2维原子晶体材料的研究现状与未来

近年来,以石墨烯为代表的2维原子晶体材料因其独特的2维结构、丰富而新奇的物理化学性质与广阔的应用前景,迅速成为凝聚态物理与材料科学领域的研究前沿。本文概要地介绍了石墨烯的制备、石墨烯的物理与物性、石墨烯的可能应用及其他2维原子晶体材料的研究进展,并对2维原子晶体材料的未来发展趋势进行了分析与讨论。     

Ultrafast growth of large single crystals of monolayer WS2 and WSe2

Monolayer transition metal dichalcogenides (TMDs) have attracted considerable attention as atomically thin semiconductors for the ultimate transistor scaling. For practical applications in integrated electronics, large monolayer single crystals are essential for ensuring consistent electronic properties and high device yield. The TMDs available today are generally obtained by mechanical exfoliation or chemical vapor deposition (CVD) growth, but are often of mixed layer thickness, limited single crystal domain size or have very slow growth rate. Scalable and rapid growth of large single crystals of monolayer TMDs requires maximization of lateral growth rate while completely suppressing the vertical growth, which represents a fundamental synthetic challenge and has motivated considerable efforts. Herein we report a modified CVD approach with controllable reverse flow for rapid growth of large domain single crystals of monolayer TMDs. With the use of reverse flow to precisely control the chemical vapor supply in the thermal CVD process, we can effectively prevent undesired nucleation before reaching optimum growth temperature and enable rapid nucleation and growth of monolayer TMD single crystals at a high temperature that is difficult to attain with use of a typical thermal CVD process. We show that monolayer single crystals of 450 μm lateral size can be prepared in 10 s, with the highest lateral growth rate up to 45 μm/s. Electronic characterization shows that the resulting monolayer WSe₂ material exhibits excellent electronic properties with carrier mobility up to 90 cm² V⁻¹ s⁻¹, comparable to that of the best exfoliated monolayers. Our study provides a robust pathway for rapid growth of high-quality TMD single crystals.     

Carbon nanotubes for flexible batteries: recent progress and future perspective

Flexible batteries, which maintain their functions potently under various mechanical deformations, attract increasing interest due to potential applications in emerging portable and wearable electronics. Significant efforts have been devoted to material synthesis and structural designs to realize the mechanical flexibility of various batteries. Carbon nanotubes (CNTs) have a unique one-dimensional (1D) nanostructure and are convenient to further assemble into diverse macroscopic structures, such as 1D fibers, 2D films and 3D sponges/aerogels. Due to their outstanding mechanical and electrical properties, CNTs and CNT-based hybrid materials are superior building blocks for different components in flexible batteries. This review summarizes recent progress on the application of CNTs in developing flexible batteries, from closed-system to open-system batteries, with a focus on different structural designs of CNT-based material systems and their roles in various batteries. We also provide perspectives on the challenges and future research directions for realizing practical applications of CNT-based flexible batteries.     

A general aerosol-assisted biosynthesis of functional bulk nanocomposites

Although a variety of nanoparticles with better-than-bulk material performances can be synthesized, it remains a challenge to scale the extraordinary properties of individual nanoscale units to the macroscopic level for bulk nanostructured materials. Here, we report a general and scalable biosynthesis strategy that involves simultaneous growth of cellulose nanofibrils through microbial fermentation and co-deposition of various kinds of nanoscale building blocks (NBBs) through aerosol feeding on solid culture substrates. We employ this biosynthesis strategy to assemble a wide range of NBBs into cellulose nanofibril-based bulk nanocomposites. In particular, the biosynthesized carbon nanotubes/bacterial cellulose nanocomposites that consist of integrated 3D cellulose nanofibril networks simultaneously achieve an extremely high mechanical strength and electrical conductivity, and thus exhibit outstanding performance as high-strength lightweight electromagnetic interference shielding materials. The biosynthesis approach represents a general and efficient strategy for large-scale production of functional bulk nanocomposites with enhanced performances for practical applications. Industrial-scale production of these bulk nanocomposite materials for practical applications can be expected in the near future.     

Algorithm-improved high-speed and non-invasive confocal Raman imaging of 2D materials

Confocal Raman microscopy is important for characterizing 2D materials, but its low throughput significantly hinders its applications. For metastable materials such as graphene oxide (GO), the low throughput is aggravated by the requirement of extremely low laser dose to avoid sample damage. Here we introduce algorithm-improved confocal Raman microscopy (ai-CRM), which increases the Raman scanning rate by one to two orders of magnitude with respect to state-of-the-art works for a variety of 2D materials. Meanwhile, GO can be imaged at a laser dose that is two to three orders of magnitude lower than previously reported, such that laser-induced variations of the material properties can be avoided. ai-CRM also enables fast and spatially resolved quantitative analysis, and is readily extended to 3D mapping of composite materials. Since ai-CRM is based on general mathematical principles, it is cost-effective, facile to implement and universally applicable to other hyperspectral imaging methods.     

Vitamin D: Actions for the new millennium

The past two decades have witnessed new facets in vitamin D metabolism. Free vitamin D₃ till now considered to be limited to animal sources, has been shown to occur in plants. Further, the extrarenal synthesis of active vitamin D₃ or calcitriol has been documented in physiological as well as in certain pathological conditions. At the cellular level, calcitriol acts through a dual mechanism. The genomic pathway involves the vitamin D receptor (VDR) which is of ubiquitous distribution and linked with various diseases. Besides, a nongenomic VDR—independent pathway also exists. The biological effects of calcitriol can no longer be dismissed by merely referring to calcium/bone homeostasis. It enhances the perinatal growth and suppresses the abnormal growth, as well. The effects on the endocrine, immune, cardiovascular, reproductive and nervous systems have also been characterized. It is compelling to believe that calcitriol and/or its analogues will find extensive applications at least in the treatment of osteoporosis, perinatal growth retardation, neoplasia, psoriasis, insulin resistance and transplantation.     

Novel 2D CaCl crystals with metallicity,room-temperature ferromagnetism,heterojunction, piezoelectricity-like property and monovalent calcium ions

Under ambient conditions, the only known valence state of calcium ions is +2, and the corresponding crystals with calcium ions are insulating and nonferromagnetic. Here, using cryo-electron microscopy, we report direct observation of two-dimensional (2D) CaCl crystals on reduced graphene oxide (rGO) membranes, in which the calcium ions are only monovalent (i.e. +1). Remarkably, metallic rather than insulating properties are displayed by those CaCl crystals. More interestingly, room-temperature ferromagnetism, graphene–CaCl heterojunction, coexistence of piezoelectricity-like property and metallicity, as well as the distinct hydrogen storage and release capability of the CaCl crystals in rGO membranes are experimentally demonstrated. We note that such CaCl crystals are obtained by simply incubating rGO membranes in salt solutions below the saturated concentration, under ambient conditions. Theoretical studies suggest that the formation of those abnormal crystals is attributed to the strong cation-π interactions of the Ca cations with the aromatic rings in the graphene surfaces. The findings highlight the realistic potential applications of such abnormal CaCl material with unusual electronic properties in designing novel transistors and magnetic devices, hydrogen storage, catalyzers, high-performance conducting electrodes and sensors, with a size down to atomic scale.     

Mass production of 2D materials by intermediate-assisted grinding exfoliation

The scalable and high-efficiency production of 2D materials is a prerequisite to their commercial use. Currently, only graphene and graphene oxide can be produced on a ton scale, and the inability to produce other 2D materials on such a large scale hinders their technological applications. Here we report a grinding exfoliation method that uses micro-particles as force intermediates to resolve applied compressive forces into a multitude of small shear forces, inducing the highly efficient exfoliation of layer materials. The method, referred to as intermediate-assisted grinding exfoliation (iMAGE), can be used for the large-scale production of many 2D materials. As an example, we have exfoliated bulk h-BN into 2D h-BN with large flake sizes, high quality and structural integrity, with a high exfoliation yield of 67%, a high production rate of 0.3 g h⁻¹ and a low energy consumption of 3.01 × 10⁶ J g⁻¹. The production rate and energy consumption are one to two orders of magnitude better than previous results. Besides h-BN, this iMAGE technology has been used to exfoliate various layer materials such as graphite, black phosphorus, transition metal dichalcogenides, and metal oxides, proving its universality. Molybdenite concentrate, a natural low-cost and abundant mineral, was used as a demo for the large-scale exfoliation production of 2D MoS₂ flakes. Our work indicates the huge potential of the iMAGE method to produce large amounts of various 2D materials, which paves the way for their commercial application.     

Biomimetic micro∕nanostructured functional surfaces for microfluidic and tissue engineering applications

This paper reviews our work on the application of ultrafast pulsed laser micro∕nanoprocessing for the three-dimensional (3D) biomimetic modification of materials surfaces. It is shown that the artificial surfaces obtained by femtosecond-laser processing of Si in reactive gas atmosphere exhibit roughness at both micro- and nanoscales that mimics the hierarchical morphology of natural surfaces. Along with the spatial control of the topology, defining surface chemistry provides materials exhibiting notable wetting characteristics which are potentially useful for open microfluidic applications. Depending on the functional coating deposited on the laser patterned 3D structures, we can achieve artificial surfaces that are (a) of extremely low surface energy, thus water-repellent and self-cleaned, and (b) responsive, i.e., showing the ability to change their surface energy in response to different external stimuli such as light, electric field, and pH. Moreover, the behavior of different kinds of cells cultured on laser engineered substrates of various wettabilities was investigated. Experiments showed that it is possible to preferentially tune cell adhesion and growth through choosing proper combinations of surface topography and chemistry. It is concluded that the laser textured 3D micro∕nano-Si surfaces with controllability of roughness ratio and surface chemistry can advantageously serve as a novel means to elucidate the 3D cell-scaffold interactions for tissue engineering applications.     

Microfluidic devices for cell cultivation and proliferation

Microfluidic technology provides precise, controlled-environment, cost-effective, compact, integrated, and high-throughput microsystems that are promising substitutes for conventional biological laboratory methods. In recent years, microfluidic cell culture devices have been used for applications such as tissue engineering, diagnostics, drug screening, immunology, cancer studies, stem cell proliferation and differentiation, and neurite guidance. Microfluidic technology allows dynamic cell culture in microperfusion systems to deliver continuous nutrient supplies for long term cell culture. It offers many opportunities to mimic the cell-cell and cell-extracellular matrix interactions of tissues by creating gradient concentrations of biochemical signals such as growth factors, chemokines, and hormones. Other applications of cell cultivation in microfluidic systems include high resolution cell patterning on a modified substrate with adhesive patterns and the reconstruction of complicated tissue architectures. In this review, recent advances in microfluidic platforms for cell culturing and proliferation, for both simple monolayer (2D) cell seeding processes and 3D configurations as accurate models of in vivo conditions, are examined.     

Partially hydroxylated ultrathin iridium nanosheets as efficient electrocatalysts for water splitting

Ultrathin two-dimensional (2D) materials have attracted considerable attention for their unique physicochemical properties and promising applications; however, preparation of freestanding ultrathin 2D noble metal remains a significant challenge. Here, for the first time, we report use of a wet-chemical method to synthesize partially hydroxylated ultrathin Ir nanosheets (Ir-NSs) of only five to six atomic layers’ thickness. Detailed analysis indicates that the growth confinement effect of carbon monoxide and the partially hydroxylated surface play a critical role in formation of the ultrathin structure. The ultrathin Ir-NSs exhibit excellent performance for both the hydrogen evolution reaction and oxygen evolution reaction in a wide pH range, outperforming the state-of-the-art Pt/C and IrO₂, respectively. Density-functional theory calculations reveal that the partial hydroxylation not only enhances the surface electron transfer between Ir-sites and intermediate O-species, but also guarantees efficient initial activation of bond cleavage of H-O-H for first-step H₂O splitting. This, ultimately, breaks through barriers to full water splitting, with efficient electron transfer essentially maintained.     

Learning entity-centric document representations using an entity facet topic model

Learning semantic representations of documents is essential for various downstream applications, including text classification and information retrieval. Entities, as important sources of information, have been playing a crucial role in assisting latent representations of documents. In this work, we hypothesize that entities are not monolithic concepts; instead they have multiple aspects, and different documents may be discussing different aspects of a given entity. Given that, we argue that from an entity-centric point of view, a document related to multiple entities shall be (a) represented differently for different entities (multiple entity-centric representations), and (b) each entity-centric representation should reflect the specific aspects of the entity discussed in the document.In this work, we devise the following research questions: (1) Can we confirm that entities have multiple aspects, with different aspects reflected in different documents, (2) can we learn a representation of entity aspects from a collection of documents, and a representation of document based on the multiple entities and their aspects as reflected in the documents, (3) does this novel representation improves algorithm performance in downstream applications, and (4) what is a reasonable number of aspects per entity? To answer these questions we model each entity using multiple aspects (entity facets¹), where each entity facet is represented as a mixture of latent topics. Then, given a document associated with multiple entities, we assume multiple entity-centric representations, where each entity-centric representation is a mixture of entity facets for each entity. Finally, a novel graphical model, the Entity Facet Topic Model (EFTM), is proposed in order to learn entity-centric document representations, entity facets, and latent topics.Through experimentation we confirm that (1) entities are multi-faceted concepts which we can model and learn, (2) a multi-faceted entity-centric modeling of documents can lead to effective representations, which (3) can have an impact in downstream application, and (4) considering a small number of facets is effective enough. In particular, we visualize entity facets within a set of documents, and demonstrate that indeed different sets of documents reflect different facets of entities. Further, we demonstrate that the proposed entity facet topic model generates better document representations in terms of perplexity, compared to state-of-the-art document representation methods. Moreover, we show that the proposed model outperforms baseline methods in the application of multi-label classification. Finally, we study the impact of EFTM’s parameters and find that a small number of facets better captures entity specific topics, which confirms the intuition that on average an entity has a small number of facets reflected in documents.     

Ultra-thin metal-organic framework nanoribbons

Structure engineering of metal-organic frameworks (MOFs) at the nanometer scale is attracting increasing interest due to their unique properties and new functions that normally cannot be achieved in bulk MOF crystals. Here, we report the preparation of ultra-thin MOF nanoribbons (NRBs) by using metal-hydroxide nanostructures as the precursors. Importantly, this general method can be used to synthesize various kinds of ultra-thin MOF NRBs, such as MBDC (M = Co, Ni; BDC = 1,4-benzenedicarboxylate), NiCoBDC, CoTCPP (TCPP = tetrakis(4-carboxyphenyl)porphyrin) and MIL-53(Al) NRBs. As a proof-of-concept application, the as-prepared ultra-thin CoBDC NRBs have been successfully used as a fluorescent sensing platform for DNA detection, which exhibited excellent sensitivity and selectivity. The present strategy might open an avenue to prepare MOF nanomaterials with new structures and unique properties for various promising applications.     

A new twist on graphene: an interview with Pablo Jarillo-Herrero and Allan MacDonald

Graphene is the building block of graphite, made of carbon atoms bonded into sheets of hexagonal rings just a single atom thick. Although such isolated sheets had been predicted for many decades to exist, and had been grown on other surfaces, interest in this material exploded after the discovery in 2004 that single sheets could be made easily and cheaply by separating them mechanically from graphite flakes (a process called exfoliation). Although graphene is often advertised as a ‘wonder material’—electronically conducting, transparent and extremely strong and flexible—much of the interest in it is more fundamental. As a 2D conductor, graphene shows unusual electronic and magnetic properties that enable the study of quantum-mechanical effects of confinement and of correlations between electron motions—some of which might find applications in electronic devices. The excitement of this discovery was reflected in the award of the 2010 Nobel Prize in Physics to two pioneers in the field: Andre Geim and Konstantin Novoselov of the University of Manchester in the UK.This rich behavior is broadened still further when two graphene sheets are brought close enough to interact with one another. In particular, the electronic properties may then depend on the relative orientation of the sheets: how aligned the two ‘honeycomb’ lattices are. Two grids superimposed on one another may create ‘superlattices’: regularities at larger scales than the grid spacing, due to registry (commensurability) between the two at certain angles. This so-called moiré effect is sometimes evident for two closely spaced grid-like fences seen from afar. Experimentally exploring the electronic properties of such ‘twisted bilayer graphene’ requires an ability to precisely control the position and orientation of the two sheets. These phenomena are now recognized as generic to other 2D materials, such as hexagonal sheets of boron nitride. They have revealed a fertile playground for condensed-matter physics. In particular, striking electronic properties appear at certain ‘magic-angle’ twists of the layers.NSR spoke to two of the leading experts in the study of magic-angle twisted bilayer graphene (MATBG): experimentalist Pablo Jarillo-Herrero of the Massachusetts Institute of Technology and theorist Allan MacDonald of the University of Texas at Austin.     

Graph-based discovery and analysis of atomic-scale one-dimensional materials

Recent decades have witnessed an exponential growth in the discovery of low-dimensional materials (LDMs), benefiting from our unprecedented capabilities in characterizing their structure and chemistry with the aid of advanced computational techniques. Recently, the success of two-dimensional compounds has encouraged extensive research into one-dimensional (1D) atomic chains. Here, we present a methodology for topological classification of structural blocks in bulk crystals based on graph theory, leading to the identification of exfoliable 1D atomic chains and their categorization into a variety of chemical families. A subtle interplay is revealed between the prototypical 1D structural motifs and their chemical space. Leveraging the structure graphs, we elucidate the self-passivation mechanism of 1D compounds imparted by lone electron pairs, and reveal the dependence of the electronic band gap on the cationic percolation network formed by connections between structure units. This graph-theory-based formalism could serve as a source of stimuli for the future design of LDMs.     

Halogen bonding in the co-crystallization of potentially ditopic diiodotetrafluorobenzene: a powerful tool for constructing multicomponent supramolecular assemblies

Halogen bonding is emerging as a significant driving force for supramolecular self-assembly and has aroused great interest during the last two decades. Among the various halogen-bonding donors, we take notice of the ability of 1,4-diiodotetrafluorobenzene (1,4-DITFB) to co-crystallize with diverse halogen-bonding acceptors in the range from neutral Lewis bases (nitrogen-containing compounds, N-oxides, chalcogenides, aromatic hydrocarbons and organometallic complexes) to anions (halide ions, thio/selenocyanate ions and tetrahedral oxyanions), leading to a great variety of supramolecular architectures such as discrete assemblies, 1D infinite chains and 2D/3D networks. Some of them act as promising functional materials (e.g. fluorescence, phosphorescence, optical waveguide, laser, non-linear optics, dielectric and magnetism) and soft materials (e.g. liquid crystal and supramolecular gel). Here we focus on the supramolecular structures of multicomponent complexes and their related physicochemical properties, highlight representative examples and show clearly the main directions that remain to be developed and improved in this area. From the point of view of crystal engineering and supramolecular chemistry, the complexes summarized here should give helpful information for further design and investigation of the elusive category of halogen-bonding supramolecular functional materials.     

The differential impact of privately and publicly funded R&D on R&D investment and innovation: the Italian case

This paper explores the impact of a specific R&D policy instrument, the Italian Fondo per le Agevolazioni della Ricerca (FAR), on industrial R&D and technological output at the firm level. Our objective is threefold: first, to identify the presence or absence of private R&D investment additionality/crowding-out within a pooled sample and in various firm subsets (identified by region, size, level of technology, and other features), while also taking into account the effect of single policy instruments or mixes of them. Secondly, to analyse the output (innovation) additionality by comparing the differential impact of privately funded R&D and publicly funded R&D expenditure on applications for patents filed by firms. Thirdly, the paper will compare the structural characteristics of firms showing additionality with those of firms showing crowding-out, in order to determine the firm characteristics associated with successful policy interventions. Our results suggest that FAR is effective in the pooled sample, although no effect emerges in some firm subsets. In particular, while large firms seem to have been decisive for the success of this policy, small firms present a more marked crowding-out effect. Furthermore, the firms’ growth strategies and ability to transform R&D input into innovation output (patents) seem to have a positive effect in terms of additionality.     

Unprecedented and highly stable lithium storage capacity of (001) faceted nanosheet-constructed hierarchically porous TiO2/rGO hybrid architecture for high-performance Li-ion batteries

Active crystal facets can generate special properties for various applications. Herein, we report a (001) faceted nanosheet-constructed hierarchically porous TiO₂/rGO hybrid architecture with unprecedented and highly stable lithium storage performance. Density functional theory calculations show that the (001) faceted TiO₂ nanosheets enable enhanced reaction kinetics by reinforcing their contact with the electrolyte and shortening the path length of Li⁺ diffusion and insertion-extraction. The reduced graphene oxide (rGO) nanosheets in this TiO₂/rGO hybrid largely improve charge transport, while the porous hierarchy at different length scales favors continuous electrolyte permeation and accommodates volume change. This hierarchically porous TiO₂/rGO hybrid anode material demonstrates an excellent reversible capacity of 250 mAh g^–1 at 1 C (1 C = 335 mA g^–1) at a voltage window of 1.0–3.0 V. Even after 1000 cycles at 5 C and 500 cycles at 10 C, the anode retains exceptional and stable capacities of 176 and 160 mAh g^–1, respectively. Moreover, the formed Li₂Ti₂O₄ nanodots facilitate reversed Li⁺ insertion-extraction during the cycling process. The above results indicate the best performance of TiO₂-based materials as anodes for lithium-ion batteries reported in the literature.     

Light-emitting self-assembled metallacages

Coordination-driven self-assembly of metallacages has garnered significant interest because of their 3D layout and cavity-cored nature. The well-defined, highly tunable metallacage structures render them particularly attractive for investigating the properties of luminophores, as well as for inducing novel photophysical characters that enable widespread applications. In this review, we summarize the recent advances in synthetic methodologies for light-emitting metallacages, and highlight some representative applications of these metallacages. In particular, we focus on the favorable photophysical properties—including high luminescence efficiency in various physical states, good modularity in photophysical properties and stimulus responsiveness—that have resulted from incorporating ligands displaying aggregation-induced emission (AIE) into metallacages. These features show that the synergy between carrying out coordination-driven self-assembly and using luminophores with novel photophysical characteristics like AIE could stimulate the development of supramolecular luminophores for applications in fields as diverse as sensing, biomedicine and catalysis.     

Six-membered-ring inorganic materials: definition and prospects

The six-membered ring (SMR) is a common structure unit for numerous material systems. These materials include, but are not limited to, the typical two-dimensional materials such as graphene, h-BN, and transition metal dichalcogenides, as well as three-dimensional materials such as beryllium, magnesium, MgB₂ and Bi₂Se₃. Although many of these materials have already become ‘stars’ in materials science and condensed-matter physics, little attention has been paid to the roles of the SMR unit across a wide range of compositions and structures. In this article, we systematically analyze these materials with respect to their very basic SMR structural unit, which has been found to play a deterministic role in the occurrence of many intriguing properties and phenomena, such as Dirac electronic and phononic spectra, superconductivity and topology. As a result, we have defined this group of materials as SMR inorganic materials, opening up a new perspective on materials research and development. With their unique properties, SMR materials deserve wide attention and in-depth investigation from materials design, new physical discoveries to target-wizard applications. It is expected that SMR materials will find niche applications in next-generation information technology, renewable energy, space, etc.