Magnetically oriented nanosheet interlayer for dynamic regeneration in lithium metal batteries.

Lithium (Li) metal has been recognized as a promising anode to advance the energy density of current Li-based batteries. However, the growth of the solid-electrolyte interphase (SEI) layer and dendritic Li microstructure pose significant challenges for the long-term operation of Li metal batteries (LMBs). Herein, we propose the utilization of a suspension electrolyte with dispersed magnetically responsive nanosheets whose orientation can be manipulated by an external magnetic field during cell operation for realizing in situ regeneration in LMBs. The regeneration mechanism arises from the redistribution of the ion flux and the formation of an inorganic-rich SEI for uniform and compact Li deposition. With the magnetic-field-induced regeneration process, we show that a Li||Li symmetric cell stably operates for 350 h at 2 mA cm-2 and 2 mA h cm-2, ~5 times that of the cell with the pristine electrolyte. Furthermore, the cycling stability can be significantly extended in the Li||NMC full cell of 3 mA h cm-2, showing a capacity retention of 67% after 500 cycles at 1C. The dynamic Li metal regeneration demonstrated here could bring useful design considerations for reviving the operating cells for achieving high-energy, long-duration battery systems.

Vertically assembled nanosheet networks for high-density thick battery electrodes.

As one of the prevailing energy storage systems, lithium-ion batteries (LIBs) have become an essential pillar in electric vehicles (EVs) during the past decade, contributing significantly to a carbon-neutral future. However, the complete transition to electric vehicles requires LIBs with yet higher energy and power densities. Here, we propose an effective methodology via controlled nanosheet self-assembly to prepare low-tortuosity yet high-density and high-toughness thick electrodes. By introducing a delicate densification in a three-dimensionally interconnected nanosheet network to maintain its vertical architecture, facile electron and ion transports are enabled despite their high packing density. This dense and thick electrode is capable of delivering a high volumetric capacity >1,600 mAh cm-3, with an areal capacity up to 32 mAh cm-2, which is among the best reported in the literature. The high-performance electrodes with superior mechanical and electrochemical properties demonstrated in this work provide a potentially universal methodology in designing advanced battery electrodes with versatile anisotropic properties.

Chemically coupling SnO2 quantum dots and MXene for efficient CO2 electroreduction to formate and Zn-CO2 battery.

Electrochemical conversion of CO2 into formate is a promising strategy for mitigating the energy and environmental crisis, but simultaneously achieving high selectivity and activity of electrocatalysts remains challenging. Here, we report low-dimensional SnO2 quantum dots chemically coupled with ultrathin Ti3C2Tx MXene nanosheets (SnO2/MXene) that boost the CO2 conversion. The coupling structure is well visualized and verified by high-resolution electron tomography together with nanoscale scanning transmission X-ray microscopy and ptychography imaging. The catalyst achieves a large partial current density of -57.8 mA cm-2 and high Faradaic efficiency of 94% for formate formation. Additionally, the SnO2/MXene cathode shows excellent Zn-CO2 battery performance, with a maximum power density of 4.28 mW cm-2, an open-circuit voltage of 0.83 V, and superior rechargeability of 60 h. In situ X-ray absorption spectroscopy analysis and first-principles calculations reveal that this remarkable performance is attributed to the unique and stable structure of the SnO2/MXene, which can significantly reduce the reaction energy of CO2 hydrogenation to formate by increasing the surface coverage of adsorbed hydrogen.

Light-Triggered Reversible Change in the Electronic Structure of MoO3 Nanosheets via an Excited-State Proton Transfer Mechanism.

Light is an attractive source of energy for regulating stimulus-responsive chemical systems. Here, we use light as a gating source to control the redox state, the localized surface plasmonic resonance (LSPR) peak, and the structure of molybdenum oxide (MoO3) nanosheets, which are important for various applications. However, the light excitation is not that of the MoO3 nanosheets but rather that of pyranine (HPTS) photoacids, which in turn undergo an excited-state proton transfer (ESPT) process. We show that the ESPT process from HPTS to the nanosheets and the intercalation of protons within the MoO3 nanosheets trigger the reduction of the nanosheets and the broadening of the LSPR peak, a process that is reversible, meaning that in the absence of light, the LSPR peak diminishes and the nanosheets return to their oxidized form. We further show that this reversible process is accompanied by a change in the nanosheet size and morphology.

Controlled Growth of Two-Dimensional SnSe/SnS Core/Crown Heterostructures.

We present a novel, straightforward, and reproducible one-pot heating up technique to synthesize core/crown SnSe/SnS nanosheets by a careful adjustment of the sulfur and selenium precursor reactivity. Here, the SnSe nanosheets are prepared via a wet-chemical route using SnCl2 and selenium phosphines. By adding a highly reactive S-oleylamine complex during the growth of the SnSe sheets at 240 °C, SnS crowns were formed within the SnSe sheets. The number of SnS crowns can be tailored upon repeated addition of S-oleylamine. A combination of transmission electron microscopy, high-resolution transmission electron microscopy, atomic force microscopy, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy proves the formation of highly crystalline core/crown structures.

Atomic Layer Engineering of Pd Nanosheets for an Enhanced Hydrogen Evolution Reaction.

Thickness control of two-dimensional (2D) metal nanosheets (metallenes) has scientific significance for energy and catalyst applications, yet is unexplored owing to the lack of an efficient approach for the tailored synthesis of metallenes with controlled atomic layers. Here we report a 2D template-directed synthesis of ultrathin Pd nanosheets with well-controlled thicknesses. Molecularly thin single-crystalline Pd nanosheets with well-defined hexagonal morphologies were synthesized via a one-pot method with 2,4,6-trichlorophenyl formate. Such Pd nanosheets were used as hard templates for the tailored synthesis of the Pd nanosheets with controlled thicknesses (9, 11, 13, and 15 atomic layers). Hard X-ray photoelectron spectroscopy and density functional theory calculations revealed unique electronic states in thickness-controlled Pd nanosheets; these states included reduced surface charges to bulk, increased work functions, and decreased d-band centers. Thus, atomic layer engineering of Pd nanosheets enabled the fine-tuning of the surface electronic states to improve the hydrogen evolution reaction.

Phase and Defect Engineering of MoSe2 Nanosheets for Enhanced NIR-II Photothermal Immunotherapy.

Inducing immunogenic cell death (ICD) during photothermal therapy (PTT) has the potential to effectively trigger photothermal immunotherapy (PTI). However, ICD induced by PTT alone is often limited by inefficient PTT, low immunogenicity of tumor cells, and a dysregulated redox microenvironment. Herein, we develop MoSe2 nanosheets with high-percentage metallic 1T phase and rich exposed active Mo centers through phase and defect engineering of MoSe2 as an effective nanoagent for PTI. The metallic 1T phase in MoSe2 nanosheets endows them with strong PTT performance, and the abundant exposed active Mo centers endow them with high activity for glutathione (GSH) depletion. The MoSe2-mediated high-performance PTT synergizing with efficient GSH depletion facilitates the release of tumor-associated antigens to induce robust ICD, thus significantly enhancing checkpoint blockade immunotherapy and activating systemic immune response in mouse models of colorectal cancer and triple-negative metastatic breast cancer.

Two-Dimensional Sulfonate-Functionalized Metal-Organic Framework Membranes for Efficient Lithium-Ion Sieving.

Two-dimensional (2D) membranes have shown promising potential for ion-selective separation but often suffer from the trade-off between permeability and selectivity. Herein, we report an ultrathin 2D sulfonate-functionalized metal-organic framework (MOF) membrane for efficient lithium-ion sieving. The narrow pores with angstrom precision in the MOF assist hydrated ions to partially remove the hydration shell, according to different hydration energies. The abundant sulfonate groups in the MOF channels serve as hopping sites for fast lithium-ion transport, contributing to a high Li-ion permeability. Then, the difference in affinity of the Li+, Na+, K+, and Mg2+ ions to the terminal sulfonate groups further enhances the Li-ion selectivity. The reported ultrathin MOF membrane overcomes the trade-off between permeability and selectivity and opens up a new avenue for highly permselective membranes.

Vapor Phase Growth of Air-Stable Hybrid Perovskite FAPbBr3 Single-Crystalline Nanosheets.

Organic-inorganic hybrid perovskites have attracted tremendous attention owing to their fascinating optoelectronic properties. However, their poor air stability seriously hinders practical applications, which becomes more serious with thickness down to the nanoscale. Here we report a one-step vapor phase growth of HC(NH2)2PbBr3 (FAPbBr3) single-crystalline nanosheets of tunable size up to 50 µm and thickness down to 20 nm. The FAPbBr3 nanosheets demonstrate high stability for over months of exposure to air with no degradation in surface roughness and photoluminescence efficiency. Besides, the FAPbBr3 photodetectors exhibit superior overall performance as compared to previous devices based on nonlayered perovskite nanosheets, such as an ultralow dark current of 24 pA, an ultrahigh responsivity of 1033 A/W, an external quantum efficiency over 3000%, a rapid response time around 25 ms, and a high on/off ratio of 104. This work provides a strategy to tackle the challenges of hybrid perovskites toward integrated optoelectronics with requirements of nanoscale thickness, high stability, and excellent performance.

Cryoprotective Ice-Philic Black Phosphorus Nanosheets for Augmented Thawing of Frozen Cells.

Controlling ice formation is critical in fields such as atmospheric science and biological cryopreservation. However, thermal heterogeneity during freezing and thawing in cryopreservation causes uneven ice crystallization and melting, leading to mechanical and thermal stress-induced damage. This study introduces biocompatible and biodegradable black phosphorus (BP)-polyethylene glycol-amine nanosheets (NS) to address this issue. BP NS primarily localize at ice grain boundaries, while amine groups of NH2-PEG-NH2 form hydrogen bonds with H2O molecules, penetrating ice crystals. In situ cross-sectional observations confirmed that BP-PEG-NH2 NS promotes uniform melting and facilitates ice cracks and boundaries. Heat transfer analysis using a bidirectional heating system revealed that the internal heat energy varies based on BP dispersion within the ice crystals. When applied to the cryopreservation of human tongue squamous cell carcinoma cells, BP-PEG-NH2 NSs significantly improved post-thaw viability. It presents a promising strategy for designing thawing materials after cryopreservation of cells, tissues, and organs.

Controlled Growth of Submillimeter-Scale Cr5Te8 Nanosheets and the Domain Wall Nucleation Governed Magnetization Reversal Process.

Two-dimensional (2D) ferromagnets have attracted widespread attention for promising applications in compact spintronic devices. However, the controlled synthesis of high-quality, large-sized, and ultrathin 2D magnets via facile, economical method remains challenging. Herein, we develop a hydrogen-tailored chemical vapor deposition approach to fabricating 2D Cr5Te8 ferromagnetic nanosheets. Interestingly, the time period of introducing hydrogen was found to be crucial for controlling the lateral size, and a Cr5Te8 single-crystalline nanosheet of lateral size up to ∼360 µm with single-unit-cell thickness has been obtained. These samples exhibit a leading role of domain wall nucleation in governing the magnetization reversal process, providing important references for optimizing the performances of associated devices. The nanosheets also show notable magnetotransport response, including nonmonotonous magnetic-field-dependent magnetoresistance and sizable anomalous Hall resistivity, demonstrating Cr5Te8 as a promising material for constructing high-performance magnetoelectronic devices. This study presents a breakthrough of large-sized CVD-grown 2D magnetic materials, which is indispensable for constructing 2D spintronic devices.

Self-Interface in Rh Nanosheets-Supported Tetrahedral Rh Nanocrystals for Promoting Electrocatalytic Oxidation of Ethanol.

Direct ethanol fuel cells hold great promise as a power source. However, their commercialization is limited by anode catalysts with insufficient selectivity toward a complete oxidation of ethanol for a high energy density, as well as sluggish catalytic kinetics and low stability. To optimize the catalytic performance, rationally tuning surface structure or interface structure is highly desired. Herein, a facile route is reported to the synthesis of Rh nanosheets-supported tetrahedral Rh nanocrystals (Rh THs/NSs), which possess self-supporting homogeneous interface between Rh tetrahedrons and Rh nanosheets. Due to full leverage of the structural advantages within the given structure and construction of interfaces, the Rh THs/NSs can serve as highly active electro-catalysts with excellent mass activity and selectivity toward ethanol electro-oxidation. The in situ Fourier transform infrared reflection spectroscopy showed the Rh THs/NSs exhibit the highest C1 pathway selectivity of 23.2%, far exceeding that of Rh nanotetrahedra and Rh nanosheets. Density function theory calculations further demonstrated that self-interface between Rh nanosheets and tetrahedra is beneficial for C-C bond cleavage of ethanol. Meanwhile, the self-supporting of 2D nanosheets greatly enhance the stability of tetrahedra, which improves the catalytic stability.

Nanosheet Particles with Defect-Free Block Copolymer Structures Driven by Emulsions Containing Crystallizable Surfactants.

Highly anisotropic-shaped particles with well-ordered internal nanostructures have received significant attention due to their unique shape-dependent photonic, rheological, and electronic properties and packing structures. In this work, nanosheet particles with cylindrical block copolymer (BCP) arrays are achieved by utilizing collapsed emulsions as a scaffold for BCP self-assembly. Highly elongated structures with large surface areas are formed by employing crystallizable surfactants that significantly reduce the interfacial tension of BCP emulsions. Subsequently, the stabilized elongated emulsion structures lead to the formation of BCP nanosheets. Specifically, when polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and 1-octadecanol (C18-OH) are co-assembled within an emulsion, C18-OH penetrates the surfactant layer at the emulsion interface, lowering the interfacial tension (i.e., below 1 mN m-1 ) and causing emulsion deformation. In addition, C18-OH crystallization allows for kinetic arrest of the collapsed emulsion shape during solvent evaporation. Consequently, PS-b-PDMS BCPs self-assemble into defect-free structures within nanosheet particles, exhibiting an exceptionally high aspect ratio of over 50. The particle formation mechanism is further investigated by controlling the alkyl chain length of the fatty alcohol. Finally, the coating behavior of nanosheet particles is investigated, revealing that the deposition pattern on a substrate is strongly influenced by the particle's shape anisotropy, thus highlighting their potential for advanced coating applications.

Engineering Copper-Containing Nanoparticles-Loaded Silicene Nanosheets with Triple Enzyme Mimicry Activities and Photothermal Effect for Promoting Bacteria-Infected Wound Healing.

Skin wounds accompanied by bacterial infections threaten human health, and conventional antibiotic treatments are ineffective for drug-resistant bacterial infections and chronically infected wounds. The development of non-antibiotic-dependent therapeutics is highly desired but remains a challenging issue. Recently, 2D silicene nanosheets with considerable biocompatibility, biodegradability, and photothermal-conversion performance have received increasing attention in biomedical fields. Herein, copper-containing nanoparticles-loaded silicene (Cu2.8O@silicene-BSA) nanosheets with triple enzyme mimicry catalytic (peroxidase, catalase, and oxidase-like) activities and photothermal function are rationally designed and fabricated for efficient bacterial elimination, angiogenesis promotion, and accelerated wound healing. Cu2.8O@silicene-BSA nanosheets display excellent antibacterial activity through synergistic effects of reactive oxygen species generated from multiple catalytic reactions, intrinsic bactericidal activity of released Cu2+ ions, and photothermal effects, achieving high antibacterial efficiencies on methicillin-resistant Staphylococcus aureus (MRSA) of 99.1 ± 0.7% in vitro and 97.2 ± 1.6% in vivo. In addition, Cu2.8O@silicene-BSA nanosheets exhibit high biocompatibility for promoting human umbilical vein endothelial cell (HUVEC) proliferation and angiogenic differentiation. In vivo experiments reveal that Cu2.8O@silicene-BSA nanosheets with synergistic photothermal/chemodynamic therapeutics effectively accelerate MRSA-infected wound healing by eliminating bacteria, alleviating inflammation, boosting collagen deposition, and promoting angiogenesis. This research presents a promising strategy to engineer photothermal-assisted nanozyme catalysis for bacteria-invaded wound healing.

3D Network of Liquid Metal-Embedded Graphene via Surface Coating for Flexible Thermal Management.

The rapid growth of flexible electronics has led to significant demand for relevant accessories, particularly highly efficient flexible heat dissipators. The fluidity of liquid metal (LM) makes it a candidate for realizing flexible thermal interface materials (TIMs). However, it is still challenging to combine LM with a conductive thermal network to achieve the synchronous improvement of thermal conductivity and flexibility. In this work, highly conductive flexible LM@GN/ANF films are made by coating LM nano-droplets with graphene nanosheets (GN) via sonication, and then they are combined with aramid nanofibers (ANF). The LM@GN/ANF film is found to have a thermal conductivity of 5.67 W m-1 K-1 and a 24.5% reduction in Young's modulus, making it suitable for various flexible electronic applications such as wearable devices and biosensors.

Significantly Enhanced the Energy Density of Dielectric Composites by Sandwich Structure with Highly Insulating Mica Nanosheets.

Dielectric polymer composites exhibit great application prospects in advanced pulse power systems and electric systems. However, the decline of breakdown strength by loading of single high dielectric constant nanofiller hinders the sustained increase in energy density of the composites. Here, a sandwich-structured nanocomposite prepared with mica nanosheets as the second filler exhibits decoupled modulation of dielectric constant and breakdown strength. The traditional layered clay mineral mica is exfoliated into nanosheets and filled into polyvinylidene difluoride (PVDF), which shows a special depolarization effect in the polymer matrix. In Kelvin probe microscopy characterization and thermally stimulated depolarization current indicates that the mica nanosheets provided space charge traps for the polymer matrix and effectively suppressed the carrier motion. A sandwich structure composite material with mica nanosheets as the central layer has achieved a high energy density of 11.48 J cm-3, 2.4 times higher than the pure PVDF film. This is due to the fact that randomly oriented distribution of nanosheets in a polymer matrix provide better current blocking. This work provides an effective method to improve the energy density of dielectric polymer composites by synergistically introducing insulating nanosheets and high dielectric constant nanofillers.

Stretching Aligned Hydrogen Bonding Network to Evoke Mechanically Robust and High-Energy-Density P(VDF-HFP) Dielectric Film Capacitors.

Polymer-based dielectric film capacitors are essential energy storage components in electronic and power systems due to their ultrahigh power density and ultra-fast charge storage/release capability. Nonetheless, their relatively low energy density does not fully meet the requirements of power electronics and pulsed power systems. Herein, a scalable composite dielectric film based on a ferroelectric polymer with edge hydroxylated boron nitride nanosheets (BNNS-OH) is fabricated via the construction of a hydrogen bonding network and stretching orientation strategy. The presence of hydroxyl groups on boron nitride aids in forming a robust hydrogen bonding network within the ferroelectric polymer, leading to a significant increase in Young's modulus and superior dielectric performance. Furthermore, the stretching process aligns the BNNS-OH and the hydrogen bonding network along the drawing direction via covalent and hydrogen bonding interaction, resulting in a remarkable tensile strength (109 MPa), breakdown strength (688 MV m-1), and energy density (28.2 J cm-3), outperforming mostrepresentative polymer-based dielectric films. In combining the advantages of a simple preparation process, extraordinary energy storage performance, and low-cost raw materials, this strategy is viable for large-scale production of polymer-based dielectric films with high mechanical and dielectric performance and opens a new path for the development of next-generation energy storage applications.

Mesoporous Nitrogen-Doped Holey Reduced Graphene Oxide: Preparation, Purification, and Application for Metal-Free Electrochemical Sensing of Dopamine.

Holey graphenic nanomaterials with porosity within the basal plane attract significant interest. It is observed that the perforation of graphene can enhance the specific surface area of the nanosheet, ensuring effective wetting and penetration of electrolytes to the electrode surface, facilitating rapid charge transfer, and boosting the electrocatalytic efficacy of the transducers. This study reports the first example of nitrogen-doped holey reduced graphene oxide with a mesoporous morphology of the graphene basal plane (N-MHG). It is shown that N-MHG can be synthesized through a one-step hydrothermal treatment of GO using NH3 and H2O2. A straightforward procedure for the purification of N-MHG has also been developed. AFM, TEM, and Raman analyses have revealed that N-MHG possesses a highly mesoporous network structure with a pore size ranging from 10 to 50 nm. X-ray photoelectron spectroscopy data have indicated a partial reduction of the graphene oxide sheets during the etching process but also show a 3-5 times higher content of C═O and O-C═O fragments compared to rGO. This could account for the remarkable stability of the N-MHG aqueous suspension. An electrochemical sensor for dopamine analysis is assembled on a glassy carbon electrode with N-MHG/Nafion membrane and characterized by cyclic voltammetry and electrochemical impedance spectroscopy.

Dual-Modified Electrospun Fiber Membrane as Separator with Excellent Safety Performance and High Operating Temperature for Lithium-Ion Batteries.

Polyacrylonitrile/Boric acid/Melamine/the delaminated BN nanosheets electrospun fiber membrane (PB3N1BN) with excellent mechanical property, high thermal stability, superior flame-retardant performance, and good wettability are fabricated by electrospinning PAN/DMF/H3BO3/C3H6N6/ the delaminated BN nanosheets (BNNSs) homogeneous viscous suspension and followed by a heating treatment. BNNSs are obtained by delaminating the bulk h-BN in isopropyl alcohol (IPA) with an assistance of Polyvinylpyrrolidone (PVP). Benefiting from the cross-linked pore structure and high-temperature stability of BNNSs, PB3N1BN electrospun fiber membrane delivers high thermal dimensional stability (almost no size contraction at 200 °C), excellent mechanical property (19.1 MPa), good electrolyte wettability (contact angle about 0°), and excellent flame retardancy (minimum total heat release of 3.2 MJ m-2). Moreover, the assembled LiFePO4/PB3N1BN/Li asymmetrical battery using LiFePO4 as the cathode and Li as the anode has a high capacity (169 mAh g-1 at 0.5 C), exceptional rate capability (129 mAh g-1 at 5 C), the prominent cycling stability without obvious decay after 400 cycles, and a good discharge capacity of 152 mAh g-1 at a high temperature of 80 °C. This work offers a new structural design strategy toward separators with excellent mechanical performance, good wettability, and high thermal stability for lithium-ion batteries.

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.