Single Nanosheets Research Articles

Ferroelectric Polarization Modulated Facet‐selective Charge Separation in Bi4NbO8Cl Single Crystal for Boosting Visible‐light Driven Bifunctional Water Splitting

AbstractDeveloping bifunctional water‐splitting photocatalysts is meaningful, but challenged by the harsh requirements of specific‐facet single crystals with spatially separated reactive sites and anisotropic charge transfer paths contributed by well‐built charge driving force. Herein, tunable ferroelectric polarization is introduced in Bi4NbO8Cl single crystal nanosheets to strengthen the orthogonal charge transfer channels. By manipulating the in‐plane polarization from octahedral off‐centering of Nb5+ and out‐of‐plane polarization from lone pair electron effect of anisotropic Bi3+, both the fast charge recombination in bulk catalyst and the process of charge trapping into surface states can be effectively modulated. Collaborating with modest polarization electric field and facet junction induced built‐in electric field, cooperative charge tractive force is constructed, which reinforces the spatial separation and migration of photogenerated electrons and holes to {110} reductive site facet and {001} oxidation site facet, respectively. While excessive polarization charges impair the facet‐selective charge separation characteristics and conversely promote charge recombination on the surface. As a result, polarity‐optimized Bi4NbO8Cl shows an excellent H2 and O2 evolution rate of 54.21 and 36.08 μmol ⋅ h−1 in the presence of sacrificial reagents under visible light irradiation. This work unveils the function of ferroelectric polarization in tuning the intrinsic facet‐selective charge transfer process of photocatalysts.

Single Crystalline α-Fe2O3 Nanosheets with Improved PEC Performance for Water Splitting.

We report the photoelectrochemical (PEC) performance of a densely grown single crystalline hematite (α-Fe2O3) nanosheet photoanode for water splitting. Unlike expensive ITO/FTO substrates, the sheets were grown on a piece of pure Fe through controlled thermal oxidation, which is a facile low cost and one-step synthesis route. The sheets grow with a widest surface parallel to basal plane (0001). Iron oxide formed on Fe consisting of layer structure α-Fe2O3-Fe3O4-Fe is elucidated from GIXRD and correlated to spectral features observed in Raman and UV-vis spectroscopy. The top α-Fe2O3 nanosheet layer serves as a photoanode, whereas the conducting Fe3O4 layer serves to transport photogenerated electrons to the counter electrode through its back contact. Time-resolved photoluminescence (TRPL) measurements revealed significantly prolonged carrier lifetime compared to that of bulk. Compared to the thin film of α-Fe2O3 grown on the FTO substrate, ∼3 times higher photocurrent density (0.33 mA cm-2 at 1.23 VRHE) was achieved in the nanosheet sample under solar simulated AM 1.5 G illumination. The sample shows a bandgap of 2.1 eV and n-type conductivity with carrier density 9.59 × 1017 cm-3. Electrochemical impedance spectroscopy (EIS) measurements reveal enhanced charge transport properties. The results suggest that nanosheets synthesized by the simple method yield far better PEC performance than the thin film on the FTO substrate. The anodic shifts of flat band potential, delayed electron-hole recombination, and growth direction parallel to the highly conducting basal plane (0001) being some of the contributing factors to the higher photocurrent observed in the NS photoanode are discussed. Characterizations carried out before and after the PEC reaction show excellent stability of the nanosheets in an alkaline electrochemical environment.

Epitaxial growth of metal-organic framework nanosheets into single-crystalline orthogonal arrays

Construction of two-dimensional nanosheets into three-dimensional regular structures facilitates the mass transfer and exploits the maximum potential of two-dimensional building blocks in applications such as catalysis. Here, we report the synthesis of metal-organic frameworks with an orthogonal nanosheet array. The assembly involves the epitaxial growth of single crystalline metal-organic framework nanosheets with a naturally non-preferred facet exposure as the shell on a cubic metal-organic framework as the core. The nanosheets, despite of two typical shapes and crystallographic orientations, also form a single crystalline orthogonally arrayed framework. The density and size of nanosheets in the core-shell-structured composite metal-organic frameworks can be well adjusted. Moreover, metal-organic frameworks with a single composition and hollow orthogonal nanosheet array morphology can be obtained. Benefiting from the unusual facet exposure and macroporous structure, the designed structure exhibits improved electrocatalytic oxygen evolution activity compared to conventional nanosheets.

Synthesis and Characterization of β-Cyclodextrin-Hybridized Exfoliated Kaolinite Single Nanosheets as Potential Carriers of Oxaliplatin with Enhanced Loading, Release, and Cytotoxic Properties.

Natural kaolinite was subjected to a successful exfoliation process into separated kaolinite nanosheets (KNs), followed by hybridization with β-cyclodextrin biopolymer (β-CD), forming an advanced bio-nanocomposite (β-CD/KNs). The synthetic products were evaluated as enhanced delivery structures for oxaliplatin chemotherapy (OXAPN). The hybridization of KNs with β-CD polymer notably enhanced the loading capacity to 355.3 mg/g (β-CD/KNs) as compared to 304.9 mg/g for KNs. The loading of OXAPN into both KNs and β-CD/KNs displayed traditional pseudo-first-order kinetics (R2 > 0.85) and a conventional Langmuir isotherm (R2 = 0.99). The synthetic β-CD/KNs validates a greater occupied effective site density (98.7 mg/g) than KNs (66.3 mg/g). Furthermore, the values of the n steric parameter (4.7 (KNs) and 3.6 (β-CD/KNs)) reveal the vertical orientation of the loaded molecules and the loading of them by multi-molecular mechanisms. These mechanisms are mainly physical processes based on the obtained Gaussian energy (<8 KJ/mol) and loading energy (<40 KJ/mol). The release profiles of both KNs and β-CD/KNs extend for about 120 h, with remarkably faster rates for β-CD/KNs. According to the release kinetic findings, the release of OXAPN displays non-Fickian transport behavior involving the cooperation of diffusion and erosion mechanisms. The KNs and β-CD/KNs as free particles showed considerable cytotoxicity and anticancer properties against HCT-116 cancer cell lines (71.4% cell viability (KNs) and 58.83% cell viability (β-CD/KNs)). Additionally, both KNs and β-CD/KNs significantly enhanced the OXAPN's cytotoxicity (2.04% cell viability (OXAPN/KNs) and 0.86% cell viability (OXAPN/β-CD/KNs).

Insight into the Morphological Properties of Nano-Kaolinite (Nanoscrolls and Nanosheets) on Its Qualification as Delivery Structure of Oxaliplatin: Loading, Release, and Kinetic Studies

Natural kaolinite underwent advanced morphological-modification processes that involved exfoliation of its layers into separated single nanosheets (KNs) and scrolled nanoparticles as nanotubes (KNTs). Synthetic nanostructures have been characterized as advanced and effective oxaliplatin-medication (OXAP) delivery systems. The morphological-transformation processes resulted in a remarkable enhancement in the loading capacity to 304.9 mg/g (KNs) and 473 mg/g (KNTs) instead of 29.6 mg/g for raw kaolinite. The loading reactions that occurred by KNs and KNTs displayed classic pseudo-first-order kinetics (R2 &gt; 0.90) and conventional Langmuir isotherms (R2 = 0.99). KNTs exhibit a higher active site density (80.8 mg/g) in comparison to KNs (66.3 mg/g) and raw kaolinite (6.5 mg/g). Furthermore, compared to KNs and raw kaolinite, each site on the surface of KNTs may hold up to six molecules of OXAP (n = 5.8), in comparison with five molecules for KNs. This was accomplished by multi-molecular processes, including physical mechanisms considering both the Gaussian energy (&lt;8 KJ/mol) and the loading energy (&lt;40 KJ/mol). The release activity of OXAP from KNs and KNTs exhibits continuous and regulated profiles up to 100 h, either by KNs or KNTs, with substantially faster characteristics for KNTs. Based on the release kinetic investigations, the release processes have non-Fickian transport-release features, indicating cooperative-diffusion and erosion-release mechanisms. The synthesized structures have a significant cytotoxicity impact on HCT-116 cancer cell lines (KNs (71.4% cell viability and 143.6 g/mL IC-50); KNTs (11.3% cell viability and 114.3 g/mL IC-50). Additionally, these carriers dramatically increase OXAP’s cytotoxicity (2.04% cell viability, 15.4 g/mL IC-50 (OXAP/KNs); 0.6% cell viability, 4.5 g/mL IC-50 (OXAP/KNTs)).

Spontaneous Dewetting of Au-Thin Layers on Oxide- and Fluorine-Terminated Single Crystalline Anatase and Efficient Use in Photocatalytic H2 Production.

In the present work, the spontaneous dewetting of thin Au layers on single crystalline anatase nanosheets into narrow-disperse Au nanoparticles is investigated. Patterns of the Au particles can be formed on the main facets of anatase that provide a high co-catalytic activity for photocatalytic generation of H2 . Dewetting is distinctly influenced by the respective facets (001) and (101), the deposit thickness, and secondary thermal dewetting, but most strongly by the surface termination of the nanosheets. Fluoride termination not only leads to an enhanced Au-phobic behavior but strongly affects the co-catalytic activity for photocatalytic generation of H2 . While fluoride termination with or without Au decoration is detrimental for hole transfer, the interplay of the Au co-catalyst and surface fluoride yields highly beneficial effect for electron transfer. This results in a three-times higher photocatalytic H2 production for the F-terminated surface. The findings suggest that dewetting of Au on surface fluorinated TiO2 is an effective way to modulate surface dewetting and achieve a strongly enhanced photocatalytic activity.

Ultrafine Homologous Ni2P–Co2P Heterostructures via Space‐Confined Topological Transformation for Superior Urea Electrolysis

AbstractConstructing effective electrocatalysts based on ultrafine heterostructures is a promising strategy for boosting catalytic performance by exposing active sites and increasing specific surface area. However, the fabrication of catalytically active heterostructures with elaborate architectures is still poorly developed owing to synthetic challenges, and the intrinsic mechanism of heterogeneous interfaces remains unclear because of insufficient evidence regarding real active sites. In this study, ultrafine homologous Ni2P–Co2P heterostructures (Ni2P–Co2P/C) are created using a topological transformation strategy from a Ni–Co layered double hydroxide/carbon (Ni–Co LDH/C) interconnected structure in a single nanosheet. When employed as catalysts in urea oxidation reaction (UOR), the Ni2P–Co2P/C heterostructures exhibit superior activity and stability, attributed to the optimized geometric and electronic structures of the catalytic sites. Specifically, it takes an ultralow potential of 1.27 V to reach a current density of 10 mA cm−2 with a small Tafel slope of 28.71 mV dec−1. The operando analyses and calculation results reveal that cobalt incorporation can reduce the generation potential of the surface reconstructive active species and optimize the absorption/desorption energy of the intermediates. Overall, this study proposes an efficient and cost‐effective UOR electrocatalyst and offers a new high‐performance homologous heterostructure design for widespread application.

Ultra-stable, sensitive and broadband photodetector based on large-area 2D bismuth oxyselenide film for multiband image sensing

Two-dimensional (2D) materials have proven to be a highly promising candidate for applications in electronic and optoelectronic devices due to their attractive structure and properties. However, the micron-scale dimensions, random distribution on the substrate, and complex transfer processes of 2D materials inevitably cause difficulties in device integration, which limits practical applications in photodetection. Herein, high-quality 2D Bi2O2Se film (2×2 cm) composed of numerous single crystal nanosheets on SrTiO3 substrate was prepared employing the chemical vapor deposition method. The layered Bi2O2Se film features a perfect atomic alignment free of lattice mismatch and a sharp interface with the SrTiO3 substrate. Afterward, a broadband photodetector based on 2D Bi2O2Se film was directly constructed, which covered the ultraviolet, visible and infrared range from 365 to 940 nm and demonstrated a fast response speed of 32 ms and 44 ms, maximum responsivity and detectivity of 136 mA/W and 2×109 Jones. Importantly, fast on/off behavior for 100 cycles and reliable photoresponse after storage in air for 1 year confirmed the excellent cycling stability and air stability of the Bi2O2Se photodetector. Furthermore, the Bi2O2Se photodetector as a single point sensing pixel was capable to perform high-resolution imaging of “H, I, T” patterns. This research affirms the huge potential of Bi2O2Se photodetectors to perform as reliable multi-band detection units in complex systems.

Study of Self Heating Effect in the wake of complete and partial bottom dielectric insertion under 5 nm Stacked Nanosheet Transistor

Beyond 7 nm technology nodes, a Stacked Nanosheet Field Effect Transistor (SNT) is a potential candidate to continue device scaling due to its higher ON/OFF current ratio and less Short Channel Effect than FinFET. However, its gate all-around structure with low thermal conductive HiK oxide material exacerbates the Self-Heating Effect (SHE) issue in the SNT. Further, a dielectric inserted beneath SNT to reduce leakage current disrupts the primary heat flow path through the substrate, aggravating the Self Heating Effect (SHE). This study focuses on exploring the thermal aspect of the SNT with partial and complete dielectric insertion under the device from a performance and reliability perspective. A 3D electrothermal analysis has been performed using Synopsys TCAD tool. The effect of partial and complete dielectric insertion under the device on lattice temperature was investigated in the case of single and double-stack nanosheet transistors. The effects of dielectric insertion on channel and substrate temperature were analyzed. Its variation with width, extension length, interface thermal resistance, and the number of sheets and stack pitch of SNT are discussed. Sheet-dependent heat flow through the substrate and source/drain contact explained for different types of SNT structures and its effect on device performance and reliability discussed. To discuss the effect of multiple parameters variation on the lattice temperature of the device, Analysis of Variance (ANOVA) method was used. It was found that complete dielectric insertion leads to a severe heating issue in the SNT compared to partial and without dielectric insertion.

Characterization of Kaolinite Single Methoxy Nano-Sheets as Potential Carriers of Oxaliplatin Drug of Enhanced Loading, Release, and Cytotoxicity Properties During the Treatment of Colorectal Cancer

Characterization of Kaolinite Single Methoxy Nano-Sheets as Potential Carriers of Oxaliplatin Drug of Enhanced Loading, Release, and Cytotoxicity Properties During the Treatment of Colorectal Cancer

Langmuir-Blodgett deposition and physicochemical surface characterization of two-dimensional perovskite nanosheets on ITO-PET substrates

We successfully obtained Ca2NaNb4O13− single perovskite nanosheets by delaminating x = 4 Dion-Jacobson type KCa2NaNb4O13 layered materials. These nanosheets were then deposited onto conductive, transparent, and flexible indium tin oxide-polyethylene terephthalate (ITO-PET) substrates using the Langmuir-Blodgett (LB) technique. The polar and apolar (dispersive) surface tension components of LB nanofilms composed of Ca2NaNb4O13− perovskite nanosheets and the work of adhesion between the nanofilms and silicon and ITO-PET substrates were determined through contact angle measurements combined with mathematical modeling based on surface thermodynamics. The results showed that the apolar surface tension components had similar values for all surfaces studied, while the polar surface tension components of the nanofilms deposited on the substrates had higher values than those of the bare substrates. The higher polar interaction observed between the nanofilm and ITO-PET resulted in higher total work of adhesion of the nanofilm to the ITO-PET surface in water, while the total work of adhesion computed between the nanofilm and Si was higher in air.

Investigation on the conductive properties of single MoO2 nanosheet

Although metallic MoO2 is arising as a new type of conductive transition metal oxide in optoelectrical application. However, the contact and intrinsic conductive properties remain unknown. Here, the contact characteristic and intrinsic conductive of single MoO2 nanosheet grown by CVD method were investigated. It’s found that the contact of Ag with MoO2 was better than that of Au. At low bias condition, the measured intrinsic conductivity of MoO2 is as high as (2.5 ± 1.3) × 104 S/cm. With increasing bias, non-linear behavior in IV characteristic and breakdown behavior is observed due to the contact effect. The supported current density is around 107 A/cm2. The result shows that the MoO2 is a superior conductive transition metal oxide material for the low-voltage application.

Single Unit-Cell Layered Bi2 Fe4 O9 Nanosheets: Synthesis, Formation Mechanism, and Anisotropic Thermal Expansion.

As an important multiferroic material, pure and low-dimensional phase-stable bismuth ferrite has wide applications. Herein, one-pot hydrothermal method was used to synthesize bismuth ferrite. Almost pure Bi2 Fe4 O9 , BiFeO3 , and their mixture were successfully obtained by controlling the KOH concentration in the hydrothermal solutions. The as-prepared Bi2 Fe4 O9 products were crystalline with Pbam space group, had nanosheet morphology, and tended to aggregate into nanofloret or random stacking. Each Bi2 Fe4 O9 nanosheet was a single crystal with (001) plane as its exposed surface. Single unit-cell layered Bi2 Fe4 O9 nanosheets had a uniform thickness of 1 nm. The surface energies of various (100), (010), and (001) planes were 3.6-4.0, 5.6-15.1, and 1.7-3.0 J m-2 , respectively, in the Bi2 Fe4 O9 crystal. The formation mechanism and structural model of the as-prepared single unit-cell layered Bi2 Fe4 O9 nanosheets have been given. The growth of Bi2 Fe4 O9 nanosheets was discussed. Thermal analysis showed that the Bi2 Fe4 O9 phase was stable up to 1260 K. The thermal expansion behavior of the Bi2 Fe4 O9 nanosheet was nonlinear. The thermal expansion coefficients of the ultrathin Bi2 Fe4 O9 nanosheets on the a-, b-, c-axes, and on the unit-cell volume V were determined, showing an anisotropic thermal expansion behavior. This study is helpful for the controllable synthesis of ultrathin Bi2 Fe4 O9 nanosheets.

2D nanosheets of layered double perovskites: synthesis, photostable bright orange emission and photoluminescence blinking.

Lead (Pb)-free layered double perovskites (LDPs) with exciting optical properties and environmental stability have sparked attention in optoelectronics, but their high photoluminescence (PL) quantum yield and understanding of the PL blinking phenomenon at the single particle level are still elusive. Herein, we not only demonstrate a hot-injection route for the synthesis of two-dimensional (2D) ∼2-3 layer thick nanosheets (NSs) of LDP, Cs4CdBi2Cl12 (pristine), and its partially Mn-substituted analogue [i.e., Cs4Cd0.6Mn0.4Bi2Cl12 (Mn-substituted)], but also present a solvent-free mechanochemical synthesis of these samples as bulk powders. Bright and intense orange emission has been perceived for partially Mn-substituted 2D NSs with a relatively high PL quantum yield (PLQY) of ∼21%. The PL and lifetime measurements both at cryogenic (77 K) and room temperatures were employed to understand the de-excitation pathways of charge carriers. With the implementation of super-resolved fluorescence microscopy and time-resolved single particle tracking, we identified the occurrence of metastable non-radiative recombination channels in a single NS. In contrast to the rapid photo-bleaching that resulted in a PL blinking-like nature of the controlled pristine NS, the 2D NS of the Mn-substituted sample displayed negligible photo-bleaching with suppression of PL fluctuation under continuous illumination. The blinking-like nature in pristine NSs appeared due to a dynamic equilibrium flanked by the active and in-active states of metastable non-radiative channels. However, the partial substitution of Mn2+ stabilized the in-active state of the non-radiative channels, which increased the PLQY and suppressed PL fluctuation and photo-bleaching events in Mn-substituted NSs.

In situ fabrication of a NiO nanoparticles/single-layered MXene nanosheet Schottky heterojunction toward sensing xylene and formaldehyde

A NiO nanoparticle decorated single layered MXene nanosheet based gas sensor shows excellent dual selectivity for detecting xylene and formaldehyde.

Preactivated zeolite nanosheet plate-tiled membrane on porous PVDF film: Synthesis and study of proton-selective ion conduction

Preactivated MFI zeolite nanosheet plates (ZNPs) with large areas (∼2.0 × 2.0 μm2) and nanometer thicknesses (∼60 nm) were prepared directly in liquid-dispersed state. The individual ZNP was a stack of 4-nm-thick single crystalline zeolite nanosheets (ZNs) interlinked by Si–O–Si bonds between neighboring ZN surfaces. The dispersed open-pore ZNPs allowed formulating suspensions for tiling ZNP membranes on polymer substrates without requiring post-coating activation. A pinhole-free ZNP-tiled (ZNPT) membrane has been achieved on macroporous PVDF film by a self-repairing vacuum-assisted filtration coating method. The resultant ZNPT layer was ∼500 nm-thick consisting of about 7 ZNP layers with inter-ZNP width and inter-ZNP entrance porosity around 9 nm and 2%, respectively. The ZNPT-PVDF membrane exhibited high selectivity to proton transport over vanadyl ion and low resistances to proton conduction in aqueous solutions. The membrane also demonstrated to function as an efficient ion separator for the vanadium redox flow battery. The reported synthesis of preactivated ZNP suspension may overcome the major hurdle to realizing polymer-supported ZN membranes, which is the inefficiency of existing methods in obtaining readily dispersible open-pore ZNs. The ZNPT-PVDF membrane can be a more affordable and sustainable alternative to the Nafion-based ion separation membranes.

Plasmonic imaging of the layer-dependent electrocatalytic activity of two-dimensional catalysts

Studying the localized electrocatalytic activity of heterogeneous electrocatalysts is crucial for understanding electrocatalytic reactions and further improving their performance. However, correlating the electrocatalytic activity with the microscopic structure of two-dimensional (2D) electrocatalysts remains a great challenge due to the lack of in situ imaging techniques and methods of tuning structures with atomic precision. Here, we present a general method of probing the layer-dependent electrocatalytic activity of 2D materials in situ using a plasmonic imaging technique. Unlike the existing methods, this approach was used to visualize the surface charge density and electrocatalytic activity of single 2D MoS2 nanosheets, enabling the correlation of layer-dependent electrocatalytic activity with the surface charge density of single MoS2 nanosheets. This work provides insights into the electrocatalytic mechanisms of 2D transition metal dichalcogenides, and our approach can serve as a promising platform for investigating electrocatalytic reactions at the heterogeneous interface, thus guiding the rational design of high-performance electrocatalysts.

Defect-State Transition Associated Hole Dynamics in Cuprous Iodide Nanosheets

The cuprous iodide of zinc-blende structure (γ-CuI) is a p-type semiconductor with a wide band gap of 3.1 eV. It is considered promising as the third generation of semiconductors, in applications of hole transport layer and transparent electrode due to the high hole density and carrier mobility, but its carrier transport characteristics have not yet been understood in detail. We synthesized γ-CuI nanosheets with large sizes and measured the carrier dynamics by femtosecond transient absorption (TA) spectroscopy. We observed signals of defect trapping photogenerated carriers during band-edge transitions, as well the weak band filling and photoinduced absorption directly associated with defect states. The species and lifetimes of defect assisted transition are identified and quantified based on TA measurements with various excitation fluences, and the changes of spectra and kinetics of defect band filling are correlated to the trend of density of Cu and I vacancies in samples with different thicknesses, based on the observations on a single nanosheet. We extract a diffusion coefficient of ∼71 cm2 s–1 and derive a diffusion length longer than the sample thickness, which possibly makes a remarkable contribution to the generation of a photocurrent. Our findings are expected to offer help for harnessing the defects in γ-CuI and improving its performances in optoelectronic applications.

Preparation of anode material zinc ferrite by molten salt method and its electrochemical performance

• For the first time, zinc ferrite nanomaterials were synthesized by molten salt method which is an innovation in method. • The use of zinc, iron and other metals widely distributed in nature as anodes not only has low cost, but also has no pollution to the environment. It is very likely to replace carbon as a commercial lithium ion battery anode material. • Materials synthesized by molten salt method, high phase purity, good material characterization, stable cycle performance. Ternary zinc-based oxides are considered as excellent anode materials for lithium-ion batteries. In the present research, because the poor cycling stability, rapid capacity decay and poor rate performance of metal oxides as battery anodes limit its use to some extent, the electrochemical performance is improved by reducing the material particle size. The ZnFe 2 O 4 synthesized by molten salt method with NaCl and KCl as salt medium reaches the nanometer level and has great morphology. Through high temperature combustion at 838 °C, the material exhibits lamellar structure. The pure phase of ZnFe 2 O 4 is confirmed by X-ray diffractometer, and the diameter of the submicron stacks is about 100 - 400 nm by scanning with field emission electron microscope. After transmission electron microscopy analysis, the size of a single nanosheet is between 80 nm and 100 nm, and the lattice fringe at (311) crystal plane is confirmed to be 0.2475 nm by high-resolution transmission. Confirming the material image analysis and characterization analysis, the material is electrochemically tested. The first discharge capacity reaches 1285.8 mAh g −1 at the current density of 200 mA g −1 by using the Land test system, the charge specific capacity is 654.8 mAh g −1 , and the coulombic efficiency is 50.93%. After 300 cycles, the high reversible discharge capacity of 550 mAh g −1 is still maintained, keep that zinc ferrite synthesized by molten salt method not only has high capacity, but also has cycle stability compared with other anode materials, which can be used as anode materials for lithium-ion batteries.

Polycations inclusion to simultaneously boost permeation and selectivity of two-dimensional TaS2 membranes for acid recovery

Two dimensional (2D) TaS2 laminates have highly regular and ordered transfer mass channels, thus being promising acid recovery membrane candidates for diffusion dialysis (DD) applications to discern H+ and metallic ions. However, it remains a daunting task to get access to high-performance 2D acid recycling membranes made from single TaS2 nanosheets. Here, we report manipulation of the chemical environments of TaS2 channels to develop excellent acid recycling 2D membranes. As demonstration projects, positively charged poly(diallyldimethylammonium chloride) (PDDA) and poly(4-vinylpyridine) (P4VP) in acid solution were chosen as polycation intercalators to modify the TaS2 2D channels. Under the DD mode, the TaS2 membrane exhibits a H+ dialysis coefficient (UH+) of 3.72 × 10−3 m h−1 and separation factor (S) of 9 towards the simulated acid pickle. In contrast, the UH+ and S value of the PDDA@TaS2 membrane improve to 12.7 × 10−3 m h−1 and 34.4 respectively. Those of the P4VP@TaS2 membrane increase to 12.5 × 10−3 m h−1 and 29.1 respectively. The reported acid recovery properties of PDDA@TaS2 and P4VP@TaS2 membranes exceed the commercial DF-120 acid recovery membranes. The experiment and simulation results reveal that the synergistical enhancements of UH+ and S originate from the incorporating polycations in PDDA@TaS2 and P4VP@TaS2 composite channels.