Biomimetic MXene membranes with negatively thermo-responsive switchable 2D nanochannels for graded molecular sieving

Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted significantly on account of low water permeability and poor dynamic tunability of 2D nanochannels under temperature stimulation.Here,we present a biomimetic negatively thermo-responsive MXene membrane by covalently grafting poly(N-isopropylacrylamide)(PNIPAm)onto MXene nanosheets.The uniformly grafted PNIPAm polymer chains can enlarge the interlayer spacings for increasing water permeability while also allowing more tunability of 2D nanochannels for enhancing the capability of gradually separating multiple molecules of different sizes.As expected,the constructed membrane exhibits ultrahigh water permeance of 95.6 L m^(-2) h^(-1) bar^(-1) at 25℃,which is eight-fold higher than the state-of-the-art negatively thermoresponsive 2D membranes.Moreover,the highly temperature-tunable 2D nanochannels enable the constructed membrane to perform excellent graded molecular sieving for dye-and antibiotic-based ternary mixtures.This strategy provides new perspectives in engineering smart 2D membrane and expands the scope of temperature-responsive membranes,showing promising applications in micro/nanofluidics and molecular separation.

Synthesis, Characterization and X-Ray Structure of a Ba(II)/Ag(I)/Cr(III)-Oxalate Salt with Water-Filled Nanochannels

A novel mixed barium(II)/silver(I)/chromium(III) oxalate salt, Ba0.5Ag2[Cr(C2O4)3]·5H2O (1), with open architecture has been synthesized in water and characterized by elemental analysis, vibrational and electronic spectra, and single crystal X-ray structure determination. Compound 1 crystallizes in a monoclinic space group C2/c, with unit cell parameters a = 18.179(3), b = 14.743(2), c = 12.278(2)Å, β = 113.821(3), V = 3010.34(90) Å3, Z = 8. The structure is characterized by a network of anionic [Cr(C2O4)3]3- units connected through the O atoms of the oxalates to Ba2+ and Ag+ sites, forming a three-dimensional coordination polymer with one-dimensional isolated nanochannels parallel to the c axis, and encapsulating hydrogen-bonded guest water molecules. The bulk structure is consolidated by O–H···O bridgings within the nanochannels and by coulombic interactions.

On flow characteristics of liquid-solid mixed-phase nanofluid inside nanochannels

The atomic behavior of liquid-solid mixed-phase nanofluid flows inside nanochannels is investigated by a molecular dynamics simulation （MDS）. The results of visual observation and statistic analysis show that when the nanoparticles reach near each other, the strong interatomic force will make them attach together. This aggrega- tion continues until all nanoparticles make a continuous cluster. The effect of altering the external force magnitude causes changes in the agglomeration rate and system enthalpy. The density and velocity profiles are shown for two systems, i.e., argon （Ar）-copper （Cu） nanofluid and simple Ar fluid between two Cu walls. The results show that using nanopar- ticles changes the base fluid particles ordering along the nanochannel and increases the velocity. Moreover, using nanoparticles in simple fluids can increase the slip length and push the near-wall fluid particles into the main flow in the middle of the nanochannel.

Impacts of multi-foulings on salinity gradient energy conversion process in negatively charged conical nanochannels

Membrane fouling inevitably occurs during nanofluidic reverse electrodialysis.Herein,the impact of multi-fouling on the energy conversion performance of negatively charged conical nanochannels under asymmetrical configurations is systematically investigated.The results reveal that in Configuration I,where a high-concentration solution is applied at the tip side,at small concentration ratios,multiple foulings reduce the electric power.In Configuration II,where a low-concentration solution is applied at the tip side,multiple foulings near the base side contribute to the electric power.Any fouling that formed near the lowconcentration entrance diminished the electric power and energy conversion efficiency.Multi-fouling lowered the electrical power consumption by 69.27%and 99.94%in Configurations I and II,respectively.In Configuration I,the electric power first increased with increasing fouling surface charge density,reached its maximum value,and thereafter decreased.In Configuration II,the electric power first decreased with increasing fouling surface charge density,reached its minimum value,and thereafter increased.Large negative or positive charge densities of fouling contribute to the electric power and energy conversion efficiency.

Outer-surface Covering of Nanochannels with Hydrogel for Highly Sensitive and Specific Cr(VI)Detection Through Analyte-caused Charge Change in Hydrogel

Nanochannels have made great progress and are a promising platform for detecting a series of targets.However,most nanochannels are modified on the inner wall,while ignoring the outer surface.Here,we modified the outer surface of nanochannels with hydrogel.Different from other reported outer-surface modification methods,we directly cover nanochannels with hydrogel to form heterogeneous membrane.The selected hydrogel hardly adsorbs other ions and shows specific adsorption for Cr(VI).The adsorption sites in hydrogel are homogeneous,and Cr(VI)adsorption onto hydrogel is endothermic and spontaneous.The charge in hydrogel changes after Cr(VI)adsorption,and the resulting current changes can be used for the detection of Cr(VI)with the detection limit of 10−11 mol/L.Our platform is expected to be used for Cr(VI)detection in living organisms,especially within cells.This work provides a new approach for outer-surface modification of nanochannels and offers a new choice for nanochannel detection platforms.

Nanopores/Nanochannels Based on Electrical and Optical Dual Signal Response for Application in Biological Detection

Cancers and chronic diseases have always been global health problems. The occurrence and development of such diseases are closely related to the abnormalities of proteins, nucleic acids, ions or small molecules in the body. Nowadays, nanopores/nanochannels have emerged as a powerful platform for detecting these biomolecules based on the electrical signal variation caused by biomolecules passing. However, detection relied on the electrical signal easily suffered from the clogging defects, low throughput, and strong background signals. Fortunately, the emergence of designing nanopores/nanochannels based on electrical and optical dual signal response has brought innovative impetus to biological detection, which can also identify the chemical compositions and conformations of the biomolecules. In this review, we summarize the reasonable preparation of nanopores/nanochannels with electrical and optical dual signal response and their application in biological detection. According to different biomolecules, we divide the targets into four types, including nucleic acids, small molecules, ions and proteins. In each section, the design of representative examples and the principle of dual signal generation are introduced and discussed. Finally, the prospects and challenges of nanopores/nanochannels based on electrical and optical dual signal response are also discussed.

Water’s motions in x–y and z directions of 2D nanochannels:Entirely different but tightly coupled

Two-dimensional(2D)material-based membrane separation has attracted increasing attention due to its promising performance compared with traditional membranes.However,in-depth understanding of water transportation behavior in such confined nanochannels is still lacking,which hinders the development of 2D nanosheets membranes.Herein,we investigated water confined in graphene or MoS_(2)nanochannels by molecular dynamics(MD)simulations and found water’s diffusivity always varied linearly with their mean square displacement along z direction(Δz^(2))when system variables(e.g.,water molecules’number,channel height,nonbonded interaction parameter,harmonic potential constraining water’s z-coordinate)changed.Such linear correlation applies to different water models and different force fields(FFs)of channel walls(e.g.,different Lennard–Jones parameters or even flexible FF),no matter whether water molecules form 3-,2-,or quasi-2-layer structure in the nanochannel.This indicates,though water molecules’motion along z direction(z-fluctuation,confined within 1 nm)and that in xy plane(xydiffusion)are entirely different,they are tightly coupled:Violent z-fluctuation would produce more transient void to facilitate xydiffusion,which is to the sharp contrary of bulk water,where motions in x,y,z directions are symmetric,but independent.Our work could help design high performance 2D nanochannels and discover more novel principles in nano-fluidics and membrane separation fields.

Construction and application of bioinspired nanochannels based on two-dimensional materials

With the development of nanotechnology and materials science,bioinspired nanochannels appeared by mimicking the intelligent functions of biological ion channels.They have attracted a great deal of at-tention in recent years due to their controllable structure and tunable chemical properties.Inspired by the layered microstructure of nacre,2D layered materials as excellent matrix material of nanochannel come into our field of vision.Bionic nanochannels based on 2D materials have the advantages of facile preparation,tunable channel size and length,easy expansion,and modification,etc.Therefore,the 2D layered nanofluid system based on bionic nanochannels from 2D layered materials has great potential in biomimetic microsensors,membrane separations,energy conversion,and so on.In this paper,we focus on the construction and application of bionic nanochannels based on 2D layer materials.First,a basic understanding of nanochannels based on 2D materials is briefly introduced,we also present the property of the 2D materials and construction strategies of bionic nanochannels.Subsequently,the application of these nanochannels in responsive channels and energy conversion is discussed.The unsolved challenges and prospects of 2D materials-based nanochannels are proposed in the end.

Tuning the primary selective nanochannels of MOF thin-film nanocomposite nanofiltration membranes for efficient removal of hydrophobic endocrine disrupting compounds

Metal organic framework(MOF)incorporated thin-film nanocomposite(TFN)membranes have the potential to enhance the removal of endocrine disrupting compounds(EDCs).In MOF-TFN membranes,water transport nanochannels include(i)pores of polyamide layer,(ii)pores in MOFs and(iii)channels around MOFs(polyamide-MOF interface).However,information on how to tune the nanochannels to enhance EDCs rejection is scarce,impeding the refinement of TFN membranes toward efficient removal of EDCs.In this study,by changing the polyamide properties,the water transport nanochannels could be confined primarily in pores of MOFs when the polyamide layer became dense.Interestingly,the improved rejection of EDCs was dependent on the water transport channels of the TFN membrane.At low monomer concentration(i.e.,loose polyamide structure),the hydrophilic nanochannels of MIL-101(Cr)in the polyamide layer could not dominate the membrane separation performance,and hence the extent of improvement in EDCs rejection was relatively low.In contrast,at high monomer concentration(i.e.,dense polyamide structure),the hydrophilic nanochannels of MIL-101(Cr)were responsible for the selective removal of hydrophobic EDCs,demonstrating that the manipulation of water transport nanochannels in the TFN membrane could successfully overcome the permeability and EDCs rejection trade-off.Our results highlight the potential of tuning primary selective nanochannels of MOF-TFN membranes for the efficient removal of EDCs.

Self-assembled lamellar nanochannels in polyoxometalate-polymer nanocomposites for proton conduction

The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials,as it can enhance ion conductivity by offering short ion-transport pathways.In this work,we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels,by the electrostatic self-assembly of a polyoxometalate H_(3)PW1_(2)O_(4)O(PW)and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone).PW can effectively regulate the self-assembling order of polymer moieties to form a large-ra nge lamellar structure,meanwhile,introducing protons into the nanoscale lamellar domains to build proton transport channels.Moreover,the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites.The lamellar nanocomposite exhibits a conductivity of 4.3×10^(-4)S/cm and a storage modulus of 1.1×10^(7)Pa at room temperature.This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials.

Biomimetic smart nanochannels for power harvesting

With the increasing requirements of reliable and environmentally friendly energy resources, porous materials for sustainable energy conversion technologies have attracted intensive interest in the past decades. As an important block of porous materials, biomimetic smart nanochannels （BSN） have been developed rapidly into an attractive field for their well-tunable geometry and chemistry. With inspiration from nature, many works have been reported to utilize BSN to harvest clean energy. In this review, we summarize recent progress in the BSN for power harvesting from four parts of brief introduction of BSN, biological prototypes for power harvesting, BSN-based energy conversion, and conclusion and outlook. Overall, by learning from nature, exploiting new avenues and improving the performance of BSN, a number of exciting developments in the near future may be anticipated.

Shape effect of nanochannels on water mobility

Confinement can induce unusual behaviors of water. Inspired by the fabrication of carbon nanotubes with noncircular cross sections, we performed molecular dynamics simulations to investigate the mobilities of water confined in carbon nanochannels with circular, square, and equilateral triangular cross sections over a variety of dimensions. We find that water exhibits disparate mobilities across different types of channels below 0.796 nm(2). Notably, compared with the other two channels, water in equilateral triangular channels displays the greatest mobilities. Moreover, at 0.425 nm(2), different ordered structures are found in the three channels, and water inside the square channel exhibits an extremely low mobility. It is also found that above 0.796 nm(2), the mobilities along the tube axis of water converge to that of the bulk. These phenomena are understood by analyzing the structure, dynamics, and hydrogen bonding of water. Our work explores the mobilities of water across noncircular carbon nanochannels, which may expand the prospect of noncircular nanochannels in scientific studies and practical applications, such as desalination and drug delivery.

Temperature Fluctuations in a Rectangular Nanochannel

We consider an incompressible fluid in a rectangular nanochannel. We solve numerically the three dimensional Fourier heat equation to get the steady solution for the temperature. Then we set and solve the Langevin equation for the temperature. We have developed equations in order to determine relaxation time of the temperature fluctuations, τT = 4.62 × 10-10s. We have performed a spectral analysis of the thermal fluctuations, with the result that temporal correlations are in the one-digit ps range, and the thermal noise excites the thermal modes in the two-digit GHz range. Also we observe long-range spatial correlation up to more than half the size of the cell, 600 nm;the wave number, q, is in the 106 m-1 range. We have also determined two thermal relaxation lengths in the z direction: l1 = 1.18 nm and l2 = 9.86 nm.

Anionic Nanochanneled Silver-Deficient Oxalatochromate(III) Complex with Hydroxonium as Counter Ion: Synthesis, Characterization and Crystal Structure

Reaction of Ba0.50[Ag2Cr(C2O4)3]·5H2O with Ag2SO4 in an aqueous solution of sulfuric acid (pH ≈ 3) yielded the silver(I)/chromium(III) oxalate salt H0.50[Ag2.50Cr(C2O4)3]·5H2O (1). Compound 1 can be best described as an anionic silver-deficient oxalatochromate(III) complex [Ag2.50Cr(C2O4)3]0.5- with nanochannels containing hydrogen-bonded water molecules and protons. Thermal analyses show significant weight losses corresponding to the elimination of water molecules of crystallization followed by the decomposition of the network.

Electrokinetic pumping system based on nanochannel membrane for liquid delivery

Nonmechanical pumping of liquids is of key importance for applications from the biomedical microfluidic chip to drug delivery systems. In this paper, a new electrokinetic pump （EOP） system with polycarbonate nanoehannel membrane sandwiched between two membrane holders was constructed. The pump was tested with water and phosphate buffer at 1-6 V applied voltage, the maximum pressure and flow rate are 0.32 MPa （3.2 atm） and 4.2 μL/min for phosphate buffer, respectively. This proof-of-concept pump shows its potential use for drugs or chemical agents delivery by the usage of different membrane materials.

Fluctuating hydrodynamic methods for fluid-structure interactions in confined channel geometries

We develop computational teractions subject to thermal fluctuations geometry. The methods take into account methods for the study of fluid-structure in- when confined within channels with slit-like the hydrodynamic coupling and diffusivity of microstructures when influenced by their proximity to no-slip walls. We develop stochas- tic numerical methods subject to no-slip boundary conditions using a staggered finite volume discretization. We introduce techniques for discretizing stochastic systems in a manner that ensures results consistent with statistical mechanics. We show how an exact fluctuation-dissipation condition can be used for this purpose to discretize the stochastic driving fields and combined with an exact projection method to enforce incompressibil- ity. We demonstrate our computational methods by investigating how the proximity of ellipsoidal colloids to the channel wall affects their active hydrodynamic responses and passive diffusivity. We also study for a large number of interacting particles collective drift-diffusion dynamics and associated correlation h/actions. We expect the introduced stochastic computational methods to be broadly applicable to applications in which con- finement effects play an important role in the dynamics of microstructures subject to hydrodynamic coupling and thermal fluctuations.

Controlling Diffusion by Varying Width of Layers in Nano Channel

Diffusive dynamics of fluid forming layers of high and low density regions in a nanochannel has been investigated.Diffusion coefficient in direction parallel and perpendicular to the confining wall has been found to show behaviour which is not observed in micro channel or bulk systems.The behaviour of diffusion is found to be controlled by the width of layers formed in nanochannel due to wall and particle interactions.This is an important result as width of layers and hence flow of fluid inside nano pores/tube can be controlled by an external source.

NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS

Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, self-assembly, selective domain crosslinking, and sometimes selective domain removal. Preparation of thin films withnanochannels was used to illustrate the strategy we took. In this particular case, a linear triblock copolymer polyisoprenc-block-poly(2-cinnamoylethyl methacrylate)-block-poly(t-butyl acrylate), PI-b-PCEMA-b-PtBA, was used. Films, 25 to50 μm thick, were prepared from casting on glass slides a toluene solution of PI-b-PCEMA-b-PtBA and PtBA homopolymer,hPtBA, where hPtBA is shorter than the PtBA block. At the hPtBA mass faction of 20% relative to the triblock or the totalPtBA (hPtBA and PtBA block) volume fraction of 0.44, hPtBA and PtBA formed a seemingly continuous phase in the matrixof PCEMA and Pl. Such a block segregation pattern was locked in by photocrosslinking the PCEMA domain. Nanochannelswere formed by extracting out hPtBA with solvent. Alternatively. larger channels were obtained from extracting out hPtBAand hydrolyzing the t-butyl groups of the PtBA block. Such membranes were not liquid permeable but had gas permeabilityconstants ～6 orders of magnitude higher than that of low-density polyethylene films.

Nanoconfinement-induced water molecules and hydrogen molecules transport behaviors in ball-in-ball structure photocatalysts to improve hydrogen evolution

The diffusion,adsorption/desorption behaviors of water molecules and hydrogen molecules are of great importance in heterogeneous photocatalytic hydrogen production.In the study of structure-property-performance relationships,nanoconfined space provides an ideal platform to promote mass diffusion and transfer due to their extraordinary properties that are different from the bulk systems.Herein,we designed and prepared a nanoconfined CdS@SiO_(2)-NH_(2) nanoreactor,whose shell is composed of amino-functionalized silica nanochannels,and encapsulates spherical CdS as a photocatalyst inside.Experimental and simulated results reveal that the amino-functionalized nanochannels promote water molecules’and hydrogen molecules’directional diffusion and transport.Water molecules are enriched in the nanocavity between the core and the shell,and promote the interfacial photocatalytic reaction.As a result,the maximized water enrichment and minimized hydrogen-occupied active sites enable photocatalyst with optimized mass transfer kinetics and localization electron distribution on the CdS surface,leading to superior hydrogen production performance with activity as high as 37.1 mmol·g^(-1)·h^(-1).