Conversion of non-van der Waals solids to 2D transition-metal chalcogenides.

Although two-dimensional (2D) atomic layers, such as transition-metal chalcogenides, have been widely synthesized using techniques such as exfoliation1-3 and vapour-phase growth4,5, it is still challenging to obtain phase-controlled 2D structures6-8. Here we demonstrate an effective synthesis strategy via the progressive transformation of non-van der Waals (non-vdW) solids to 2D vdW transition-metal chalcogenide layers with identified 2H (trigonal prismatic)/1T (octahedral) phases. The transformation, achieved by exposing non-vdW solids to chalcogen vapours, can be controlled using the enthalpies and vapour pressures of the reaction products. Heteroatom-substituted (such as yttrium and phosphorus) transition-metal chalcogenides can also be synthesized in this way, thus enabling a generic synthesis approach to engineering phase-selected 2D transition-metal chalcogenide structures with good stability at high temperatures (up to 1,373 kelvin) and achieving high-throughput production of monolayers. We anticipate that these 2D transition-metal chalcogenides will have broad applications for electronics, catalysis and energy storage.

Ion Transport Behavior in van der Waals Gaps of 2D Materials.

2D materials, with advantages of atomic thickness and novel physical/chemical characteristics, have emerged as the vital building blocks for advanced lamellar membranes which possess promising potential in energy storage, ion separation, and catalysis. When 2D materials are stacked together, the van der Waals (vdW) force generated between adjacent layered nanosheets induces the construction of an ordered lamellar membrane. By regulating the interlayer spacing down to the nanometer or even sub-nanometer scale, rapid and selective ion transport can be achieved through such vdW gaps. The further improvement and application of qualified 2D materials-based lamellar membranes (2DLMs) can be fulfilled by the rational design of nanochannels and the intelligent micro-environment regulation under different stimuli. Focusing on the newly emerging advances of 2DLMs, in this review, the common top-down and bottom-up synthesis approaches of 2D nanosheets and the design strategy of functional 2DLMs are briefly introduced. Two essential ion transport mechanisms within vdW gaps are also involved. Subsequently, the responsive 2DLMs based on different types of external stimuli and their unique applications in nanofluid transport, membrane-based filters, and energy storage are presented. Based on the above analysis, the existing challenges and future developing prospects of 2DLMs are further proposed.

Precise Atomic Structure Regulation of Single-Atom Platinum Catalysts toward Highly Efficient Hydrogen Evolution Reaction.

Noble metal single-atom-catalysts (SACs) have demonstrated significant potential to improve atom utilization efficiency and catalytic activity for hydrogen evolution reaction (HER). However, challenges still remain in rationally modulating active sites and catalytic activities of SACs, which often results in sluggish kinetics and poor stability, especially in neutral/alkaline media. Herein, precise construction of Pt single atoms anchored on edge of 2D layered Ni(OH)2 (Pt-Ni(OH)2-E) is achieved utilizing in situ electrodeposition. Compared to the single-atom Pt catalysts anchored on the basal plane of Ni(OH)2 (Pt-Ni(OH)2-BP), the Pt-Ni(OH)2-E possesses superior electron affinity and high intrinsic catalytic activity, which favors the strong adsorption and rapid dissociation toward water molecules. As a result, the Pt-Ni(OH)2-E catalyst requires low overpotentials of 21 and 34 mV at 10 mA cm-2 in alkaline and neutral conditions, respectively. Specifically, it shows the high mass activity of 23.6 A mg-1 for Pt at the overpotential of 100 mV, outperforming the reported catalysts and commercial Pt/C. This work provides new insights into the rational design of active sites for preparing high-performance SACs.

Fast Lithium Ion Transport Pathways Constructed by Two-Dimensional Boron Nitride Nanoflakes in Quasi-Solid-State Polymer Electrolyte.

Quasi-solid-state electrolytes (QSSEs) are gaining huge popularity because of their significantly improved safety performance over nonaqueous liquid electrolytes and superior process adaptability over all-solid-state electrolytes. However, because of the existence of liquid molecules, QSSEs typically have low lithium ion transference numbers and compromised thermal stability. In this work, we present the fabrication of a well-rounded QSSE by introducing hexagonal boron nitride nanoflakes (BNNFs) as an inorganic filler in a poly(vinylene carbonate) matrix. BNNFs, in contrast to most inorganic fillers used as anion trappers, are used to build fast lithium ion transport pathways directly on their two-dimensional surfaces. We confirm the attractive coupling between lithium ions and BNNFs, and we confirm that with the help of BNNFs, lithium ions can migrate with less damping and a lower transport energy barrier. As a result, the designed electrolyte exhibits good ion transportability, promoted fire retardancy, and good compatibility with lithium metal anodes and commercial cathodes.

High-Pressure Synthesis of Single-Crystalline SnS Nanoribbons.

Two-dimensional tin monosulfide (SnS) is attractive for the development of electronic and optoelectronic devices with anisotropic characteristics. However, its shape-controlled synthesis with an atomic thickness and high quality remains challenging. Here, we show that highly crystalline SnS nanoribbons can be produced via high-pressure (0.5 GPa) and thermal treatment (400 °C). These SnS nanoribbons have a length of several tens of micrometers and a thickness down to 5.8 nm, giving an average aspect ratio of ∼30.6. The crystal orientation along the zigzag direction and the in-plane structural anisotropy of the SnS nanoribbons are identified by transmission electron microscopy and polarized Raman spectroscopy, respectively. An ionic liquid-gated field-effect transistor fabricated using the SnS nanoribbon exhibits an on/off current ratio of >103 and a field-effect mobility of ∼0.7 cm2 V-1 s-1. This work provides a unique way to achieve one-dimensional growth of SnS.

Twisted Bilayer Graphene Induced by Intercalation.

Twisted bilayer graphene (tBLG) has gained significant attention due to its unique physical and electronic properties. However, efficient fabrication of high-quality tBLG with diverse twist angles is crucial to expedite research on angle-dependent physics and potential applications. In this study, an intercalation strategy utilizing organic molecules, such as 1,2-dichloroethane, is developed to weaken the interlayer interaction and induce slide or rotation of the topmost graphene layer for tBLG fabrication. The proportion of tBLGs in the resulting 1,2-dichloroethane-treated BLG (dtBLG) reaches up to 84.4% for twist angles ranging from 0° to 30°, surpassing previously reported methods using chemical vapor deposition (CVD). Moreover, the twist angle distribution is not uniform and tends to concentrate in the ranges of 0-10° and 20-30°. This facile and rapid intercalation-based methodology provides a practical solution for studying angle-dependent physics and advancing the utilization of twisted two-dimensional materials.

Chiral Two-Dimensional Hybrid Organic-Inorganic Perovskites for Piezoelectric Ultrasound Detection.

Hybrid organic-inorganic perovskites (HOIPs) have exhibited striking application potential in piezoelectric energy harvesting and sensing due to their high piezoelectricity, light weight, and solution processability. However, to date, the application of piezoelectric HOIPs in ultrasound detection has not yet been explored. Here, we report the synthesis of a pair of chiral two-dimensional piezoelectric HOIPs, R-(4-bromo-2-butylammonium)2PbBr4 and S-(4-bromo-2-butylammonium)2PbBr4 [R-(BrBA)2PbBr4 and S-(BrBA)2PbBr4], which show low mechanical strength and significant piezoelectric strain coefficients that are advantageous for mechanoelectrical energy conversion. Benefiting from these virtues, the R-(BrBA)2PbBr4@PBAT and S-(BrBA)2PbBr4@PBAT [PBAT = poly(butyleneadipate-co-terephthalate)] composite films show prominent underwater ultrasound detection performance with a transmission effectivity of 12.0% using a 10.0 MHz probe, comparable with that of a polyvinylidene fluoride (PVDF) device fabricated in the same conditions. Density functional theory calculations reveal that R-(BrBA)2PbBr4 and S-(BrBA)2PbBr4 have a beneficial acoustic impedance (5.07-6.76 MRayl) compatible with that of water (1.5 MRayl), which is responsible for the facile ultrasound-induced electricity generation. These encouraging results open up new possibilities for applying piezoelectric HOIPs in underwater ultrasound detection and imaging technologies.

High-Entropy Laminates with High Ion Conductivities for High-Power All-Solid-State Lithium Metal Batteries.

Solid-state electrolytes (SSEs) are crucial to high-energy-density lithium metal batteries, but they commonly suffer from slow Li+ transfer kinetics and low mechanical strength, severely hampering the application for all-solid-state batteries. Here, we develop a two-dimensional (2D) high-entropy lithium-ion conductor, lithium-containing transition-metal phosphorus sulfide, HE-LixMPS3 (Lix(Fe1/5Co1/5Ni1/5Mn1/5Zn1/5)PS3) with five transition-metal atoms and lithium ions (Li+) dispersed into [P2S6]2- framework layers, exhibiting high lattice distortions and a large amount of cation vacancies. Such unique features enable to efficiently accelerate the migration of Li+ in 2D [P2S6]2- interlamination, delivering a high ionic conductivity of 5 × 10-4 S cm-1 at room temperature. Moreover, the HE-LixMPS3 laminate can be employed as a building block to construct an ultrathin SSE film (∼10 µm) based on strong C-S bonding between HE-LixMPS3 and nitrile-butadiene rubber. The SSE film delivers a strong mechanical robustness (6.0 MPa, 310% elongation) and a high ionic conductivity of 4 × 10-4 S cm-1, showing a long cycle stability of 800 h in lithium symmetric cells. Coupled with LiFePO4 cathode and lithium anode, the all-solid-state battery presents a high Coulombic efficiency of 99.8% within 2000 cycles at 5.0 C.

Single-Atom Pt Anchored on Oxygen Vacancy of Monolayer Ti3C2Tx for Superior Hydrogen Evolution.

Two-dimensional (2D) MXene-loaded single-atom (SA) catalysts have drawn increasing attention. SAs immobilized on oxygen vacancies (OV) of MXene are predicted to have excellent catalytic performance; however, they have not yet been realized experimentally. Here Pt SAs immobilized on the OV of monolayer Ti3C2Tx flakes are constructed by a rapid thermal shock technique under a H2 atmosphere. The resultant Ti3C2Tx-PtSA catalyst exhibits excellent hydrogen evolution reaction (HER) performance, including a small overpotential of 38 mV at 10 mA cm-2, a high mass activity of 23.21 A mgPt-1, and a large turnover frequency of 23.45 s-1 at an overpotential of 100 mV. Furthermore, density functional theory calculations demonstrate that anchoring the Pt SA on the OV of Ti3C2Tx helps to decrease the binding energy and the hybridization strength between H atoms and the supports, contributing to rapid hydrogen adsorption-desorption kinetics and high activity for the HER.

SiOxCy Microspheres with Homogeneous Atom Distribution for a High-Performance Li-Ion Battery.

The broad application of silicon-based materials is limited by large volume fluctuation, high preparation costs, and complicated preparation processes. Here, we synthesized SiOxCy microspheres on 3D copper foams by a simple chemical vapor deposition method using a low-cost silane coupling agent (KH560) as precursors. The SiOxCy microspheres are available with a large mass loading (>3 mg/cm2) on collectors and can be directly used as the electrode without any binders or extra conductive agents. As a result, the as-prepared SiOxCy shows a high reversible capacity of ∼1240 mAh g-1 and can be cycled more than 1900 times without decay. Ex situ characterizations show that the volume change of the microspheres is only 55% and the spherical morphology as well as the 3D structure remain intact after cycles. Full-cell electrochemical tests paired with LiFePO4 as cathodes show 87% capacity retention after 500 cycles, better than most reported results, thus showing the commercial potential of the material.

Thickness-Tunable Growth of Composition-Controllable Two-Dimensional FexGeTe2.

Two-dimensional (2D) magnetic materials provide an ideal platform for investigating novel magnetism and spin behavior in low-dimensional systems while being restricted by the deficiency of accurate bottom-up synthesis. To overcome this difficulty, a facile and universal flux-assisted growth (FAG) method is proposed to synthesize the multicomponent FexGeTe2 (x = 3-5) with different Fe contents and even alloyed with hetero metal atoms. This one-to-one method ensures the stoichiometry consistency from the FexGeTe2 and MyFe5-yGeTe2 (M = Co, Ni) bulk crystal precursors to the 2D nanosheets, with controllable composition. Tuning the growth temperatures can provide thickness-tunable products. Changeable magnetic properties of FexGeTe2 and alloyed CoyFe5-yGeTe2 are substantiated by the superconducting quantum interference device and reflective magnetic circular dichroism. This method generates thickness-tunable high-crystallinity FexGeTe2 samples without phase separation and exhibits a high tolerance to different substrates and a large temperature window, providing a new avenue to synthesize and explore such multicomponent 2D magnets and even the alloyed ones.

Three-Dimensional Fe Single-Atom Catalyst for High-Performance Cathode of Zn-Air Batteries.

Designing cost-effective and highly active oxygen reduction reaction (ORR) catalysts is critical for the development of Zn-air batteries (ZABs). Iron-nitrogen-carbon (Fe-N-C) catalysts with single-atom Fe-Nx active sites are considered as one of the most promising alternatives to noble Pt but are hindered by unsatisfactory activity and durability. Herein, a NaCl template-assisted in situ pyrolysis technique is utilized to massively fabricate Fe-N-C single-atom catalysts (SACs) anchored on the three-dimensional open-pore carbon networks (denoted as 3D SAFe). The 3D SAFe catalyst exhibits ultrahigh activity with a half-wave potential of 0.90 V (vs RHE), benefiting from the enhanced mass diffusion and the increased amount of effective Fe-N4 sites. Consequently, the ZABs assembled with 3D SAFe deliver high peak power density up to 156 mW cm-2 and outstanding durability of 80 h, suggesting the application potential of the 3D SAFe catalyst. This work inspires the rational design and synthesis of highly efficient SACs for ZABs.

Stable Lithium Plating and Stripping Enabled by a LiPON Nanolayer on PP Separator.

The practical application of the Li metal anode (LMA) is hindered by its low coulombic efficiency and dendrite formation. Although solid-state electrolytes hold promise as ideal partners for LMA, their effectiveness is limited by the poor workability and ionic conductivity. Herein, a modified separator combining the rapid Li+ transport of a liquid electrolyte and the interfacial stability of a solid-state electrolyte is explored to realize stable cycling of the LMA. A conformal nanolayer of LiPON is coated on a polypropylene separator by a scalable magnetron sputtering method, which is compatible with current Li-ion battery production lines and promising for the practical applications. The resulting LMA-electrolyte/separator interface is Li+ -conductive, electron-insulating, mechanically and chemically stable. Consequently, Li|Li cells maintain stable dendrite-free cycling with overpotentials of 10 and 40 mV over 2000 h at 1 and 5 mA cm-2 , respectively. Additionally, the Li|LiFePO4 full cells achieve a capacity retention of 92% after 550 cycles, confirming its application potential.

A New Hybrid Lead-Free Metal Halide Piezoelectric for Energy Harvesting and Human Motion Sensing.

Hybrid organic-inorganic piezoelectrics have attracted attention due to their simple synthesis, mechanical flexibility, and designability, which have promising application potential in flexible sensing and self-powered energy harvesting devices. Although some hybrid piezoelectrics are discovered, most of their structures are limited by the perovskite-type and often contain lead. Herein, the synthesis, structure, and piezoelectric properties of a new hybrid lead-free metal halide, (BTMA)2 CoBr4 (BTMA = benzyltrimethylammonium) are reported. The experimental and theoretical results demonstrate that this material simply composed of [CoBr4 ]2- tetrahedra and BTMA+ cations exhibits significant piezoelectricity (d22 = 5.14, d25 = 12.40 pC N-1 ), low Young's and shear moduli (4.11-17.56 GPa; 1.86-7.91 GPa). Moreover, the (BTMA)2 CoBr4 /PDMS (PDMS = polydimethylsiloxane) composite thin films are fabricated and optimized. The 10% (BTMA)2 CoBr4 /PDMS-based flexible devices show attractive performance in energy harvesting with an open-circuit voltage of 19.70 V, short-circuit current of 4.24 µA, and powder density of 11.72 µW cm-2 , catching up with those of piezoelectric ceramic composites. Meanwhile, these film devices show excellent capability in accurately sensing human body motions, such as finger bending and tapping. This work demonstrates that (BTMA)2 CoBr4 and related piezoelectric lead-free halides can be promising molecular materials in modern energy and sensing applications.

Self-Healing Nucleation Seeds Induced Long-Term Dendrite-Free Lithium Metal Anode.

Seeded lithium (Li) nucleation has been considered as a promising strategy to achieve uniform Li deposition. However, problems of agglomeration and pulverization quickly invalidate the nucleation seeds, resulting in Li dendrite growth during repeated charge/discharge processes. Herein, liquid gallium-indium (GaIn) nanoparticles with structural self-healing properties are utilized to guide uniform metallic Li nucleation and deposition. Ultrafine GaIn nanoparticles (∼25 nm) uniformly decorated on the surface of carbon layers effectively homogenize the lithium-ion flux. After fully Li stripping, lithiophilic GaIn nanoparticles return to the liquid binary eutectic phase, thereby healing the deformed structure and enabling them to continuously guide dendrite-free Li deposition. Li metal anodes with such nucleation seeds exhibit nearly zero nucleation overpotential even after hundreds of cycles and a high average Coulombic efficiency of 99.03% for more than 400 cycles. The design of self-healing nucleation seeds provides important insights for obtaining high-performance lithium metal anodes.

Ni(OH)2 Templated Synthesis of Ultrathin Ni3 S2 Nanosheets as Bifunctional Electrocatalyst for Overall Water Splitting.

Ultrathin nickel (Ni)-based sulfide nanosheets have been reported as excellent electrocatalysts for overall water splitting; however, the uncontrollability over thickness due to the nonlayered structure still hampers its practical application. Herein, a simple topochemical conversion strategy is employed to synthesize cobalt-doped Ni3 S2 (Co-Ni3 S2 ) ultrathin nanosheets on Ni foam. The Co-Ni3 S2 nanosheets are controlled synthesized by using Co-Ni(OH)2 ultrathin nanosheets as templates with anneal and sulfurization treatment, showing exceptional electrocatalytic activity. This template-assisted method can also be applied to obtain Ni, NiO, and NiPx nanosheets, providing a universal strategy to synthesize ultrathin nanosheets of nonlayered materials. The overall water splitting of this Co-Ni3 S2 ultrathin nanosheets achieves a low voltage of 1.54 V at a current density of 10 mA cm-2 and high durability in 1 m KOH, comparable to the best performance of electrochemical water splitting ever reported. The detailed structural transformation of Ni-based sulfides in the catalytic process and its mechanism are further explored both experimentally and theoretically.

Correlating the three-dimensional atomic defects and electronic properties of two-dimensional transition metal dichalcogenides.

The electronic, optical and chemical properties of two-dimensional transition metal dichalcogenides strongly depend on their three-dimensional atomic structure and crystal defects. Using Re-doped MoS2 as a model system, here we present scanning atomic electron tomography as a method to determine three-dimensional atomic positions as well as positions of crystal defects such as dopants, vacancies and ripples with a precision down to 4 pm. We measure the three-dimensional bond distortion and local strain tensor induced by single dopants. By directly providing these experimental three-dimensional atomic coordinates to density functional theory, we obtain more accurate electronic band structures than derived from conventional density functional theory calculations that relies on relaxed three-dimensional atomic coordinates. We anticipate that scanning atomic electron tomography not only will be generally applicable to determine the three-dimensional atomic coordinates of two-dimensional materials, but also will enable ab initio calculations to better predict the physical, chemical and electronic properties of these materials.

A subthermionic tunnel field-effect transistor with an atomically thin channel.

The fast growth of information technology has been sustained by continuous scaling down of the silicon-based metal-oxide field-effect transistor. However, such technology faces two major challenges to further scaling. First, the device electrostatics (the ability of the transistor's gate electrode to control its channel potential) are degraded when the channel length is decreased, using conventional bulk materials such as silicon as the channel. Recently, two-dimensional semiconducting materials have emerged as promising candidates to replace silicon, as they can maintain excellent device electrostatics even at much reduced channel lengths. The second, more severe, challenge is that the supply voltage can no longer be scaled down by the same factor as the transistor dimensions because of the fundamental thermionic limitation of the steepness of turn-on characteristics, or subthreshold swing. To enable scaling to continue without a power penalty, a different transistor mechanism is required to obtain subthermionic subthreshold swing, such as band-to-band tunnelling. Here we demonstrate band-to-band tunnel field-effect transistors (tunnel-FETs), based on a two-dimensional semiconductor, that exhibit steep turn-on; subthreshold swing is a minimum of 3.9 millivolts per decade and an average of 31.1 millivolts per decade for four decades of drain current at room temperature. By using highly doped germanium as the source and atomically thin molybdenum disulfide as the channel, a vertical heterostructure is built with excellent electrostatics, a strain-free heterointerface, a low tunnelling barrier, and a large tunnelling area. Our atomically thin and layered semiconducting-channel tunnel-FET (ATLAS-TFET) is the only planar architecture tunnel-FET to achieve subthermionic subthreshold swing over four decades of drain current, as recommended in ref. 17, and is also the only tunnel-FET (in any architecture) to achieve this at a low power-supply voltage of 0.1 volts. Our device is at present the thinnest-channel subthermionic transistor, and has the potential to open up new avenues for ultra-dense and low-power integrated circuits, as well as for ultra-sensitive biosensors and gas sensors.

In-Situ Formed Protecting Layer from Organic/Inorganic Concrete for Dendrite-Free Lithium Metal Anodes.

In this work, a separator modified by composite material of graphite fluoride nanosheets and poly(vinylidene difluoride) (GFNs-PVDF) is fabricated to in-situ construct a protective layer on Li metal anodes. The much-improved mechanical properties of this organic/inorganic protecting layer ensure efficient restriction on the growth of Li dendrites. The LiF and graphene nanosheets generated by the reaction of GFNs with lithium metal can not only provide fast transport channels for Li ions but also protect the Li metal anode from continuous corrosion of electrolytes. In addition, GFNs' lithiophilic nature guarantees the uniform Li nucleation site and perfect contact between li metal and the protecting layer without void space, leading to a low interfacial impedance and layer-by-layer lithium deposition. Together with the scalable method and cheap raw materials, this strategy provides new insights toward practical applications of Li metal batteries.

Large-Scale Modification of Commercial Copper Foil with Lithiophilic Metal Layer for Li Metal Battery.

The application and development of lithium metal battery are severely restricted by the uncontrolled growth of lithium dendrite and poor cycle stability. Uniform lithium deposition is the core to solve these problems, but it is difficult to be achieved on commercial Cu collectors. In this work, a simple and commercially viable strategy is utilized for large-scale preparation of a modified planar Cu collector with lithiophilic Ag nanoparticles by a simple substitution reaction. As a result, the Li metal shows a cobblestone-like morphology with similar size and uniform distribution rather than Li dendrites. Interestingly, a high-quality solid electrolyte interphase layer in egg shell-like morphology with fast ion diffusion channels is formed on the interface of the collector, exhibiting good stability with long-term cycles. Moreover, at the current density of 1 mA cm-2 for 1 mAh cm-2 , the Ag modified planar Cu collector shows an ultralow nucleation overpotential (close to 0 mV) and a stable coulombic efficiency of 98.54% for more than 600 cycles as well as long lifespan beyond 900 h in a Li|Cu-Ag@Li cell, indicating the ability of this method to realize stable Li metal batteries. Finally, full cells paired with LiNi0.8 Co0.1 Mn0.1 O2 show superior rate performance and stability compared with those paired with Li foil.