二维过渡金属硫族化合物缺陷工程

二维过渡金属硫族化合物(two-dimensional transition metal dichalcogenides,TMDs)具有厚度在原子级别、禁带宽度随层数在1～2 eV内变化、高载流子迁移率(如MoS₂载流子迁移率达到了200 cm²·V^-1·s^-1)等特点,在光学、电学等领域具有广泛应用。TMDs的超薄特性使此类材料与块体材料相比,更容易受到缺陷调控的影响,改变材料原有性能。在本综述中,首先介绍了TMDs的晶体结构和相结构,并根据维度特征对缺陷的类型进行了分类;接着从缺陷的抑制和修复,以及缺陷的制造两方面出发,总结了缺陷调控TMDs材料性能的最新研究进展;在此基础上,介绍了缺陷工程在电学、光学、磁学、电催化等领域的具体应用;最后,本综述讨论了缺陷工程在应用过程中面临的实际问题,并对其未来的研究及发展方向进行了展望。     

基于过渡金属二硫族化物析氢催化的研究进展

解决全球气候变化和能源危机的有效途径之一是用氢能源(H₂)代替传统的化石能源. 析氢反应(Electrochemical hydrogen evolution reaction, HER) 被认为是绿色环保的可持续产氢途径, 通常电解过程需要催化剂以降低电化学电位, 提高能量利用效率. 目前最先进的催化剂仍然依赖于贵金属, 但是研究表明, 过渡金属二硫族化物(Transition metal dichalcogenides, TMDs)同样具有优异的催化活性, 与贵金属相比, TMDs产量大、 价格低、 催化活性好、 便于调控和修饰, 有望替代贵金属在催化领域的应用. 基于此, 本文讨论了近年来TMDs在析氢方面的研究情况以及TMDs材料的性能调控, 包含原子工程、 相工程和异质结. 并总结和展望了TMDs催化材料的挑战与机遇.     

Preparation and Crystal Growth of Transition Metal Dichalcogenides

Dichalcogenides are known from almost all transition metals. The representatives of this class of compounds show a number of interesting physical and chemical properties depending on their constituent transition metal and crystal structure, which makes them interesting for basic studies and applications in high-end electronics, spintronics, optoelectronics, energy storage, flexible electronics, DNA sequencing and personalized medicine to this day. Many of these properties and effects can only be investigated on chemically and crystallographically pure samples - usually on single crystals. The vast majority of these compounds can be crystallized using chemical vapour transport. However crystallization from the melt is also possible in a considerable number of compounds, including the frequently used self-flux technique. For several compounds the crystallization from different solvents or solvent mixtures by means of solvothermal or hydrothermal synthesis is described.     

Electrochemical Sensors Using Two‐Dimensional Layered Nanomaterials

Two‐dimensional (2D) layered nanomaterials, e.g. graphene and molybdenum disulfide (MoS₂), have rapidly emerged in material sciences due to their unique physical, chemical and mechanical properties. In the meanwhile, there is a growing interest in constructing electrochemical sensors for a wide range of chemical and biological molecules by using these 2D nanomaterials. In this review, we summarize recent advances on using graphene and MoS₂ for the development of electrochemical sensors for small molecules, proteins, nucleic acids and cells detection. We also provide our perspectives in this rapidly developing field.     

Stacking of Exfoliated Two‐Dimensional Materials: A Review

In recent years, two‐dimensional (2D) atomic crystals represented by graphene have opened up new fields of 2D physics. Layered materials with atomic layer thickness are self‐assembled into van der Waals heterostructures by weak van der Waals forces without considering lattice matching. Van der Waals heterostructures can not only enhance the performance of its constituent materials but also show new characteristics. High‐quality heterostructures require mechanically cleaved intrinsic 2D materials and flexible 2D material stacking techniques. Here, we summarize in detail the reliable exfoliation methods for large‐area single‐layer 2D materials and the dry and wet stacking techniques with high success rates. The twisted bilayer graphene is used as an example to briefly introduce the single‐crystal tearing method, which is currently the most practical method for preparing isotropic twisted heterostructures with high‐precision rotation angles. We hope to provide a valuable reference for researchers of 2D materials.     

Two‐Dimensional Noble‐Metal Chalcogenides and Phosphochalcogenides

Noble‐metal chalcogenides, dichalcogenides, and phosphochalcogenides are an emerging class of two‐dimensional materials. Quantum confinement (number of layers) and defect engineering enables their properties to be tuned over a broad range, including metal‐to‐semiconductor transitions, magnetic ordering, and topological surface states. They possess various polytypes, often of similar formation energy, which can be accessed by selective synthesis approaches. They excel in mechanical, optical, and chemical sensing applications, and feature long‐term air and moisture stability. In this Minireview, we summarize the recent progress in the field of noble‐metal chalcogenides and phosphochalcogenides and highlight the structural complexity and its impact on applications.     

Functionalization of Liquid‐Exfoliated Two‐Dimensional 2H‐MoS2

Layered two‐dimensional (2D) inorganic transition‐metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS₂. We found that the reaction of liquid‐exfoliated 2D MoS₂, with M(OAc)₂ salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS₂–M(OAc)₂ materials. Importantly, this method furnished the 2H‐polytype of MoS₂ which is a semiconductor. X‐ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT–IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS₂ surface sulfur atoms to the M(OAc)₂ salt. Interestingly, functionalization of 2H‐MoS₂ allows for its dispersion/processing in more conventional laboratory solvents.     

二维过渡金属硫族化合物在超级电容器中的研究进展

近年来, 过渡金属硫族化合物(TMDs)作为一种新兴的二维材料, 因其独特的层状结构及电学特性成为超级电容器电极材料的理想候选者之一. 本文介绍了二维TMDs的常用合成方法, 阐述了钼基、 钨基和钒基等TMDs在超级电容器中的研究进展, 分析了形貌、 尺寸和改性方法等因素对TMDs材料电化学性能的影响, 并对TMDs在超级电容器领域的工业化应用和挑战进行了总结与展望.     

化学气相沉积法合成二维过渡金属硫族化合物研究进展

二维晶体材料所独有的二维平面结构赋予了这类材料诸多独特的性质. 近年来围绕二维过渡金属硫族化合物的相关研究发展迅速. 本文以二维MoS₂、WS₂为代表概述了利用化学气相沉积法合成过渡金属硫族化合物二维晶体的研究进展, 阐述了基本合成策略, 讨论了主要影响因素, 归纳了以MoS₂、WS₂为结构基元的二维合金及异质结构的合成方法, 最后阐明了利用化学气相沉积法合成二维晶体存在的主要问题并展望了这一领域的发展前景.     

二维过渡金属硫族化合物在生物医学中的应用

二维过渡金属硫族化合物(TMDs)是继石墨烯纳米材料发展之后一类新型的二维纳米材料. 由于其特殊的物理化学性质, TMDs二维纳米材料在能源、光电器件、催化反应等多个领域引起了人们广泛的研究兴趣. 近年来这类材料在纳米生物医学方面也得到人们广泛的关注. 这篇综述简单介绍TMDs二维层状纳米材料的制备、表面修饰、生物成像、肿瘤治疗和毒理学研究, 并对二维TMDs纳米材料未来在生物医学领域的发展做出展望.     

Two‐Dimensional Boron Monolayers Mediated by Metal Substrates

Two‐dimensional (2D) materials, such as graphene and boron nitride, have specific lattice structures independent of external conditions. In contrast, the structure of 2D boron sensitively depends on metal substrate, as we show herein using the cluster expansion method and a newly developed surface structure‐search method, both based on first‐principles calculations. The preferred 2D boron on weaker interacting Au is nonplanar with significant buckling and numerous polymorphs as in vacuum, whereas on more reactive Ag, Cu, and Ni, the polymorphic energy degeneracy is lifted and a particular planar structure is found to be most stable. We also show that a layer composed of icosahedral B₁₂ is unfavorable on Cu and Ni but unexpectedly becomes a possible minimum on Au and Ag. The substrate‐dependent 2D boron choices originate from a competition between the strain energy of buckling and chemical energy of electronic hybridization between boron and metal.     

二维过渡金属硫族化合物纳米材料的制备与应用研究进展

二维过渡金属硫族化合物（TMDCs）纳米材料是一种新型的类石墨烯材料,具有优异的电学、光学及催化特性.简要介绍了TMDCs的晶体结构和电子特性;详细综述了常用的制备方法,主要包括机械剥离法、水（溶剂）热合成法、化学气相合成法等,并总结了各种方法的优缺点;归纳了二维TMDCs在电子器件、光电器件、传感器、微波吸收、储能和催化等方面的应用研究进展;最后总结了该领域存在的问题,展望了研究前景.     

Growth of Single-crystalline Transition Metal Dichalcogenides Monolayers with Large-size

Two-dimensional(2D) transition metal dichalcogenides(TMDCs) semiconductors, such as monolayers of molybdenum disulfide(MoS₂) and tungsten disulfide(WS₂) can potentially serve as ultrathin channel materials for building short channel field-effect transistors(FETs) to further extend Moore's Law. It is essential to develop controllable approaches for the synthesis of large single crystals of these 2D semiconductors to promote their practical applications in future electronics. In this short review, we summarized the recent advances on the chemical vapor deposition(CVD) of single crystalline semiconducting 2D TMDCs with a large size. We first discussed the driving force and urgent demands on developing controllable approaches for the growth of large 2D TMDCs single crystals and then summarized the current strategies and representative studies on the CVD growth of large 2D single crystals. Finally, we discussed the challenges and future directions in this topic.     

Design Concepts of Transition Metal Dichalcogenides for High-Performance Aqueous Zn-Ion Storage

Aqueous Zn-ion batteries (AZIBs) are considered as promising large-scale energy storage devices due to their high safety and low cost. Transition metal dichalcogenides (TMDs) as the potential aqueous Zn-storage cathode materials are under the research spotlight because of their facile 2D ion-transport channels and weak electrostatic interactions with Zn²⁺. In this concept article, we summarize the intrinsic structural features and aqueous Zn-storage mechanisms of the TMDs-based electrodes. More significantly, the latest design concepts of TMDs materials for high-performance AZIBs are discussed in detail from three aspects of interlayer expansion engineering, phase transition engineering, and structure defects engineering. Finally, the current challenges facing TMDs cathodes and possible remedies are outlined for future developments towards efficient, rapid, and stable aqueous Zn-ion storage.     

Synthesis of Two‐Dimensional Transition‐Metal Phosphates with Highly Ordered Mesoporous Structures for Lithium‐Ion Battery Applications

Materials with ordered mesoporous structures have shown great potential in a wide range of applications. In particular, the combination of mesoporosity, low dimensionality, and well‐defined morphology in nanostructures may exhibit even more attractive features. However, the synthesis of such structures is still challenging in polar solvents. Herein, we report the preparation of ultrathin two‐dimensional (2D) nanoflakes of transition‐metal phosphates, including FePO₄, Mn₃(PO₄)₂, and Co₃(PO₄)₂, with highly ordered mesoporous structures in a nonpolar solvent. The as‐obtained nanoflakes with thicknesses of about 3.7 nm are constructed from a single layer of parallel‐packed pore channels. These uniquely ordered mesoporous 2D nanostructures may originate from the 2D assembly of cylindrical micelles formed by the amphiphilic precursors in the nonpolar solvent. The 2D mesoporous FePO₄ nanoflakes were used as the cathode for a lithium‐ion battery, which exhibits excellent stability and high rate capabilities.     

Transitional Metal/Chalcogen Dependant Interactions of Hairpin DNA with Transition Metal Dichalcogenides,MX2

Owing to the attractive properties that transition metal dichalcogenides (TMDs) display, they have found recent application in the fabrication of biosensing devices. These devices involve the immobilization of a recognition element such as DNA onto the surface of TMDs. Therefore, it is imperative to examine the interactions between TMDs and DNA. Herein, we explore the effect of different transition metals (Mo and W) and chalcogens (S and Se) on the interactions between hairpin DNA and TMDs of both bulk and t‐BuLi exfoliated forms. We discovered that the interactions are strongly dependent on the metal/chalcogen composition in TMDs.     

Amine‐Templated One‐Dimensional Metal Sulfates Including a Mixed‐Valent Fe Compound with a Half‐Kagome Structure

Organically templated metal sulfates are relatively new. Six amine‐templated transition‐metal sulfates with different types of chain structures, including a novel iron sulfate with a chain structure corresponding to one half of the kagome structure, were synthesized by hydro/solvothermal methods. Amongst the one‐dimensional metal sulfates, [C₁₀N₂H₁₀][Zn(SO₄)Cl₂] ( 1 ) is the simplest, being formed by corner‐linked ZnO₂Cl₂ and SO₄ tetrahedra. [C₆N₂H₁₈][Mn(SO₄)₂(H₂O)₂] ( 2 ) and [C₂N₂H₁₀][Ni(SO₄)₂(H₂O)₂] ( 3 ) have ladder structures comprising four‐membered rings formed by SO₄ tetrahedra and metal–oxygen octahedra, just as in the mineral kröhnkite. [C₄N₂H₁₂][V^III(OH)(SO₄)₂]?H₂O ( 4 ) and [C₄N₂H₁₂][VF₃(SO₄)] ( 5 ) exhibit chain topologies of the minerals tancoite and butlerite, respectively. The structure of [C₄N₂H₁₂][H₃O][Fe^IIIFe^II F₆(SO₄)] ( 6 ) is noteworthy in that it corresponds to half of the hexagonal kagome structure. It exhibits ferrimagnetic properties at low temperatures and the absence of frustration, unlike the mixed‐valent iron sulfate with the full kagome structure.     

Functionalization of Two‐Dimensional MoS2: On the Reaction Between MoS2 and Organic Thiols

Two‐dimensional layered transition metal dichalcogenides (TMDs) have attracted great interest owing to their unique properties and a wide array of potential applications. However, due to their inert nature, pristine TMDs are very challenging to functionalize. We demonstrate a general route to functionalize exfoliated 2H‐MoS₂ with cysteine. Critically, MoS₂ was found to be facilitating the oxidation of the thiol cysteine to the disulfide cystine during functionalization. The resulting cystine was physisorbed on MoS₂ rather than coordinated as a thiol (cysteine) filling S‐vacancies in the 2H‐MoS₂ surface, as originally conceived. These observations were found to be true for other organic thiols and indeed other TMDs. Our findings suggest that functionalization of two‐dimensional MoS₂ using organic thiols may not yield covalently or datively tethered functionalities, rather, in this instance, they yield physisorbed disulfides that are easily removed.