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.

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.

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.

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).

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.

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.

Facile, Atom-Economic, Chemical Thinning Strategy for Ultrathin Lithium Foils.

Metallic lithium is considered as the ultimate anode material for lithium-based batteries due to its highest energy density. However, as an anode, commercial Li metal foils are too thick, with a large amount of trouble to balance its exorbitant areal capacity with common cathodes in full cells. Here, a new chemical thinning strategy is proposed via a simple surface dissolving reaction between lithium and naphthalene, which enables scalable, continuous, and roll-to-roll preparation of ultrathin Li foil. A Li foil less than 15 µm with a clean surface can be successfully obtained within 20 min. The thinning rate and thickness of the lithium foil can be easily adjusted by changing the concentration, temperature, and operation mode. The produced Li-Naph solution after thinning can also be used as a multifunctional reagent of great value, and the Li ions in the final waste solution can be further extracted in the form of Li2CO3, showing superior lithium atom economy of our strategy.

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.

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.

Ultrahigh-Current-Density and Long-Term-Durability Electrocatalysts for Water Splitting.

Hydrogen economy is imagined where excess electric energy from renewable sources stored directly by electrochemical water splitting into hydrogen is later used as clean hydrogen fuel. Electrocatalysts with the superhigh current density (1000 mA cm-2 -level) and long-term durability (over 1000 h), especially at low overpotentials (<300 mV), seem extremely critical for green hydrogen from experiment to industrialization. Along the way, numerous innovative ideas are proposed to design high efficiency electrocatalysts in line with industrial requirements, which also stimulates the understanding of the mass/charge transfer and mechanical stability during the electrochemical process. It is of great necessity to summarize and sort out the accumulating knowledge in time for the development of laboratory to commercial use in this promising field. This review begins with examining the theoretical principles of achieving high-efficiency electrocatalysts with high current densities and excellent durability. Special attention is paid to acquaint efficient strategies to design perfect electrocatalysts including atomic structure regulation for electrical conductivity and reaction energy barrier, array configuration constructing for mass transfer process, and multiscale coupling for high mechanical strength. Finally, the importance and the personal perspective on future opportunities and challenges, is highlighted.

Van der Waals Epitaxy of Bi2 Te2 Se/Bi2 O2 Se Vertical Heterojunction for High Performance Photodetector.

Bismuth oxyselenide (Bi2 O2 Se) has emerged as a promising candidate for electronic and optoelectronic applications due to its outstanding electron mobility and ambient stability. However, high dark current and relatively slow photoresponse that originate from high charge carrier concentration as well as bolometric effect in Bi2 O2 Se inhibit further improvement of Bi2 O2 Se based photodetectors. Here, a one-step van der Waals (vdW) epitaxy synthesis of Bi2 Te2 Se/Bi2 O2 Se vertical heterojunction with type-II band alignment and high-quality interface is demonstrated. The crystal quality and uniformity of the heterojunction are supported by Raman, transmission electron microscopy and energy dispersive spectroscopy results. A photodetector based on Bi2 Te2 Se/Bi2 O2 Se heterojunction demonstrates steady photoresponse over a large wavelength range (532-1456 nm), with a high specific responsivity of 2.21 × 103 A W-1 at 532 nm and fast response speed of 50 ms. Moreover, field effect regulation allows for further improvement of the photoresponse performance of the heterojunction field effect transistor device, where the responsivity can be increased to 3.34 × 103 A W-1 with a 60 V gate voltage. Overall, the one-step vdW epitaxy process is a promising and convenient route towards constructing high quality Bi2 O2 Se based heterojunction for improving its photodetection performance.

Cellulose-Based Hybrid Structural Material for Radiative Cooling.

Structural materials with excellent mechanical properties are vitally important for architectural application. However, the traditional structural materials with complex manufacturing processes cannot effectively regulate heat flow, causing a large impact on global energy consumption. Here, we processed a high-performance and inexpensive cooling structural material by bottom-up assembling delignified biomass cellulose fiber and inorganic microspheres into a 3D network bulk followed by a hot-pressing process; we constructed a cooling lignocellulosic bulk that exhibits strong mechanical strength more than eight times that of the pure wood fiber bulk and greater specific strength than the majority of structural materials. The cellulose acts as a photonic solar reflector and thermal emitter, enabling a material that can accomplish 24-h continuous cooling with an average dT of 6 and 8 °C during day and night, respectively. Combined with excellent fire-retardant and outdoor antibacterial performance, it will pave the way for the design of high-performance cooling structural materials.

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.

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.

In Situ Halogen-Ion Leaching Regulates Multiple Sites on Tandem Catalysts for Efficient CO2 Electroreduction to C2+ Products.

Tandem catalysts can divide the reaction into distinct steps by local multiple sites and thus are attractive to trigger CO2 RR to C2+ products. However, the evolution of catalysts generally exists during CO2 RR, thus a closer investigation of the reconstitution, interplay, and active origin of dual components in tandem catalysts is warranted. Here, taking AgI-CuO as a conceptual tandem catalyst, we uncovered the interaction of two phases during the electrochemical reconstruction. Multiple operando techniques unraveled that in situ iodine ions leaching from AgI restrained the entire reduction of CuO to acquire stable active Cu0 /Cu+ species during the CO2 RR. This way, the residual iodine species of the Ag matrix accelerated CO generation and iodine-induced Cu0 /Cu+ promotes C-C coupling. This self-adaptive dual-optimization endowed our catalysts with an excellent C2+ Faradaic efficiency of 68.9 %. Material operando changes in this work offer a new approach for manipulating active species towards enhancing C2+ products.

Dual-Regulation of Defect Sites and Vertical Conduction by Spiral Domain for Electrocatalytic Hydrogen Evolution.

Insufficient active sites and weak vertical conduction are the intrinsic factors that restrict the electrocatalytic HER for transition-metal dichalcogenides. As a prototype, we proposed a model of spiral MoTe2 to optimize collectively the above issues. The conductive atomic force microscopy of an individual spiral reveals that the retentive vertical conduction irrespective of layer thickness benefits from the connected screw dislocation lines between interlayers. Theoretical calculations uncover that the regions near the edge step of the spiral structures more easily form Te vacancies and have lower ΔGH * as extra active sites. A single spiral MoTe2 -based on-chip microcell was fabricated to extract HER activity and achieved an ultrahigh current density of 3000 mA cm-2 at an overpotential of 0.4 V, which is about two orders of magnitude higher than the exfoliated counterpart. Profoundly, this unusual spiral model will initiate a new pathway for triggering other inert catalytic reactions.

Effect of Strong Intermolecular Interaction in 2D Inorganic Molecular Crystals.

Strong intermolecular interactions in 2D organic molecular crystals arising from π-π stacking have been widely explored to achieve high thermal stability, high carrier mobility, and novel physical properties, which have already produced phenomenal progress. However, strong intermolecular interactions in 2D inorganic molecular crystals (2DIMCs) have rarely been investigated, severely limiting both the fundamental research in molecular physics and the potential applications of 2DIMCs for optoelectronics. Here, the effect of strong intermolecular interactions induced by unique short intermolecular Se-Se and P-Se contacts in 2D α-P4Se3 nanoflakes is reported. On the basis of theoretical calculations of the charge density distribution and an analysis of the thermal expansion and plastic-crystal transition, the physical picture of strong intermolecular interactions can be elucidated as a higher charge density between adjacent P4Se3 molecules, arising from an orderly and close packing of P4Se3 molecules. More importantly, encouraged by the strong intermolecular coupling, the in-plane mobility of α-P4Se3 nanoflakes is first calculated with a quantum nuclear tunneling model, and a competitive hole mobility of 0.4 cm2 V-1 s-1 is obtained. Our work sheds new light on the intermolecular interactions in 2D inorganic molecular crystals and is highly significant for promoting the development of molecular physics and optoelectronics.

Recent Advances in 2D Group VB Transition Metal Chalcogenides.

2D materials have received considerable research interest owing to their abundant material systems and remarkable properties. Among them, 2D group VB transition metal chalcogenides (GVTMCs) stand out as emerging 2D metallic materials and significantly broaden the research scope of 2D materials. 2D GVTMCs have great advantages in electrical transport, 2D magnetism, charge density wave, sensing, catalysis, and charge storage, making them attractive in the fields of functional devices and energy chemistry. In this review, the recent progress of 2D GVTMCs is summarized systematically from fundamental properties, growth methodologies to potential applications. The challenges and prospects are also discussed for future research in this field.

On-chip electrocatalytic microdevice: an emerging platform for expanding the insight into electrochemical processes.

Electrochemical conversion is an important process in renewable energy conversion, and electrocatalysts play a vital role since they can improve the rate and efficiency of chemical transformations. Thus, the continuing interest in electrocatalysis is fueled both in terms of mechanism exploration and performance optimization, and this field is continuously being updated. However, conventional electrochemical methods still have room to be explored, such as in situ dynamic monitoring, external field regulation, and single-entity electrocatalytic detection. Noteworthily, inspired by the recent success in nanoelectronic semiconductor devices, the emerging field of on-chip electrocatalytic microdevices, focusing on the electrochemical behaviors at individual nanowire/nanosheet as the working electrode, has emerged as a powerful alternative platform to the traditional techniques. This unique device configuration enables several advantages, such as in situ electronic/electrochemical measurements and adjustable microstructure of individual catalysts, which is constantly expanded to directly probe electrochemical processes to obtain previously inaccessible information. Hence, herein, we first introduce the device configuration and its advantages as an emerging platform. Subsequently, the attempts to expand the insight into electrochemical processes through this type of microdevice are explicitly analyzed and summarized including dynamic monitoring, external field regulation, identification of active sites, and single structural factor regulation. Finally, some personal perspectives on the challenges and future research directions in this promising area are also presented. We believe that this review will provide new insight into electrochemical processes, ranging from dynamic exploration to performance optimization.

Shaping Li Deposits from Wild Dendrites to Regular Crystals via the Ferroelectric Effect.

Manipulating the Li plating behavior remains a challenging task toward Li-based high-energy batteries. Generally, the Li plating process is kinetically controlled by ion transport, concentration gradient, local electric field, etc. A myriad of strategies have been developed for homogenizing the kinetics; however, such kinetics-controlled Li plating nature is barely changed. Herein, a ferroelectric substrate comprised of homogeneously distributed BaTiO3 was deployed and the Li plating behavior was transferred from a kinetic-controlled to a thermodynamic-preferred mode via ferroelectric effect. Such Li deposits with uniform hexagonal and cubic shapes are highly in accord with the thermodynamic principle where the body-centered cubic Li is apt to expose more (110) facets as possible to maximally minimize its surface energy. The mechanism was later confirmed due to the spontaneous polarization of BTO particles trigged by an applied electric field. The instantly generated reverse polarized field and charged ends not only neutralized the electric field but also leveled the ion distribution at the interface.