Recent Strategies for the Synthesis of Phase-Pure Ultrathin 1T/1T' Transition Metal Dichalcogenide Nanosheets.

The past few decades have witnessed a notable increase in transition metal dichalcogenide (TMD) related research not only because of the large family of TMD candidates but also because of the various polytypes that arise from the monolayer configuration and layer stacking order. The peculiar physicochemical properties of TMD nanosheets enable an enormous range of applications from fundamental science to industrial technologies based on the preparation of high-quality TMDs. For polymorphic TMDs, the 1T/1T' phase is particularly intriguing because of the enriched density of states, and thus facilitates fruitful chemistry. Herein, we comprehensively discuss the most recent strategies for direct synthesis of phase-pure 1T/1T' TMD nanosheets such as mechanical exfoliation, chemical vapor deposition, wet chemical synthesis, atomic layer deposition, and more. We also review frequently adopted methods for phase engineering in TMD nanosheets ranging from chemical doping and alloying, to charge injection, and irradiation with optical or charged particle beams. Prior to the synthesis methods, we discuss the configuration of TMDs as well as the characterization tools mostly used in experiments. Finally, we discuss the current challenges and opportunities as well as emphasize the promising fields for the future development.

Fast Lithium Ion Conductivity in Layered (Li-Ag)CrS2.

Fast ionic conductors are of great importance for novel technologies in high-performance and rechargeable energy storage components with reliable safety and thermal stability. Here, we demonstrate a new concept of the pillar effect to construct two-dimensional (2D) fast Li+ conductors. Our developed layered LixAg1-xCrS2 (0 < x < 0.4) structure, with larger-radius Ag+ served as "pillars" to effectively rigidify the interlayer ionic channel, leads to multi-ion concerted migration behavior and thus contributes to low activation energy and fast Li+ diffusion. Consequently, the room-temperature ionic conductivity in (Li-Ag)CrS2 system reaches up to 19.6 mS·cm-1 for x is 0.31, which is comparable to that of currently best Li-ion conductors. Furthermore, the pillared structure exhibits unique ionic transport that the conductivity decreases as temperature elevated, which can be ascribed to the competition between Li+ and Ag+ migration through tetrahedral viods in 2D channel. We anticipated that pillar effect would pave a new way to explore new catalogue of Li superionic conductors.

Electron Transport in Low Dimensional Solids: A Surface Chemistry Perspective.

Electron transport is a fundamental process that controls the intrinsic chemical and physical properties of solid materials. The surface phase becomes dominant when downsized dimensionality into cluster scale in nanomaterials, and surface chemistry plays more and more important role in regulating electron transport. During past decades, varieties of chemical approaches have been developed to modify the surface of low dimensional solids, substantially providing versatile perspectives on engineering electron transport. In this Perspective, we focus on recent researches concerning surface chemical modification strategies, such as surface molecular adsorption, atomic incorporation, defect engineering and spin scattering to engineer electron transport of typical one-/two-dimensional systems. Under the framework of Drude's transport model, we highlight the core role of micro degrees of freedom, i.e., charge, lattice, and spin, in molecular-level understanding and optimizing the regulation effect of surface chemistry. Finally, based on the discussion and current achievements of surface chemistry effect on electron transport of low dimensional solids, some personal perspectives on the future development are also presented.

Solution Processing for Lateral Transition-Metal Dichalcogenides Homojunction from Polymorphic Crystal.

Homojunctions comprised of transition-metal dichalcogenides (TMD) polymorphs are attractive building blocks for next-generation two-dimensional (2D) electronic circuitry. However, the synthesis of such homojunctions, which usually involves elaborate manipulation at the nanoscale, still remains a great challenge. Herein, we demonstrated a solution-processing strategy to successfully harvest lateral semiconductor-metal homojunctions with high yield. Specially, through precisely controlled lithiation process, precursors of polymorphic crystal arranged with 1T-2H domains were successfully achieved. A programmed exfoliation procedure was further employed to orderly laminate each phase in the polymorphic crystal, thus leading to 1T-2H TMD homojunction monolayers with sizes up to tens of micrometers. Moreover, the atomically sharp boundaries and superior band alignment improved the device on the basis of the semiconductor-metal homojunction with 50% decrease of electric field strength required in the derivation of state transition. We anticipate that solution processing based on programmed exfoliation would be a powerful tool to produce new configurations of 2D nanomaterials.

Freestanding Cubic ZrN Single-Crystalline Films with Two-Dimensional Superconductivity.

The successful fabrication of freestanding two-dimensional (2D) crystals that exhibit unprecedented high crystal quality and macroscopic continuity renovates the conventional cognition that 2D long-range crystalline order cannot stably exist at finite temperatures. Current progresses are primarily limited to van der Waals (vdW) layered materials, while studies on how to obtain 2D materials from nonlayered bulk crystals remain sparse. Herein, we report the experimental realization of vdW-like cubic ZrN single crystal and emphasize the significant role of confined electrons in stabilizing the atomic structure at the 2D limit. Furthermore, the exfoliated ZrN single-crystal films with a few nanometers thick exhibit dimensional crossover effect of emerging 2D superconductivity with the unconventional upper critical field beyond Pauli paramagnetic limit, which suggests a dimensional effect in the pairing mechanism of dimensionally confined superconductors.

Acid-Assisted Exfoliation toward Metallic Sub-nanopore TaS2 Monolayer with High Volumetric Capacitance.

Conductive porous structures are favorable as active electrode materials for energy storage by boosting the active sites and specific surface area but have been rarely achieved in transition metal dichalcogenides. Here, we developed acid-assisted exfoliation for the first time, to successfully exfoliate TaS2 into very large-sized conductive monolayers with controllable in-plane sub-nanopores. By inducing both interlayer lattice expansion and basal in-plane etching, hydrogen ion, previously regarded disastrous in charged system, was creatively utilized as an efficient and easily accessible assistant in simultaneous exfoliation and controllable structural modification. Benefiting from pore size (∼0.95 nm) matching well with electrolyte ion size, coexistence of ultrahigh conductivity and fast ion transport was achieved in metallic large-sized monolayers. Notably, the as-produced TaS2-based electrode delivers large volumetric capacitance (508 F/cm3 at scan rate of 10 mV/s) and high energy density (58.5 Wh/L) when fabricated into a micro-supercapacitor. We anticipate acid-assisted exfoliation to be a promising strategy in constructing 2D nanomaterials with novel structure for wide energy applications.

Two-Dimensional Tellurium Nanosheets Exhibiting an Anomalous Switchable Photoresponse with Thickness Dependence.

Two-dimensional (2D) tellurium (Te) was recently predicted to be promising for diverse electronic and optoelectronic applications. However, the synthesis of high-quality 2D Te structures remains challenging, which greatly hinders the exploration of its full properties. Herein, an anomalous photoresponse from negative to positive as a function of thickness in Te nanosheets is reported. Ultrathin Te layers with large size and clean interface were obtained through a topotactic transformation, in which the 2D Te structure was derived from a layered MTe2 (M=Ti, Mo, W) matrix by excessive lithiation. Prominently, the photoresponse in Te nanosheets exhibits negative behavior when the thickness is less than 5 nm, which turns positive as the thickness increases. This unusual photoresponse will shed light on the full exploration of 2D non-layered materials with exotic properties.

Double-Exchange Effect in Two-Dimensional MnO2 Nanomaterials.

Electronic state transitions, especially metal-insulator transitions (MIT), offer physical properties that are useful in intriguing energy applications and smart devices. But to-date, very few simple metal oxides have been shown to undergo electronic state transitions near room temperature. Herein, we demonstrate experimentally that chemical induction of double-exchange in two-dimensional (2D) nanomaterials brings about a MIT near room temperature. In this case, valence-state regulation of a 2D MnO2 nanosheet induces a Mn(III)-O-Mn(IV) structure with the double-exchange effect, successfully triggering a near-room-temperature electronic transition with an ultrahigh negative magneto-resistance (MR). Double-exchange in 2D MnO2 nanomaterials exhibits an ultrahigh MR value of up to -11.3% (0.1 T) at 287 K, representing the highest reported negative MR values in 2D nanomaterials approaching room temperature. Also, the MnO2 nanosheet displays an infrared response of 7.1% transmittance change on going from 270 to 290 K. We anticipate that dimensional confinement of double-exchange structure promises novel magneto-transport properties and sensitive responses for smart devices.

Molecule-Confined Engineering toward Superconductivity and Ferromagnetism in Two-Dimensional Superlattice.

Superconductivity is mutually exclusive with ferromagnetism, because the ferromagnetic exchange field is often destructive to superconducting pairing correlation. Well-designed chemical and physical methods have been devoted to realize their coexistence only by structural integrity of inherent superconducting and ferromagnetic ingredients. However, such coexistence in freestanding structure with nonsuperconducting and nonferromagnetic components still remains a great challenge up to now. Here, we demonstrate a molecule-confined engineering in two-dimensional organic-inorganic superlattice using a chemical building-block approach, successfully realizing first freestanding coexistence of superconductivity and ferromagnetism originated from electronic interactions of nonsuperconducting and nonferromagnetic building blocks. We unravel totally different electronic behavior of molecules depending on spatial confinement: flatly lying Co(Cp)2 molecules in strongly confined SnSe2 interlayers weaken the coordination field, leading to spin transition to form ferromagnetism; meanwhile, electron transfer from cyclopentadienyls to the Se-Sn-Se lattice induces superconducting state. This entirely new class of coexisting superconductivity and ferromagnetism generates a unique correlated state of Kondo effect between the molecular ferromagnetic layers and inorganic superconducting layers. We anticipate that confined molecular chemistry provides a newly powerful tool to trigger exotic chemical and physical properties in two-dimensional matrixes.

Very Large-Sized Transition Metal Dichalcogenides Monolayers from Fast Exfoliation by Manual Shaking.

For two-dimensional transition metal dichalcogenides (TMD) materials, achieving large size with high quality to provide a basis for the next generation of electronic device geometries has been a long-term need. Here, we demonstrate that, by only manual shaking within several seconds, very large-sized TMD monolayers that cover a wide range of group IVB-VIB transition metal sulfides and selenides can be efficiently harvested from intercalated single-crystal counterparts. Taking TaS2 as examples, monolayers up to unprecedented size (>100 µm) are obtained while maintaining high crystalline quality and the phase structure of the starting materials. Furthermore, benefiting from the gentle manual shaking, we unraveled the atomic-level correlation between the intercalated lattice-strain effects and exfoliated nanosheets, and that strong tensile strain usually led to very large sizes. This work helps to deepen the understanding of exfoliation mechanism and provides a powerful tool for producing large-sized and high-quality TMD nanosheets appealing for further applications.

Surface chemical-modification for engineering the intrinsic physical properties of inorganic two-dimensional nanomaterials.

Two-dimensional (2D) nanomaterials, especially the inorganic ultrathin nanosheets with single or few-atomic layers, have been extensively studied due to their special structures and rich physical properties coming from the quantum confinement of electrons. With atomic-scale thickness, 2D nanomaterials have an extremely high specific surface area enabling their surface phase to be as important as bulk counterparts, and therefore provide an alternative way of modifying the surface phase for engineering the intrinsic physical properties of inorganic 2D nanomaterials. In this review, we focus on recent research concerning surface chemical modification strategies to effectively engineer the intrinsic physical properties of inorganic 2D nanomaterials. We highlight the newly developed regulation strategies of surface incorporation, defect engineering, and structure modulation of inorganic 2D nanomaterials, which respectively influence the intrinsic conductivity, band structure, and magnetism while maintaining the primary 2D freestanding structures that are vital for 2D based ultrasensitive electronic response, enhanced catalytic and magnetocaloric capabilities.

Hydrogen Treatment for Superparamagnetic VO2 Nanowires with Large Room-Temperature Magnetoresistance.

One-dimensional (1D) transition metal oxide (TMO) nanostructures are actively pursued in spintronic devices owing to their nontrivial d electron magnetism and confined electron transport pathways. However, for TMOs, the realization of 1D structures with long-range magnetic order to achieve a sensitive magnetoelectric response near room temperature has been a longstanding challenge. Herein, we exploit a chemical hydric effect to regulate the spin structure of 1D V-V atomic chains in monoclinic VO2 nanowires. Hydrogen treatment introduced V(3+) (3d(2) ) ions into the 1D zigzag V-V chains, triggering the formation of ferromagnetically coupled V(3+) -V(4+) dimers to produce 1D superparamagnetic chains and achieve large room-temperature negative magnetoresistance (-23.9 %, 300 K, 0.5 T). This approach offers new opportunities to regulate the spin structure of 1D nanostructures to control the intrinsic magnetoelectric properties of spintronic materials.

Metallic Nickel Hydroxide Nanosheets Give Superior Electrocatalytic Oxidation of Urea for Fuel Cells.

The direct urea fuel cell (DUFC) is an important but challenging renewable energy production technology, it offers great promise for energy-sustainable developments and mitigating water contamination. However, DUFCs still suffer from the sluggish kinetics of the urea oxidation reaction (UOR) owing to a 6 e(-) transfer process, which poses a severe hindrance to their practical use. Herein, taking ß-Ni(OH)2 nanosheets as the proof-of-concept study, we demonstrated a surface-chemistry strategy to achieve metallic Ni(OH)2 nanosheets by engineering their electronic structure, representing a first metallic configuration of transition-metal hydroxides. Surface sulfur incorporation successfully brings synergetic effects of more exposed active sites, good wetting behavior, and effective electron transport, giving rise to greatly enhanced performance for UOR. Metallic nanosheets exhibited a much higher current density, smaller onset potential and stronger durability.

Superparamagnetic Reduced Graphene Oxide with Large Magnetoresistance: A Surface Modulation Strategy.

The graphene system is actively pursued in spintronics for its nontrivial sp electron magnetism and its potential for the flexible surface chemical tuning of magnetoelectronic functionality. The magnetoresistance (MR) of graphene can be effectively tuned under high magnetic fields at cryogenic temperatures, but it remains a challenge to achieve sensitive magnetoelectric response under ambient conditions. We report the use of surface modulation to realize superparamagnetism in reduced graphene oxide (rGO) with sensitive magnetic field response. The superparamagnetic rGO was obtained by a mild oxidation process to partially remove the thiol groups covalently bound to the carbon framework, which brings about large low-field negative MR at room temperature (-8.6 %, 500 Oe, 300 K). This strategy provides a new approach for optimizing the intrinsic magnetoelectric properties of two-dimensional materials.

In situ unravelling structural modulation across the charge-density-wave transition in vanadium disulfide.

A deep understanding of the relationship between electronic and structure ordering across the charge-density-wave (CDW) transition is crucial for both fundamental study and technological applications. Herein, using in situ X-ray absorption fine structure (XAFS) spectroscopy coupled with high-resolution transmission electron microscopy (HRTEM), we have illustrated the atomic-level information on the local structural evolution across the CDW transition and its influence on the intrinsic electrical properties in VS2 system. The structure transformation, which is highlighted by the formation of vanadium trimers with derivation of V-V bond length (ΔR = 0.10 Å), was clearly observed across the CDW process. Moreover, the corresponding influence of lattice variation on the electronic behavior was clearly characterized by experimental results as well as theoretical analysis, which demonstrated that vanadium trimers drive the deformation of space charge density distribution into √3 ×√3 periodicity, with the conductivity of a1g band reducing by half. These observations directly unveiled the close connection between lattice evolution and electronic property variation, paving a new avenue for understanding the intrinsic nature of electron-lattice interactions in the VS2 system and other isostructural transition metal dichalcogenides across the CDW transition process.

Large negative magnetoresistance induced by anionic solid solutions in two-dimensional spin-frustrated transition metal chalcogenides.

We report an anionic solid solution process that induces frustrated magnetic structures within two-dimensional transition metal chalcogenides, which leads to huge negative magnetoresistance effects. Ultrathin nanosheets of TiTe(2-x)I(x) solid solutions, which are a new class of inorganic two-dimensional magnetic material, exhibit negative magnetoresistance with a value of up to -85%, due to the spin-dependent scattering effects of local Ti(3+) 3d(1) moments that are antiferromagnetically coupled. Moreover, TiTe(2-x)I(x) serials show unique transport behaviors with continuous evolution from metallic to semiconducting states. We anticipate that anionic doping will be a powerful tool for optimizing the intrinsic physical properties of two-dimensional transition metal chalcogenide system.

Hydrogen-incorporated TiS2 ultrathin nanosheets with ultrahigh conductivity for stamp-transferrable electrodes.

As a conceptually new class of two-dimensional (2D) materials, the ultrathin nanosheets as inorganic graphene analogues (IGAs) play an increasingly vital role in the new-generation electronics. However, the relatively low electrical conductivity of inorganic ultrathin nanosheets in current stage significantly hampered their conducting electrode applications in constructing nanodevices. We developed the unprecedentedly high electrical conductivity in inorganic ultrathin nanosheets. The hydric titanium disulfide (HTS) ultrathin nanosheets, as a new IGAs, exhibit the exclusively high electrical conductivity of 6.76 × 10(4) S/m at room temperature, which is superior to indium tin oxide (1.9 × 10(4) S/m), recording the best value in the solution assembled 2D thin films of both graphene (5.5 × 10(4) S/m) and inorganic graphene analogues (5.0 × 10(2) S/m). The modified hydrogen on S-Ti-S layers contributes additional electrons to the TiS2 layered frameworks, rendering the controllable electrical conductivity as well as the electron concentrations. Together with synergic advantages of the excellent mechanical flexibility, high stability, and stamp-transferrable properties, the HTS thin films show promising capability for being the next generation conducting electrode material in the nanodevice fields.

Ultrathin nanosheets of vanadium diselenide: a metallic two-dimensional material with ferromagnetic charge-density-wave behavior.

A new metallic 2D material with high electrical conductivity (1×10(3) S m(-1)) consists of VSe2 ultrathin nanosheets with 4-8 Se-V-Se atomic layers. This is the first 2D transition-metal dichalcogenide with intrinsic room-temperature ferromagnetism. The nanosheets increase the charge-density-wave transition temperature to 135 K by dimensional reduction.

Even-Odd-Layer-Dependent Ferromagnetism in 2D Non-van-der-Waals CrCuSe2.

Van der Waals (vdW) layered materials with strong magnetocrystalline anisotropy have attracted significant interest as the long-range magnetic order in these systems can survive even when their thicknesses is reduced to the 2D limit. Even though the interlayer coupling between the neighboring magnetic layers is very weak, it has a determining effect on the magnetism of these atomic-thickness materials. Herein, a new 2D ferromagnetic material, namely, non-vdW CuCrSe2 nanosheets with even-odd-layer-dependent ferromagnetism when laminated from an antiferromagnetic bulk is reported. Monolayer and even-layer CuCrSe2 exhibit the anomalous Hall effect and a significantly enhanced magnetic ordering temperature of more than 125 K. In contrast, the linear Hall effect exists in the odd-layer samples. Theoretical calculations indicate that the layer-dependent magnetic coupling is attributable to the orbital shift of the Cr atoms in the CrSe2 layers owing to the Cu-induced breaking of the centrosymmetry. Thus, this work sheds light on the exotic magnetic properties of layered materials that exhibit phenomena beyond weak interlayer interactions.

Hierarchical palladium catalyst for highly active and stable water oxidation in acidic media.

Acidic water electrolysis is of great importance for boosting the development of renewable energy. However, it severely suffers from the trade-off between high activity and long lifespan for oxygen evolution catalysts on the anode side. This is because the sluggish kinetics of oxygen evolution reaction necessitates the application of a high overpotential to achieve considerable current, which inevitably drives the catalysts far away from their thermodynamic equilibrium states. Here we demonstrate a new oxygen evolution model catalyst-hierarchical palladium (Pd) whose performance even surpasses the benchmark Ir- and Ru-based materials. The Pd catalyst displays an ultralow overpotential (196 mV), excellent durability and mitigated degradation (66 µV h-1) at 10 mA cm-2 in 1 M HClO4. Tensile strain on Pd (111) facets weakens the binding of oxygen species on electrochemical etching-derived hierarchical Pd and thereby leads to two orders of magnitudes of enhancement of mass activity in comparison to the parent Pd bulk materials. Furthermore, the Pd catalyst displays the bifunctional catalytic properties for both oxygen and hydrogen evolutions and can deliver a current density of 2 A cm-2 at a low cell voltage of 1.771 V when fabricated into polymer electrolyte membrane electrolyser.