Interlink between Abnormal Water Imbibition in Hydrophilic and Rapid Flow in Hydrophobic Nanochannels.

Nanoscale extension and refinement of the Lucas-Washburn model is presented with a detailed analysis of recent experimental data and extensive molecular dynamics simulations to investigate rapid water flow and water imbibition within nanocapillaries. Through a comparative analysis of capillary rise in hydrophilic nanochannels, an unexpected reversal of the anticipated trend, with an abnormal peak, of imbibition length below the size of 3 nm was discovered in hydrophilic nanochannels, surprisingly sharing the same physical origin as the well-known peak observed in flow rate within hydrophobic nanochannels. The extended imbibition model is applicable across diverse spatiotemporal scales and validated against simulation results and existing experimental data for both hydrophilic and hydrophobic nanochannels.

Advances in Two-Dimensional Ion-Selective Membranes: Bridging Nanoscale Insights to Industrial-Scale Salinity Gradient Energy Harvesting.

Salinity gradient energy, often referred to as the Gibbs free energy difference between saltwater and freshwater, is recognized as "blue energy" due to its inherent cleanliness, renewability, and continuous availability. Reverse electrodialysis (RED), relying on ion-selective membranes, stands as one of the most prevalent and promising methods for harnessing salinity gradient energy to generate electricity. Nevertheless, conventional RED membranes face challenges such as insufficient ion selectivity and transport rates and the difficulty of achieving the minimum commercial energy density threshold of 5 W/m2. In contrast, two-dimensional nanostructured materials, featuring nanoscale channels and abundant functional groups, offer a breakthrough by facilitating rapid ion transport and heightened selectivity. This comprehensive review delves into the mechanisms of osmotic power generation within a single nanopore and nanochannel, exploring optimal nanopore dimensions and nanochannel lengths. We subsequently examine the current landscape of power generation using two-dimensional nanostructured materials in laboratory-scale settings across various test areas. Furthermore, we address the notable decline in power density observed as test areas expand and propose essential criteria for the industrialization of two-dimensional ion-selective membranes. The review concludes with a forward-looking perspective, outlining future research directions, including scalable membrane fabrication, enhanced environmental adaptability, and integration into multiple industries. This review aims to bridge the gap between previous laboratory-scale investigations of two-dimensional ion-selective membranes in salinity gradient energy conversion and their potential large-scale industrial applications.

Tailoring Metal-Organic Frameworks and Derived Materials for High-Performance Zinc-Air and Alkaline Batteries.

Developing multifunctional materials from earth-abundant elements is urgently needed to satisfy the demand for sustainable energy. Herein, we demonstrate a facile approach for the preparation of a metal-organic framework (MOF)-derived Fe2O3/C, composited with N-doped reduced graphene oxide (MO-rGO). MO-rGO exhibits excellent bifunctional electrocatalytic activities toward the oxygen evolution reaction (ηj=10 = 273 mV) and the oxygen reduction reaction (half-wave potential = 0.77 V vs reversible hydrogen electrode) with a low ΔEOER-ORR of 0.88 V in alkaline solutions. A Zn-air battery based on the MO-rGO cathode displays a high specific energy of over 903 W h kgZn-1 (∼290 mW h cm-2), an excellent power density of 148 mW cm-2, and an open-circuit voltage of 1.430 V, outperforming the benchmark Pt/C + RuO2 catalyst. We also hydrothermally synthesized a Ni-MOF that was partially transformed into a Ni-Co-layered double hydroxide (MOF-LDH). A MO-rGO||MOF-LDH alkaline battery exhibits a specific energy of 42.6 W h kgtotal mass-1 (106.5 µW h cm-2) and an outstanding specific power of 9.8 kW kgtotal mass-1 (24.5 mW cm-2). This work demonstrates the potential of MOFs and MOF-derived compounds for designing innovative multifunctional materials for catalysis, electrochemical energy storage, and beyond.

Cation-controlled permeation of charged polymers through nanocapillaries.

Molecular dynamics simulations are used to study the effects of different cations on the permeation of charged polymers through flat capillaries with heights below 2 nm. Interestingly, we found that, despite being monovalent, Li^{+}, Na^{+}, and K^{+} cations have different effects on polymer permeation, which consequently affects their transmission speed throughout those capillaries. We attribute this phenomenon to the interplay of the cations' hydration free energies and the hydrodynamic drag in front of the polymer when it enters the capillary. Different alkali cations exhibit different surface versus bulk preferences in small clusters of water under the influence of an external electric field. This paper presents a tool to control the speed of charged polymers in confined spaces using cations.

Beyond steric selectivity of ions using ångström-scale capillaries.

Ion-selective channels play a key role in physiological processes and are used in many technologies. Although biological channels can efficiently separate same-charge ions with similar hydration shells, it remains a challenge to mimic such exquisite selectivity using artificial solid-state channels. Although there are several nanoporous membranes that show high selectivity with respect to certain ions, the underlying mechanisms are based on the hydrated ion size and/or charge. There is a need to rationalize the design of artificial channels to make them capable of selecting between similar-sized same-charge ions, which, in turn, requires an understanding of why and how such selectivity can occur. Here we study ångström-scale artificial channels made by van der Waals assembly, which are comparable in size with typical ions and carry little residual charge on the channel walls. This allows us to exclude the first-order effects of steric- and Coulomb-based exclusion. We show that the studied two-dimensional ångström-scale capillaries can distinguish between same-charge ions with similar hydrated diameters. The selectivity is attributed to different positions occupied by ions within the layered structure of nanoconfined water, which depend on the ion-core size and differ for anions and cations. The revealed mechanism points at the possibilities of ion separation beyond simple steric sieving.

Strain engineering of hyperbolic plasmons in monolayer carbon phosphide: a first-principles study.

Natural and tunable in-plane hyperbolic plasmons have so far been elusive, and hence few two-dimensional hyperbolic materials have been theoretically and experimentally discovered. Here, comprehensive first-principles calculations were conducted to study the electronic and plasmonic properties of biaxially strained monolayer carbon phosphide (ß-CP). We found that (i) a compressed ß-CP hosts strong anisotropic Dirac-shaped fermions with robust modulated Fermi velocity, (ii) for biaxial strain of -3% an unprecedented ultra-wide hyperbolic window is extended continuously from terahertz (9 THz) to mid-visible (blue light, 693 THz), (iii) the tunable optical Van Hove singularity as the origin of hyperbolic plasmons in deformed ß-CP is disclosed, (iv) an elliptic to hyperbolic transition in the σ-near-zero regime is demonstrated in terahertz frequencies (9 THz), (v) the propagation angle of the concave wavefront can be actively tuned using biaxial strains, and (vi) hyperbolic dispersion reorientation from one principal axis to another orthogonal one under compressive strains larger than 8% is observed. This study sheds new light on the unique properties of hyperbolic two-dimensional (2D) materials having exotic optoelectronic characteristics which are promising candidates for anisotropic light control with ultimate dexterity in the flat optics.

Phase-Dependent Energy Storage Performance of the NixSey Polymorphs for Supercapacitor-Battery Hybrid Devices.

Transition-metal chalcogenides have emerged as a promising class of materials for energy storage applications due to their earth abundance, high theoretical capacity, and high electrical conductivity. Herein, we introduce a facile and one-pot electrodeposition method to prepare high-performance nickel selenide NixSey (0.5 ≤ x/y ≤ 1.5) nanostructures (specific capacity = 180.3 mA h g-1 at 1 A g-1). The as-synthesized nickel selenide (NS) nanostructure is however converted to other polymorphs of nickel selenide including orthorhombic NiSe2, trigonal Ni3Se2, hexagonal NiSe, and orthorhombic Ni6Se5 over cycling. Interestingly, NiSe2 and Ni3Se2 polymorphs that display a more metallic character and superior energy storage performance are the predominant phases after a few hundred cycles. We fabricated a hybrid device using activated carbon (AC) as a supercapacitor-type negative electrode and NS as a high-rate battery-type positive electrode (AC||NS). This hybrid device provides a high specific energy of 71 W h kg-1, an excellent specific power of up to 31 400 W kg-1, and exceptional cycling stability (80% retention of the initial capacity after 20 000 cycles). The higher energy storage performance of the device is a result of the development of high-performance NiSe2 and Ni3Se2 polymorphs. Moreover, the reduction of the critical dimension of the NS particles to the nanoscale partially induces an extrinsic pseudocapacitive behavior that improves the rate capability and durability of the device. We also explored the origin of the superior energy storage performance of the NS polymorphs using density functional theory calculations in terms of the computed density of states around the Fermi level, electrical conductivity, and quantum capacitance that follows the trend NiSe2 > Ni3Se2 > NiSe > Ni6Se5. The present study thus provides an appealing approach for tailoring the phase composition of NS as an alternative to the commonly used templated synthesis methods.

Indentation of graphene nano-bubbles.

Molecular dynamics simulations are used to investigate the effect of an AFM tip when indenting graphene nano bubbles filled by a noble gas (i.e. He, Ne and Ar) up to the breaking point. The failure points resemble those of viral shells as described by the Föppl-von Kármán (FvK) dimensionless number defined in the context of elasticity theory of thin shells. At room temperature, He gas inside the bubbles is found to be in the liquid state while Ne and Ar atoms are in the solid state although the pressure inside the nano bubble is below the melting pressure of the bulk. The trapped gases are under higher hydrostatic pressure at low temperatures than at room temperature.

Comment on 'Two-dimensional carbon nitride C6N nanosheet with egg-comb-like structure and electronic properties of a semimetal [2021,Nanotechnology32, 215702]'.

Recently, Bafekryet al(2021Nanotechnology32215702) predicted a novel two-dimensional carbon nitride with an egg-comb-like structure and a C6N stoichiometry. Their density functional theory results reveal the thermal stability of this structure at 300 K. They also examined the thermoelectric properties of this monolayer up to 500 K. By adopting the same methodology employed in the original work by Bafekryet al(2021Nanotechnology32215702), we show that this monolayer is thermally unstable and cannot be employed for practical applications. Aforementioned theoretical work also includes inaccuracies in the evaluation of thermoelectric properties of the C6N monolayer, as they did not consider the contribution of the lattice thermal conductivity.

Trilayer Metal-Organic Frameworks as Multifunctional Electrocatalysts for Energy Conversion and Storage Applications.

The need for enhanced energy storage and improved catalysts has led researchers to explore advanced functional materials for sustainable energy production and storage. Herein, we demonstrate a reductive electrosynthesis approach to prepare a layer-by-layer (LbL) assembled trimetallic Fe-Co-Ni metal-organic framework (MOF) in which the metal cations within each layer or at the interface of the two layers are linked to one another by bridging 2-amino-1,4-benzenedicarboxylic acid linkers. Tailoring catalytically active sites in an LbL fashion affords a highly porous material that exhibits excellent trifunctional electrocatalytic activities toward the hydrogen evolution reaction (ηj=10 = 116 mV), oxygen evolution reaction (ηj=10 = 254 mV), as well as oxygen reduction reaction (half-wave potential = 0.75 V vs reference hydrogen electrode) in alkaline solutions. The dispersion-corrected density functional theory calculations suggest that the prominent catalytic activity of the LbL MOF toward the HER, OER, and ORR is due to the initial negative adsorption energy of water on the metal nodes and the elongated O-H bond length of the H2O molecule. The Fe-Co-Ni MOF-based Zn-air battery exhibits a remarkable energy storage performance and excellent cycling stability of over 700 cycles that outperform the commercial noble metal benchmarks. When assembled in an asymmetric device configuration, the activated carbon||Fe-Co-Ni MOF supercapacitor provides a superb specific energy and a power of up to 56.2 W h kg-1 and 42.2 kW kg-1, respectively. This work offers not only a novel approach to prepare an LbL assembled multimetallic MOF but also provides a benchmark for a multifunctional electrocatalyst for water splitting and Zn-air batteries.

The interaction between atomic-scale pores and particles.

Using first-principles calculations for angstrom-sized pores (3-10 Å), we investigate pore-particle interaction. The translocation energy barrier (TEB) plays important role for the angstrom-scale pores created in 2D-materials such as graphene which is calculated for the translocation of rare gases (He, Ne, Ar, Xe), diatomic molecules (H2and N2), CO2, and CH4. The critical incident angle (the premeance beyond that is zero) was found to be 40°, which is different from classical model's prediction of 19-37°. The calculated TEB (Δ) and the surface diffusion energy barrier (Δ') for the particles with small kinetic diameter (He, Ne and H2), show that the direct flow is the dominant permeation mechanism (Δ ≈ 0 and Δ' > 30 meV). For the other particles with larger kinetic diameters (Ar, Kr, N2, CH4and CO2), we found that both surface diffusion and direct flow mechanisms are possible, i.e. Δ and Δ' ≠ 0. This work provides important insights into the gas permeation theory and into the design and development of gas separation and filtration devices.

Breakdown of Universal Scaling for Nanometer-Sized Bubbles in Graphene.

We report the formation of nanobubbles on graphene with a radius of the order of 1 nm, using ultralow energy implantation of noble gas ions (He, Ne, Ar) into graphene grown on a Pt(111) surface. We show that the universal scaling of the aspect ratio, which has previously been established for larger bubbles, breaks down when the bubble radius approaches 1 nm, resulting in much larger aspect ratios. Moreover, we observe that the bubble stability and aspect ratio depend on the substrate onto which the graphene is grown (bubbles are stable for Pt but not for Cu) and trapped element. We interpret these dependencies in terms of the atomic compressibility of the noble gas as well as of the adhesion energies between graphene, the substrate, and trapped atoms.

Abnormal in-plane permittivity and ferroelectricity of confined water: From sub-nanometer channels to bulk.

Dielectric properties of nano-confined water are important in several areas of science, i.e., it is relevant in the dielectric double layer that exists in practically all heterogeneous fluid-based systems. Molecular dynamics simulations are used to predict the in-plane dielectric properties of confined water in planar channels of width ranging from sub-nanometer to bulk. Because of suppressed rotational degrees of freedom near the confining walls, the dipole of the water molecules tends to be aligned parallel to the walls, which results in a strongly enhanced in-plane dielectric constant (ε∥) reaching values of about 120 for channels with height 8 Å < h < 10 Å. With the increase in the width of the channel, we predict that ε∥ decreases nonlinearly and reaches the bulk value for h > 70 Å. A stratified continuum model is proposed that reproduces the h > 10 Å dependence of ε∥. For sub-nanometer height channels, abnormal behavior of ε∥ is found with two orders of magnitude reduction of ε∥ around h ∼ 7.5 Å, which is attributed to the formation of a particular ice phase that exhibits long-time (∼µs) stable ferroelectricity. This is of particular importance for the understanding of the influence of confined water on the functioning of biological systems.

Abnormal Dielectric Constant of Nanoconfined Water between Graphene Layers in the Presence of Salt.

Ultra-low dielectric constant of nanoconfined water between two flat slabs is a subject of recent experimental and theoretical research. The impact of dissolution of sodium chloride (NaCl) with various concentrations on the dielectric properties of nanoconfined water between graphene layers are investigated using molecular dynamics simulations. We found that, with increasing salt concentration, (i) the out-of-plane dielectric constant increases and (ii) the in-plane dielectric constant decreases non-linearly. Surprisingly, for channels with heights 6.8Å < h < 8 Å, we found an abnormal increase in the in-plane dielectric constant versus salt concentration, which can be linked to the formation of 2D-ice-like structure. This study sheds light on the variation of dielectric properties of nanoconfined water between graphene layers in the presence of salt, which is of importance in ion transport and electrochemical energy storage.

Hydration effects and negative dielectric constant of nano-confined water between cation intercalated MXenes.

Using electrochemical methods a profound enhancement of the capacitance of electric double layer capacitor electrodes was reported when water molecules are strongly confined into the two-dimensional slits of titanium carbide MXene nanosheets [A. Sugahara et al., Nat. Commun., 2019, 10, 850]. We study the effects of hydration on the dielectric properties of nanoconfined water and supercapacitance properties of the cation intercalated MXene. A model for the electric double layer capacitor is constructed where water molecules are strongly confined in two-dimensional slits of MXene. We report an abnormal dielectric constant and polarization of nano-confined water between MXene layers. We found that by decreasing the ionic radius of the intercalated cations and in a critical hydration shell radius the capacitance of the system increases significantly (≃200 F g-1) which can be interpreted as a negative permittivity. This study builds a bridge between the fundamental understanding of the dielectric properties of nanoconfined water and the capability of using MXene films for supercapacitor technology, and in doing so provides a solid theoretical support for recent experiments.

Gas flow through atomic-scale apertures.

Gas flows are often analyzed with the theoretical descriptions formulated over a century ago and constantly challenged by the emerging architectures of narrow channels, slits, and apertures. Here, we report atomic-scale defects in two-dimensional (2D) materials as apertures for gas flows at the ultimate quasi-0D atomic limit. We establish that pristine monolayer tungsten disulfide (WS2) membranes act as atomically thin barriers to gas transport. Atomic vacancies from missing tungsten (W) sites are made in freestanding (WS2) monolayers by focused ion beam irradiation and characterized using aberration-corrected transmission electron microscopy. WS2 monolayers with atomic apertures are mechanically sturdy and showed fast helium flow. We propose a simple yet robust method for confirming the formation of atomic apertures over large areas using gas flows, an essential step for pursuing their prospective applications in various domains including molecular separation, single quantum emitters, sensing and monitoring of gases at ultralow concentrations.

Self-Limiting Growth of Two-Dimensional Palladium between Graphene Oxide Layers.

The ability of different materials to display self-limiting growth has recently attracted an enormous amount of attention because of the importance of nanoscale materials in applications for catalysis, energy conversion, (opto)electronics, and so forth. Here, we show that the electrochemical deposition of palladium (Pd) between graphene oxide (GO) sheets result in the self-limiting growth of 5-nm-thick Pd nanosheets. The self-limiting growth is found to be a consequence of the strong interaction of Pd with the confining GO sheets, which results in the bulk growth of Pd being energetically unfavorable for larger thicknesses. Furthermore, we have successfully carried out liquid exfoliation of the resulting Pd-GO laminates to isolate Pd nanosheets and have demonstrated their high efficiency in continuous flow catalysis and electrocatalysis.

Unconventional two-dimensional vibrations of a decorated carbon nanotube under electric field: linking actuation to advanced sensing ability.

We show that a carbon nanotube decorated with different types of charged metallic nanoparticles exhibits unusual two-dimensional vibrations when actuated by applied electric field. Such vibrations and diverse possible trajectories are not only fundamentally important but also have minimum two characteristic frequencies that can be directly linked back to the properties of the constituents in the considered nanoresonator. Namely, those frequencies and the maximal deflection during vibrations are very distinctively dependent on the geometry of the nanotube, the shape, element, mass and charge of the nanoparticle, and are vastly tunable by the applied electric field, revealing the unique sensing ability of devices made of molecular filaments and metallic nanoparticles.

Electro- and opto-mutable properties of MgO nanoclusters adsorbed on mono- and double-layer graphene.

Inspired by recent experiments, the trapping of molecules in 2D materials has gained increasing attention due to the unique ability of the molecules to modulate the electronic and optical properties of 2D materials, which calls for fundamental understanding and predictive design strategies. Herein, we focus on mono- and double-layer graphene encapsulating various MgO clusters and explore their diverse electronic and optical properties using a number of high-level first-principles calculations. By correlating the stability of adsorption, geometry, charge transfer, band structures, optical absorption spectrum, and the van der Waals pressure, our results decode various synergies in electro- and opto-mutable properties of MgO/graphene systems. We found that 2D-MgO flakes on graphene layers exhibit surface polarization effects - in contrast to their isolated neutral flakes - and show a significant charge transfer from graphene to n-doped flakes, breaking the symmetry of graphene layers. We obtained a van der Waals pressure of ∼0.7 (0.9) GPa on bilayer graphene encapsulating MgO nanoclusters, which matches extremely well with experiment. While there is one quantum emission in the visible light region for a single MgO flake, a wide range of visible light is accessible for MgO on mono- and double-layer graphene. Overall, these findings provide new physical insights and design strategies to modulate 2D materials with several applications in optoelectronics while significantly broadening the spectrum of strategies for fabricating new hybrid 2D heterostructures by encapsulating external molecules.