, and reaction time, we have successfully achieved the control of crystal structure, composition, crystallinity, morphology, and size of these 2D porous materials including transition metal oxides (TMOs), transition metal hydroxides (TMHOs), transition metal oxalates (TMOXs), transition metal coordination complexes (TMCCs) and carbon materials, as well as their derivatives and composites. We have also named some of them with CQU‐Chen (CQU is the initialism of Chongqing University, Chen is the last name of Lingyun Chen), such as CQU‐Chen‐Co?O‐1, CQU‐Chen‐Ni?O?H‐1, CQU‐Chen‐Zn?Co?O‐1, CQU‐Chen‐Zn?Co?O‐2, CQU‐Chen‐OA?Co‐2‐1, CQU‐Chen‐Co?OA‐1, CQU‐Chen‐Ni?OA‐1, CQU‐Chen‐Gly?Co‐3‐1, CQU‐Chen‐Gly?Ni‐2‐1, CQU‐Chen‐Gly?Co?Ni‐1, etc. The introduction of 2D porous materials as electrode materials for SCs improves the energy storage performances. These materials provide a large number of active sites for ion adsorption, supply plentiful channels for fast ion transport and boost electrical conductivity and facilitate electron transportation and ion penetration. The unique 2D porous structures review is mainly devoted to the introduction of our contribution in the 2D porous nanostructured materials for SC. Finally, the further directions about the preparation of 2D porous materials and electrochemical energy conversion and storage applications are also included.     

Premodified Surface Method to Obtain Ultra‐Highly Dispersed Metals and their 3D Structure Control on an Oxide Single‐Crystal Surface

Precise control of the three‐dimensional (3D) structure of highly dispersed metal species such as metal complexes and clusters attached to an oxide surface has been important for the development of next‐generation high‐performance heterogeneous catalysts. However, this is not easily achieved for the following reasons. (1) Metal species are easily aggregated on an oxide surface, which makes it difficult to control their size and orientation definitely. (2) Determination of the 3D structure of the metal species on an oxide powder surface is hardly possible. To overcome these difficulties, we have developed the premodified surface method, where prior to metal deposition, the oxide surface is premodified with a functional organic molecule that can strongly coordinate to a metal atom. This method has successfully provided a single metal dispersion on an oxide single‐crystal surface with the 3D structure precisely determined by polarization‐dependent total reflection fluorescence X‐ray absorption fine structure (PTRF‐XAFS). Here we describe our recent results on ultra‐high dispersions of various metal atoms on TiO₂(110) surfaces premodified with mercapto compounds, and show the possibility of fine tuning and orientation control of the surface metal 3D structures.     

Salt-assisted chemical vapor deposition of two-dimensional materials

Two-dimensional(2D) materials with atomic thickness are promising candidates for the applications in future semiconductor devices, owing to their fascinating physical properties and superlative optoelectronic performance. Chemical vapor deposition(CVD) is considered to be an efficient method for large-scale preparation of 2D materials toward practical applications.However, the high melting points of metal precursors and the thermodynamics instabilities of metastable phases limit the direct CVD synthesis of plenty of 2D materials. The salt has recently been introduced into the CVD process, which proved to be effective to address these issues. In this review, we highlighted the latest progress in the salt-assisted CVD growth of 2D materials, including layered and non-layered crystals. Firstly, strategies of adding salts are summarized. Then, the salt-assisted growth of various layered materials is presented, emphasizing on the transition metal chalcogenides of stable and metastable phases. Furthermore, strategies to grow ultrathin non-layered materials are discussed. We provide viewpoints into the techniques of using salt, the effects of salt, and the growth mechanisms of 2D crystals. Finally, we offer the challenges to be overcome and further research directions of this emerging salt-assisted CVD technique.     

Unique Supramolecular Liquid‐Crystal Phases with Different Two‐Dimensional Crystal Layers

We report herein a series of tetrablock‐mimic azobenzene‐containing [60]fullerene dyads that form supramolecular liquid crystals (LCs) from phase‐segregated two‐dimensional (2D) crystals. The unique double‐, triple‐, and quadruple‐layer packing structure of fullerenes in the 2D crystals leads to different smectic supramolecular LC phases, and novel LC phase transitions were observed upon changes in the fullerene packing layer number in the 2D crystals. Interestingly, by combining the LC properties with 2D crystals, these materials show excellent electron mobility in the order of 10⁻³ cm² V⁻¹ s⁻¹, despite their relatively low fullerene content. Our results provide a novel method to manipulate 2D crystal layer thickness, with promising applications in optoelectronic devices.     

Liquid crystal templating of nanomaterials with nature's toolbox

Naturally occurring biomolecules are sustainable and green precursors for the development of new materials. Within this family of natural materials, cellulose nanocrystals (CNCs) have emerged as one of the most promising materials because of their outstanding physico-chemical properties and the possibility to produce them in large quantities. One key trait of CNCs is their ability to self-assemble into a chiral nematic liquid crystalline phase. In this review, we discuss how templating can be used to transfer the three-dimensional structure of liquid crystalline CNC phases onto solid materials. This is followed by examples that illustrate the fascinating properties and potential applications that arise from the resulting nanostructured materials such as sensing and catalysis. We then summarize efforts to use the liquid crystalline phase of a selection of other biopolymers for templating. While nanocrystalline chitin, having very similar properties to CNCs, has been successfully employed to make a variety of new materials, efforts to template liquid crystal phases of other biomolecules have been met with limited success. However, we discuss virus nanoparticles and collagen as examples to highlight further possibilities for materials research.     

Nonspherical colloidal crystals fabricated by the thermal pressing of colloidal crystal chips

Nonspherical colloids and their ordered arrays may be more attractive in applications such as photonic crystals than their spherical counterparts because of their lower symmetries, although such structures are difficult to achieve. In this letter, we describe the fabrication and characterization of colloidal crystals constructed from nonspherical polyhedrons. We fabricated such nonspherical colloidal crystals by pressing spherical polymer colloidal crystal chips at a temperature slightly lower than the glass-transition temperature (T(g)) of these polymer colloids. During this process, the polymer microspheres were distinctively transformed into polyhedrons according to their crystal structures, whereas the long-range order of the 3D lattice was essentially preserved. Because a working temperature lower than T(g) effectively prevented the colloidal crystals from fusing into films, the spherical colloidal crystals were transformed greatly under pressure, which lead to obvious change in the optical properties of colloidal crystals. Besides their special symmetry and optical properties, these nonspherical colloidal crystals can be used as templates for 2D or 3D structures of special symmetry, such as 2D nano-networks. We anticipate that this fabrication technique for nonspherical colloidal crystals can also be extended to nonspherical porous materials.     

A new class of liquid crystals: methylene-1,4-dihydropyridines

A group of liquid crystal materials which contain the novel methylene-1,4-dihydropyridine substructure were synthesized and their mesogenic properties examined. Three main classes of liquid crystal compounds which differ in the structure of the aromatic core group (phenyl, azobenzene and diphenylacetylene) attached to the nitrogen of the 1,4-dihydropyridine group were studied. The synthesis of the methylene-1,4-dihydropyridine group was accomplished in excellent yield by a Knoevenagel condensation of a 4-pyridone intermediate with an active methylene compound. The liquid crystal materials prepared thus far which contain this methylene-1,4-dihydropyridine structure all possess broad enantiotropic smectic A phases and one example also possesses a tilted smectic C phase. These mesogens may possess useful properties such as high birefringence.     

Solution-based synthetic strategies for 1-D nanostructures

One-dimensional (1-D) nanostructures of materials have received great research attention because of their unique photochemistry, photophysical, and electron-transport properties different from those of bulky or nanoparticle materials. One of the main challenges in this field is how to precisely control the sizes, dimensionalities, compositions, and crystal structures of materials in nanoscale. This review summarizes the recent progress in the solution-based routes to prepare 1-D nanostructures, highlighting the contribution from this laboratory. Crystal structure as one of the inherent factors that may determine the growth behavior of the nanocrystals is emphasized in this paper. Particularly compounds with layered structures or anistropic crystal structures are given special attention in the controlled growth of 1-D nanostructures. This review aims to present a relatively general understanding of the correlation between the crystal structure and growth behavior of materials under solution-based conditions and show how to choose appropriate conditions for the growth of 1-D nanostructures.