Interlayer Delocalized Electrons Activate Basal Plane for Ultrahigh-Current-Density Hydrogen Evolution.

The basal plane of transition metal dichalcogenides (TMDCs) is inert for the hydrogen evolution reaction (HER) due to its low-efficiency charge transfer kinetics. We propose a strategy of filling the van der Waals (vdW) layer with delocalized electrons to enable vertical penetration of electrons from the collector to the adsorption intermediate vertically. Guided by density functional theory, we achieve this concept by incorporating Cu atoms into the interlayers of tantalum disulfide (TaS2). The delocalized electrons of d-orbitals of the interlayered Cu can constitute the charge transfer pathways in the vertical direction, thus overcoming the hopping migration through vdW gaps. The vertical conductivity of TaS2 increased by 2 orders of magnitude. The TaS2 basal plane HER activity was extracted with an on-chip microcell. Modified by the delocalized electrons, the current density increased by 20 times, reaching an ultrahigh value of 800 mA cm-2 at -0.4 V without iR compensation.

Engineering a Low-Strain Si@TiSi2@NC Composite for High-Performance Lithium-Ion Batteries.

The huge volume expansion/contraction of silicon (Si) during the lithium (Li) insertion/extraction process, which can lead to cracking and pulverization, poses a substantial impediment to its practical implementation in lithium-ion batteries (LIBs). The development of low-strain Si-based composite materials is imperative to address the challenges associated with Si anodes. In this study, we have engineered a TiSi2 interface on the surface of Si particles via a high-temperature calcination process, followed by the introduction of an outermost carbon (C) shell, leading to the construction of a low-strain and highly stable Si@TiSi2@NC composite. The robust TiSi2 interface not only enhances electrical and ionic transport but also, more critically, significantly mitigates particle cracking by restraining the stress/strain induced by volumetric variations, thus alleviating pulverization during the lithiation/delithiation process. As a result, the as-fabricated Si@TiSi2@NC electrode exhibits a high initial reversible capacity (2172.7 mAh g-1 at 0.2 A g-1), superior rate performance (1198.4 mAh g-1 at 2.0 A g-1), and excellent long-term cycling stability (847.0 mAh g-1 after 1000 cycles at 2.0 A g-1). Upon pairing with LiNi0.6Co0.2Mn0.2O2 (NCM622), the assembled Si@TiSi2@NC||NCM622 pouch-type full cell exhibits exceptional cycling stability, retaining 90.1% of its capacity after 160 cycles at 0.5 C.

Activating and Stabilizing a Reversible four Electron Redox Reaction of I-/I+ for Aqueous Zn-Iodine Battery.

Low capacity and poor cycle stability greatly inhibit the development of zinc-iodine batteries. Herein, a high-performance Zn-iodine battery has been reached by designing and optimizing both electrode and electrolyte. The Br- is introduced as the activator to trigger I+, and coupled with I+ forming interhalogen to stabilize I+ to achieve a four-electron reaction, which greatly promotes the capacity. And the Ni-Fe-I LDH nanoflowers serve as the confinement host to enable the reactions of I-/I+ occurring in the layer due to the spacious and stable interlayer spacing of Ni-Fe-I LDH, which effectively suppresses the iodine-species shuttle ensuring high cycling stability. As a result, the electrochemical performance is greatly enhanced, especially in specific capacity (as high as 350 mAh g-1 at 1 A g-1 far higher than two-electron transfer Zn-iodine batteries) and cycling performance (94.6 % capacity retention after 10000 cycles). This strategy provides a new way to realize high capacity and long-term stability of Zn-iodine batteries.

Fibration of powdery materials.

Non-destructive processing of powders into macroscopic materials with a wealth of structural and functional possibilities has immeasurable scientific significance and application value, yet remains a challenge using conventional processing techniques. Here we developed a universal fibration method, using two-dimensional cellulose as a mediator, to process diverse powdered materials into micro-/nanofibres, which provides structural support to the particles and preserves their own specialties and architectures. It is found that the self-shrinking force drives the two-dimensional cellulose and supported particles to pucker and roll into fibres, a gentle process that prevents agglomeration and structural damage of the powder particles. We demonstrate over 120 fibre samples involving various powder guests, including elements, compounds, organics and hybrids in different morphologies, densities and particle sizes. Customized fibres with an adjustable diameter and guest content can be easily constructed into high-performance macromaterials with various geometries, creating a library of building blocks for different fields of applications. Our fibration strategy provides a universal, powerful and non-destructive pathway bridging primary particles and macroapplications.

Reconstructing Hydrogen-Bond Network for Efficient Acidic Oxygen Evolution.

Developing highly active oxygen evolution reaction (OER) catalysts in acidic conditions is a pressing demand for proton-exchange membrane water electrolysis. Manipulating proton character at the electrified interface, as the crux of all proton-coupled electrochemical reactions, is highly desirable but elusive. Herein we present a promising protocol, which reconstructs a connected hydrogen-bond network between the catalyst-electrolyte interface by coupling hydrophilic units to boost acidic OER activity. Modelling on N-doped-carbon-layer clothed Mn-doped-Co3O4 (Mn-Co3O4@CN), we unravel that the hydrogen-bond interaction between CN units and H2O molecule not only drags the free water to enrich the surface of Mn-Co3O4 but also serves as a channel to promote the dehydrogenation process. Meanwhile, the modulated local charge of the Co sites from CN units/Mn dopant lowers the OER barrier. Therefore, Mn-Co3O4@CN surpasses RuO2 at high current density (100 mA cm-2 @ ~538 mV).

Dimethyl Sulfoxide Inhibits Bile Acid Synthesis in Healthy Mice but Does Not Protect Mice from Bile-Acid-Induced Liver Damage.

Bile acids serve a vital function in lipid digestion and absorption; however, their accumulation can precipitate liver damage. In our study, we probed the effects of dimethyl sulfoxide (DMSO) on bile acid synthesis and the ensuing liver damage in mice induced by bile acids. Our findings indicate that DMSO efficaciously curbs bile acid synthesis by inhibiting key enzymes involved in the biosynthetic pathway, both in cultured primary hepatocytes and in vivo. Contrarily, we observed that DMSO treatment did not confer protection against bile-acid-induced liver damage in two distinct mouse models: one induced by a 0.1% DDC diet, leading to bile duct obstruction, and another induced by a CDA-HFD, resulting in non-alcoholic steatohepatitis (NASH). Histopathological and biochemical analyses unveiled a comparable extent of liver injury and fibrosis levels in DMSO-treated mice, characterized by similar levels of increase in Col1a1 and Acta2 expression and equivalent total liver collagen levels. These results suggest that, while DMSO can promptly inhibit bile acid synthesis in healthy mice, compensatory mechanisms might rapidly override this effect, negating any protective impact against bile-acid-induced liver damage in mice. Through these findings, our study underscores the need to reconsider treating DMSO as a mere inert solvent and prompts further exploration to identify more effective therapeutic strategies for the prevention and treatment of bile-acid-associated liver diseases.

Scalable integration of hybrid high-κ dielectric materials on two-dimensional semiconductors.

Two-dimensional (2D) semiconductors are promising channel materials for next-generation field-effect transistors (FETs). However, it remains challenging to integrate ultrathin and uniform high-κ dielectrics on 2D semiconductors to fabricate FETs with large gate capacitance. We report a versatile two-step approach to integrating high-quality dielectric film with sub-1 nm equivalent oxide thickness (EOT) on 2D semiconductors. Inorganic molecular crystal Sb2O3 is homogeneously deposited on 2D semiconductors as a buffer layer, which forms a high-quality oxide-to-semiconductor interface and offers a highly hydrophilic surface, enabling the integration of high-κ dielectrics via atomic layer deposition. Using this approach, we can fabricate monolayer molybdenum disulfide-based FETs with the thinnest EOT (0.67 nm). The transistors exhibit an on/off ratio of over 106 using an ultra-low operating voltage of 0.4 V, achieving unprecedently high gating efficiency. Our results may pave the way for the application of 2D materials in low-power ultrascaling electronics.

An Ultrathin Inorganic Molecular Crystal Interfacial Layer for Stable Zn Anode.

Zn metal anode suffers from dendrite growth and side reactions during cycling, significantly deteriorating the lifespan of aqueous Zn metal batteries. Herein, we introduced an ultrathin and ultra-flat Sb2 O3 molecular crystal layer to stabilize Zn anode. The in situ optical and atomic force microscopes observations show that such a 10 nm Sb2 O3 thin layer could ensure uniform under-layer Zn deposition with suppressed tip growth effect, while the traditional WO3 layer undergoes an uncontrolled up-layer Zn deposition. The superior regulation capability is attributed to the good electronic-blocking ability and low Zn affinity of the molecular crystal layer, free of dangling bonds. Electrochemical tests exhibit Sb2 O3 layer can significantly improve the cycle life of Zn anode from 72 h to 2800 h, in contrast to the 900 h of much thicker WO3 even in 100 nm. This research opens up the application of inorganic molecular crystals as the interfacial layer of Zn anode.

Personal Microenvironment Management by Smart Textiles with Negative Oxygen Ions Releasing and Radiative Cooling Performance.

In recent years, significant strides have been made in the development of smart clothing, which combines traditional apparel with advanced technology. As our climate and environment undergo continuous changes, it has become critically important to invent and refine sophisticated textiles that enhance thermal comfort and human health. In this study, we present a "wearable forest-like textile". This textile is based on helical lignocellulose-tourmaline composite fibers, boasting mechanical strength that outperforms that of cellulose-based and natural macrofibers. This wearable microenvironment does more than generate approximately 18625 ions/cm3 of negative oxygen ions; it also effectively purifies particulate matter. Furthermore, our experiments demonstrate that the negative oxygen ion environment can slow fruit decay by neutralizing free radicals, suggesting promising implications for aging retardation. In addition, this wearable microenvironment reflects solar irradiation and selectively transmits human body thermal radiation, enabling effective radiative cooling of approximately 8.2 °C compared with conventional textiles. This sustainable and efficient wearable microenvironment provides a compelling textile choice that can enhance personal heat management and human health.

On the Working Mechanisms of Molecules-Based Van der Waals Dielectrics.

Sb2 O3 molecules offer unprecedented opportunities for the integration of a van der Waals (vdW) dielectric and a 2D vdW semiconductor. However, the working mechanisms underlying molecules-based vdW dielectrics remain unclear. Here, the working mechanisms of Sb2 O3 and two Sb2 O3 -like molecules (As2 O3 and Bi2 O3 ) as dielectrics are systematically investigated by combining first-principles calculations and gate leakage current theories. It is revealed that molecules-based vdW dielectrics have a considerable advantage over conventional dielectric materials: defects hardly affect their insulating properties. This shows that it is unnecessary to synthesize high-quality crystals in practical applications, which has been a long-standing challenge for conventional dielectric materials. Further analysis reveals that a large thermionic-emission current renders Sb2 O3 difficult to simultaneously satisfy the requirements of dielectric layers in p-MOS and n-MOS, which hinders its application for complementary metal-oxide-semiconductor (CMOS) devices. Remarkably, it is found that As2 O3 can serve as a dielectric for both p-MOS and n-MOS. This work not only lays a theoretical foundation for the application of molecules-based vdW dielectrics, but also offers an unprecedentedly competitive dielectric (i.e., As2 O3 ) for 2D vdW semiconductors-based CMOS devices, thus having profound implications for future semiconductor industry.

Building intercalation structure for high ionic conductivity via aliovalent substitution.

Two-dimensional (2D) materials, which possess robust nanochannels, high flux and allow scalable fabrication, provide new platforms for nanofluids. Highly efficient ionic conductivity can facilitate the application of nanofluidic devices for modern energy conversion and ionic sieving. Herein, we propose a novel strategy of building an intercalation crystal structure with negative surface charge and mobile interlamellar ions via aliovalent substitution to boost ionic conductivity. The Li2xM1-xPS3 (M = Cd, Ni, Fe) crystals obtained by the solid-state reaction exhibit distinct capability of water absorption and apparant variation of interlayer spacing (from 0.67 to 1.20 nm). The assembled membranes show the ultrahigh ionic conductivity of 1.20 S/cm for Li0.5Cd0.75PS3 and 1.01 S/cm for Li0.6Ni0.7PS3. This facile strategy may inspire the research in other 2D materials with higher ionic transport performance for nanofluids.

Gate Dielectrics Integration for 2D Electronics: Challenges, Advances, and Outlook.

2D semiconductors have emerged both as an ideal platform for fundamental studies and as promising channel materials in beyond-silicon field-effect-transistors due to their outstanding electrical properties and exceptional tunability via external field. However, the lack of proper dielectrics for 2D semiconductors has become a major roadblock for their further development toward practical applications. The prominent issues between conventional 3D dielectrics and 2D semiconductors arise from the integration and interface quality, where defect states and imperfections lead to dramatic deterioration of device performance. In this review article, the root causes of such issues are briefly analyzed and recent advances on some possible solutions, including various approaches of adapting conventional dielectrics to 2D semiconductors, and the development of novel dielectrics with van der Waals surface toward high-performance 2D electronics are summarized. Then, in the perspective, the requirements of ideal dielectrics for state-of-the-art 2D devices are outlined and an outlook for their future development is provided.

Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering.

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb2 O3 molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb2 O3 flake shows a sharp drop by 5 orders of magnitude in 0-3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.

2D Ruddlesden-Popper perovskite sensitized SnP2S6 ultraviolet photodetector enabling high responsivity and fast speed.

As the newly developed wide-bandgap semiconductors, two-dimensional layered metal phosphorus chalcogenides (2D LMPCs) exhibit enormous potential applications in ultraviolet (UV) photodetection due to their superior optoelectronic performance. However, 2D LMPC-based UV photodetectors generally suffer from low responsivity and slow response speed, which hinder their practical applications. Here, we present an effective strategy of sensitizing 2D LMPC UV photodetectors with a 2D Ruddlesden-Popper (RP) perovskite to enable high responsivity and fast response speed. As a demonstration, a hybrid heterojunction composed of RP perovskite (PEA)2PbI4 and a 2D SnP2S6 flake is fabricated by spin-coating method. Benefitting from the strong optical absorption of (PEA)2PbI4 and the efficient interfacial charge transfer caused by the favorable type-II energy band alignment, the as-fabricated 2D SnP2S6/(PEA)2PbI4 hybrid heterojunction photodetectors show high responsivity (67.1 A W-1), large detectivity (2.8 × 1011 Jones), fast rise/delay time (30/120 µs) and excellent external quantum efficiency (22825%) at 365 nm. Under field-effect modulation, the responsivity of the heterojunction photodetector can reach up to 239.4 A W-1, which is attributed to the photogating mechanism and reduced Schottky barriers. Owing to the excellent photodetection performance, the heterojunction device further shows superior imaging capability. This work provides an effective strategy for designing high-performance UV photodetectors toward future applications.

Unlocking the in situ Li plating dynamics and evolution mediated by diverse metallic substrates in all-solid-state batteries.

The mechanisms of Li deposition behaviors, which overwhelmingly affect battery performances and safety, are far to be understood in solid-state batteries. Here, using in situ micro-nano electrochemical scanning electron microscopy (SEM) manipulation platform, dynamic Li plating behaviors on 10 metallic substrates have been tracked, and the underlying mechanisms for dendrite-free Li plating are elucidated. Distinct Li deposition behaviors on Cu, Ti, Ni, Bi, Cr, In, Ag, Au, Pd, and Al are revealed quantitatively in nucleation densities, growth rates, and anisotropic ratios. For Li alloyable metals, the dynamic Li alloying process before Li growth is visually captured. It is concluded that a good affinity for Li and appropriate lattice compatibility between the substrate and Li are needed to facilitate homogeneous Li plating. Our work not only uncovers the Li plating dynamics, shedding light on the design of solid-state batteries, but also provides a powerful integrated SEM platform for future in-depth investigation of solid-state batteries.

Stabilizing the interface of PEO solid electrolyte to lithium metal anode via a g-C3N4 mediator.

g-C3N4 is introduced to the PEO electrolyte as a mediator to stabilize the interface to lithium metal anode. As a result, the interface resistance is stabilized after cycling and the symmetric cell exhibits a cycle life over 900 h, indicating that the interface stability is evidently promoted.

Stabilizing the Halide Solid Electrolyte to Lithium by a ß-Li3N Interfacial Layer.

As a new class of solid electrolytes, halide solid electrolytes have the advantages of high ionic conductivity at room temperature, stability to high-voltage cathodes, and good deformability, but they generally show a problem of being unstable to a lithium anode. Here, we report the use of Li3N as an interface modification layer to improve the interfacial stability of Li2ZrCl6 to the Li anode. We found that commercial Li3N can be easily transformed into an α-phase and a ß-phase by ball-milling and annealing, respectively, in which ß-phase Li3N simultaneously has high room-temperature ionic conductivity and good stability to both Li and Li2ZrCl6, making it a good choice for an artificial interface layer material. After the modification of the ß-Li3N interfacial layer, the interfacial impedance between Li2ZrCl6 and the Li anode decreased from 1929 to ∼400 Ω. At a current density of 0.1 mA cm-2, the overpotential of the Li symmetric cell decreased from 250 to ∼50 mV, which did not show an obvious increase for at least 300 h, indicating that the ß-Li3N interface layer effectively improves the interfacial stability between Li2ZrCl6 and Li.

Engineering a Local Free Water Enriched Microenvironment for Surpassing Platinum Hydrogen Evolution Activity.

Manipulating the catalyst-electrolyte interface to push reactants into the inner Helmholtz plane (IHP) is highly desirable for efficient electrocatalysts, however, it has rarely been implemented due to the elusive electrochemical IHP and inherent inert catalyst surface. Here, we propose the introduction of local force fields by the surface hydroxyl group to engineer the electrochemical microenvironment and enhance alkaline hydrogen evolution activity. Taking a hydroxyl group immobilized Ni/Ni3 C heterostructure as a prototype, we reveal that the local hydrogen bond induced by the surface hydroxyl group drags 4-coordinated hydrogen-bonded H2 O molecules across the IHP to become free H2 O and thus continuously supply reactants forcatalytic sites catalytic sites. In addition, the hydroxyl group coupled with the Ni/Ni3 C heterostructure further lowers the water dissociation energy by polarization effects. As a direct outcome, hydroxyl-rich catalysts surpass Pt/C activity at high current density (500 mA cm-2 @ ≈276 mV) in alkaline medium.

Bioinspired Construction of Micronano Lignocellulose into an Impact Resistance "Wooden Armor" With Bouligand Structure.

The demand for advanced safeguards has increased with a rise in terrorism and international conflicts. Traditional impact-resistant glass and ceramics have relatively high performance but have several drawbacks as well, such as inflexibility, heaviness, and high processing energy consumption. Herein, we propose sustainable lignocellulosic duplicates: the Pirarucu scale-inspired structures that can serve as "wood armor" with impressive damage tolerance. By accurately assembling a rigid laminated lignocellulose, with a soft shear-thickened fluid interlayer, into a Bouligand-like structure, the artificial wooden armor exhibits a 10-fold increase in impact resistance. This observation is similar to that of typical engineering materials (e.g., ceramics, glass, and alloys). However, our proposed material structure has the capability of blocking the enormous impact of a bullet while notably having approximately half the density of typical engineering materials. The high durability and damage resistance of wooden armor effectively prevents catastrophic damage when it is impacted upon. The design strategy presents a method for lightweight, high-performance, and sustainable bioinspired materials for special security applications.

Back-Gated van der Waals Heterojunction Manipulates Local Charges toward Fine-Tuning Hydrogen Evolution.

Charge redistribution plays a prominent role in interpreting the intrinsic electrocatalytic mechanism. Establishing a quantitative relationship between the local charges and electrochemical performance can fundamentally update the design philosophies beyond conventional methods. We describe exertion of an external electric field in the cobalt phthalocyanine (CoPc)/MoS2 heterojunction to finely manipulate intermolecular charge transfer. The injected charges (e- ) from CoPc to MoS2 migrate to natural S vacancies and enhance Mo-H bonding. Moreover, the band gap of MoS2 and CoPc can be readily tuned by the electric field, verifying band engineering at the heterointerface. In situ photoluminescence spectra and gate-dependent electrochemical measurement reveal a linear correlation between the charge accumulation and hydrogen evolution reaction (HER) activity. This approach provides a new strategy for the design of catalysts, enabling precise regulation of the electronic configuration to improve catalytic activity.