3D Confinement Research Articles

3D Confinement Strategy for Dendrite‐Free Sodium Metal Batteries

AbstractSodium metal batteries (SMBs) are attracting extensive attention for large‐scale energy storage due to the abundant reserves and low cost of sodium. However, the inevitable side reactions and uncontrollable dendrite growth in SMBs result in a continuous deterioration of the electrochemical performance and induce serious safety concerns, which severely restrict its practical application in the future. Among various improvement strategies, the 3D confinement strategy demonstrates great potential for stabilizing the Na anode owing to its optimized ion/electron transportation, lower deposition overpotential, and superior structural stability. Herein, first, the recent progress in SMBs which use the 3D confinement strategy to improve the electrochemical cycling stability of Na anode are outlined, and the potential regulation mechanism, including the transport/deposition behavior of Na+, interface engineering, and some advanced characterization techniques, are summarized. Furthermore, critical challenges and new perspectives are emphasized in detail. This review provides a deeper insight to enable construct ion of more comprehensive and effective Na metal anodes for advanced SMBs.

Polymersome formation by solvent annealing-induced structural reengineering under 3D soft confinement

A solvent annealing-induced structural reengineering approach is exploited to fabricate polymersomes from block copolymers that are hard to form vesicles through the traditional solution self-assembly route. More specifically, polystyrene-b-poly(4-vinyl pyridine) (PS-b-P4VP) particles with sphere-within-sphere structure (SS particles) are prepared by three-dimensional (3D) soft-confined assembly through emulsion-solvent evaporation, followed by 3D soft-confined solvent annealing upon the SS particles in aqueous dispersions for structural engineering. A water-miscible solvent (e.g., THF) is employed for annealing, which results in dramatic transitions of the assemblies, e.g., from SS particles to polymersomes. This approach works for PS-b-P4VP in a wide range of block ratios. Moreover, this method enables effective encapsulation/loading of cargoes such as fluorescent dyes and metal nanoparticles, which offers a new route to prepare polymersomes that could be applied for cargo release, diagnostic imaging, and nanoreactor, etc.

Three dimensional confined states in core-shell diameter modulated nanowires

Three-dimensional confined states in a GaP nanowire which partially covered by a uniform InP shell have been investigated in this paper. To this end, based on the effective mass approximation and by using the finite element method electronic energy states of the system were calculated. To attain physical insight on the numerical results, we have utilized the concept of one dimensional angular momentum dependent effective potential. Our results indicate a peculiar effect of increasing the 3D confinement of electrons in the shell which partially covered the nanowire by increasing the angular momentum. Surviving the effective potential declares that this effect arises as a consequence of contact with the semi-infinite nanowire parts of the system and, as a result, leads the bound states of higher angular momentum to lie in the energy continuum of the lower ones. On the other hand, application of external magnetic field reduces the number of 3D confined states in the core–shell region. Analysis of the reverse structure, i.e. InP nanowire which partially covered with GaP, indicates a significant increase in electronic confinement in the core–shell section with respect to the InP/GaP counterpart as a result of lower electronic effective mass of InP regarding to GaP.

Challenging the HSAB principle on molecular machines’ precursors

The Hard-and-Soft-Acids-and-Bases (HSAB) principle has been challenged for the first time on molecular machines’ precursors, while studying on calixarene-based rotaxane complexes containing tris(N-phenylureido)-calix[6]arene as wheel and a 4,4’-bipyridinium dication’s units as axle; The results clearly indicate the invariance of genuine vs. hard and soft acidic - bonding complex with the interlocked molecular system is present in terms of maintaining the chemical reactivity combined pattern of charge exchange, charge tunneling, opening and stabilizing reactivity tendency as provided within the orthogonal chemical space of chemical global indicators – in first (electronegativity and chemical hardness) and second (chemical power and electrophilicity) generations and of their principles, respectively. Moreover, we asses for the first time the molecular machine precursor system with the 3D total charge density isosuface confinement within two ends of 3D electrostatic potentials branches of the optimized interlocked rotaxane system. Further investigations are thus called for best generalizing the present findings.

Coherent crystal branches: the impact of tetragonal symmetry on the 2D confined polymer nanostructure.

The symmetry of polymer crystals greatly affects the optical, thermal con-ductivity and mechanical properties of the materials. Past studies have shown that the two-dimensional (2D) confined crystallization of polymer nanorods could produce anisotropic structures. However, few researchers have focused on understanding confined nanostructures from the perspective of crystal sym-metry. In this research, we demonstrate the molecular chain self-assembly of tetragonal crystals under cylindrical confinement. We specifically selected poly(4-methyl-1-pentene) (P4MP1) with a 41 or 72 helical conformation (usually crystallizing with a tetragonal lattice) as the model polymer. We found a coherent crystal branching of the tetragonal crystal in the P4MP1 nanorods. The unusual 45°- and 135°-{200} diffractions and the meridional 220 diffraction (from 45°-tilted crystals) have shown a uniform crystal branching between the a 1-axis crystals and the 45°-tilted crystals in the rod long axis, which originates from a structural defect associated with tetragonal symmetry. Surprisingly, this chain packing defect in the tetragonal cell can be controlled to develop along the rod long axis in 2D confinement.

Controlling Janus Nanodisc Topology through ABC Triblock Terpolymer/Homopolymer Blending in 3D Confinement

Janus particles have drawn considerable interest as colloidal surfactants, microswimmers, and building blocks for colloidal lattices. So far, research primarily focused on spherical Janus particles for which a number of fabrication methods are well established. Janus particles with geometric anisotropy offer shape-dependent properties in addition to surface anisotropy, but their synthesis is more challenging. Here, we report a variety of polymeric Janus nanoparticles synthesized from ABC triblock terpolymer microphases in microemulsion droplets. Evaporation-induced assembly of the ABC triblock terpolymers led to prolate microparticles with A/C lamellae stacked along the particle’s major axis. By admixing a B homopolymer during microphase separation, the morphology of the B microphase was gradually tuned in between the A/C lamellae. Cross-linking of the B microdomain created Janus nanodiscs, where the topology could be controlled to unconventional inner structures. We follow the morphology evolution and rationalize their stability with theoretical considerations in the strong segregation limit and dissipative particle dynamics simulations.

Multiscale Assembly of [AgS4 ] Tetrahedrons into Hierarchical Ag-S Networks for Robust Photonic Water.

There is an urgent need to assemble ultrasmall metal chalcogenides (with atomic precision) into functional materials with the required anisotropy and uniformity, on a micro- or even macroscale. Here, a delicate yet simple chemistry is developed to produce a silver-sulfur network microplate with a high monodispersity in size and morphology. Spanning from the atomic, molecular, to nanometer, to micrometer scale, the key structural evolution of the obtained microplates includes 2D confinement growth, edge-sharing growth mode, and thermodynamically driven layer-by-layer stacking, all of which are derived from the [AgS4 ] tetrahedron unit. The key to such a high hierarchical, complex, and accurate assembly is the dense deprotonated ligand layer on the surface of the microplates, forming an infinite surface with high negative charge density. This feature operates at an orderly distance to allow further hierarchical self-assembly on the microscale to generate columnar assemblies composed of microplate components, thereby endowing the feature of the 1D photonic reflector to water (i.e., photonic water). The reflective color of the resulting photonic water is highly dependent on the thickness of the building blocks (i.e., silver-sulfur microplates), and the coexistent order and fluidity help to form robust photonic water.

Physical aging of polystyrene blocks under three‐dimensional soft confinement in PS‐b‐poly(n‐butyl methacrylate) diblock copolymer: Two equilibrations on the way

AbstractPolystyrene‐block‐poly(n‐butyl methacrylate) (PS‐b‐PnBMA) was used to investigate three‐dimensional (3D) soft confinement effect on physical aging of the PS block therein. The soft confinement is constructed by phase‐separated PnBMA domains, as PnBMA is liquid on the aging temperatures of PS blocks due to its low glass transition temperature. In enthalpy recovery, aging response of PS blocks is represented by a low and broad heat capacity peak associated with an enhanced aging rate with respect to homo‐PS, when the aging temperature is relatively low. However, the aging response exhibits opposite characteristics at relatively high temperatures, compared with the results of homo‐PS. The phase‐separated morphology and thus the soft confinement on PS blocks was confirmed by atomic force microscope imaging using the Peak Force quantitative nanomechanical mapping (QNM) technique. Two local maximums of recovered enthalpy versus aging temperature indicate that two equilibration processes exist during aging of confined PS blocks, within a substantially shorter timescale to the bulk. The 3D soft confinement effect on aging of PS blocks is attributed to dual equilibration mechanisms: one dominates at higher aging temperatures, leading to a restrained aging rate, while the other plays a key role at lower aging temperatures, resulting in accelerated physical aging.

Volumetric live cell imaging with three-dimensional parallelized RESOLFT microscopy.

Elucidating the volumetric architecture of organelles and molecules inside cells requires microscopy methods with a sufficiently high spatial resolution in all three dimensions. Current methods are limited by insufficient resolving power along the optical axis, long recording times and photobleaching when applied to live cell imaging. Here, we present a 3D, parallelized, reversible, saturable/switchable optical fluorescence transition (3D pRESOLFT) microscope capable of delivering sub-80-nm 3D resolution in whole living cells. We achieved rapid (1-2 Hz) acquisition of large fields of view (~40 × 40 µm2) by highly parallelized image acquisition with an interference pattern that creates an array of 3D-confined and equally spaced intensity minima. This allowed us to reversibly turn switchable fluorescent proteins to dark states, leading to a targeted 3D confinement of fluorescence. We visualized the 3D organization and dynamics of organelles in living cells and volumetric structural alterations of synapses during plasticity in cultured hippocampal neurons.

Optical quantification of intracellular mass density and cell mechanics in 3D mechanical confinement.

Biophysical properties of cells such as intracellular mass density and cell mechanics are known to be involved in a wide range of homeostatic functions and pathological alterations. An optical readout that can be used to quantify such properties is the refractive index (RI) distribution. It has been recently reported that the nucleus, initially presumed to be the organelle with the highest dry mass density (ρ) within the cell, has in fact a lower RI and ρ than its surrounding cytoplasm. These studies have either been conducted in suspended cells, or cells adhered on 2D substrates, neither of which reflects the situation in vivo where cells are surrounded by the extracellular matrix (ECM). To better approximate the 3D situation, we encapsulated cells in 3D covalently-crosslinked alginate hydrogels with varying stiffness, and imaged the 3D RI distribution of cells, using a combined optical diffraction tomography (ODT)-epifluorescence microscope. Unexpectedly, the nuclei of cells in 3D displayed a higher ρ than the cytoplasm, in contrast to 2D cultures. Using a Brillouin-epifluorescence microscope we subsequently showed that in addition to higher ρ, the nuclei also had a higher longitudinal modulus (M) and viscosity (η) compared to the cytoplasm. Furthermore, increasing the stiffness of the hydrogel resulted in higher M for both the nuclei and cytoplasm of cells in stiff 3D alginate compared to cells in compliant 3D alginate. The ability to quantify intracellular biophysical properties with non-invasive techniques will improve our understanding of biological processes such as dormancy, apoptosis, cell growth or stem cell differentiation.

Solution processable in situ passivated silicon nanowires.

The 1D confinement of silicon in the form of a nanowire revives its newness with the emergence of new optical and electronic properties. However, the development of a production process for silicon nanowires (SiNWs) having a high quality crystalline core and exhibiting good stability in solution with effective outer-shell defect passivation is still a challenge. In this work, SiNWs are prepared from a silicon wafer using solution processing steps, and importantly outer-shell-defect passivation is achieved by in situ grafting of organic molecules based on thin films. Defect passivation and the high quality of the SiNWs are confirmed with thin films on glass and flexible plastic substrates. A dramatic enhancement in both the fluorescence lifetime and infrared photoluminescence is observed. The in situ organic passivation of SiNWs has potential application in all low-dimensional silicon devices including infrared detectors, solar cells and lithium-ion battery anodes.

Synthesis of Narrow SnTe Nanowires Using Alloy Nanoparticles

Topological crystalline insulator tin telluride (SnTe) provides a rich playground to examine interactions of correlated electronic states, such as ferroelectricity, topological surface states, and superconductivity. Making SnTe into nanowires further induces novel electronic states due to one-dimensional (1D) confinement effects. Thus, for transport measurements, SnTe nanowires must be made narrow in their diameters to ensure the 1D confinement and phase coherence of the topological surface electrons. This study reports a facile growth method to produce narrow SnTe nanowires with a high yield using alloy nanoparticles as growth catalysts. The average diameter of the SnTe nanowires grown using the alloy nanoparticles is 85 nm, nearly a factor of three reduction from the previous average diameter of 240 nm using gold nanoparticles as growth catalysts. Transport measurements reveal the effect of the nanowire diameter on the residual resistance ratio and magnetoresistance. Particularly, the ferroelectric transition temperature for SnTe is observed to change systematically with the nanowire diameter. In situ cryogenic cooling of narrow SnTe nanowires in a transmission electron microscope directly reveals the cubic to rhombohedral structural transition, which is associated with the ferroelectric transition. Thus, these narrow SnTe nanowires represent a model system to study electronic states arising from the 1D confinement, such as 1D topological superconductivity as well as a potential multi-band superconductivity.

Frustrated Microparticle Morphologies of a Semicrystalline Triblock Terpolymer in 3D Soft Confinement.

Self-assembly of block copolymers (BCPs) in three-dimensional (3D) confinement of emulsion droplets has emerged as a versatile route for the formation of functional micro- and nanoparticles. While the self-assembly of amorphous coil-coil BCPs is fairly well documented, less is known about the behavior of crystalline-coil BCPs. Here, we demonstrate that confining a linear ABC triblock terpolymer with a crystallizable middle block in oil-in-water (O/W) emulsions results in a range of microparticles with frustrated inner structure originating from the conflict between crystallization and curved interfaces. Polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA, S32E36M3293) in toluene droplets was subjected to different preparation protocols. If evaporation was performed well above the bulk crystallization temperature of the PE block (Tevap > Tc), S32E36M3293 first microphase-separated into microparticles with lamella morphology followed by crystallization into a variety of frustrated morphologies (e.g., bud-like, double staircase, spherocone). By evaporating at significantly lower temperatures that allow the PE block to crystallize from solution (Tevap < Tc), S32E36M3293 underwent crystallization-driven self-assembly into patchy crystalline-core micelles, followed by confinement assembly into lenticular microparticles with compartmentalized hexagonal cylinder lattices. The frequency of these frustrated morphologies depends on polymer concentration and the evaporation protocol. These results provide a preliminary understanding of the morphological behavior of semicrystalline block copolymers in 3D soft confinement and may provide alternative routes to structure multicompartment microparticles from a broader range of polymer properties.

Conformation and dynamics of ring polymers under symmetric thin film confinement.

Understanding the structure and dynamics of polymers under confinement has been of widespread interest, and one class of polymers that have received comparatively little attention under confinement is that of ring polymers. The properties of non-concatenated ring polymers can also be important in biological fields because ring polymers have been proven to be a good model to study DNA organization in the cell nucleus. From our previous study, linear polymers in a cylindrically confined polymer melt were found to segregate from each other as a result of the strong correlation hole effect that is enhanced by the confining surfaces. By comparison, our subsequent study of linear polymers in confined thin films at similar levels of confinements found only the onset of segregation. In this study, we use molecular dynamics simulation to investigate the chain conformations and dynamics of ring polymers under planar (1D) confinement as a function of film thickness. Our results show that conformations of ring polymers are similar to the linear polymers under planar confinement, except that ring polymers are less compressed in the direction normal to the walls. While we find that the correlation hole effect is enhanced under confinement, it is not as pronounced as the linear polymers under 2D confinement. Finally, we show that chain dynamics far above Tg are primarily affected by the friction from walls based on the monomeric friction coefficient we get from the Rouse mode analysis.

3D Finite Element Pseudodynamic Analysis of Deficient RC Rectangular Columns Confined with Fiber Reinforced Polymers under Axial Compression.

This paper utilizes the advanced potential of pseudodynamic three-dimensional finite-element modeling to study the axial mechanical behavior of square and rectangular reinforced concrete columns, confined with fiber reinforced polymer (FRP) jackets and continuous composite ropes in seismic applications. The rigorous and versatile Riedel-Hiermaier-Thoma (RHT) material model for concrete is suitably calibrated/modified to reproduce the variable behavior of characteristic retrofitted columns with deficient internal steel reinforcement detailing, suffering nonuniform local concrete cracking and crushing or bulging and bar buckling. Similarly, the 3D FRP jacket or rope confinement models may account for damage distribution, local fracture initiation and different interfacial bonding conditions. The satisfactory accuracy of the reproduced experimental stress-strain envelope behavior enables the analytical investigation of several critical design parameters that are difficult to measure reliably during experiments. Additional parametric analyses are conducted to assess the effects of steel quality. The significant variation of the field of developed strains on the FRP jacket at the ultimate and of the developed strains and deformations on steel cages among different columns are thoroughly investigated. This advanced analytical insight may be directly utilized to address missing critical parameters and allow for more reliable FRP retrofit design of seismic resistant reinforced concrete (RC) columns. Further, it allows for arbitrary 3D seismic analysis of columns (loading, unloading, cyclic or loading rate effects or preloading) or addresses predamages.

Densified MoS2/Ti3C2 films with balanced porosity for ultrahigh volumetric capacity sodium-ion battery

Developing high volumetric energy density sodium-ion batteries (SIBs) is indispensable for catering to the miniaturization and flexibility of various consumer electronics. Herein, we have reported the flexible and compact MoS2/Ti3C2 hybrid films with balanced porosity, where the few-layered MoS2 nanosheets are parallelly intercalated into the Ti3C2 interlayer space in virtue of strong electrostatic effect and difference in their sizes. The hybrid films have been stabilized by the two-dimensional (2D) confinement effect and the Ti-S-Mo bonds with a high density of ~2.9 g cm−3. Furthermore, the dual 2D compounds intrinsically possess satisfied ions conductivity, and meanwhile give rapid electrons transfer after assembling such superstructure. When directly used as SIB anode, the MoS2/Ti3C2 hybrid films deliver an exceptional volumetric specific capacity of 1510 mAh cm−3 at 0.28 mA cm−2 and 650 mAh cm−3 at 14 mA cm−2. The specific capacity remains unchanged after 300 cycles at 1.4 mA cm−2. More significantly, the areal specific capacity shows a linear relationship with the increase of film thickness from 9.6 to 43.1 μm without sacrificing the volumetric capacity.

Photocatalytically active block copolymer hybrid micelles from double hydrophilic block copolymers

Herein, we demonstrate that double hydrophilic block copolymers can be used for the preparation of photocatalytically active organic/inorganic hybrid micelles. This is realized by immobilization of CdS nanoparticles for photocatalytic water splitting within well-defined poly(2-iso-propyl-2-oxazoline)-block-poly(2-acrylamido glycolic acid) (PiPrOx-b-PAGA) block copolymers. The prepared PiPrOx-b-PAGA/CdS hybrid nanostructures were characterized regarding morphology, structure, and optical properties by UV/Vis and photoluminescence (PL) spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS), and X-ray photoelectron spectroscopy (XPS). Our results confirm spherical inorganic-organic micelles containing ultra-small CdS nanoparticles with photoluminescent character within the core. Afterwards, these hybrid nanostructures were used for photocatalytic H2 production in the presence of triethanol amine (TEOA) as sacrificial reagent in water under visible-light illumination (λ ≥ 470 nm), revealing 18-fold increased activity compared to bare CdS nanoparticles. The enhanced photocatalytic activity can be attributed to several factors, such as 3D confinement within micellar nanostructures, the presence of ultra-small CdS nanoparticles, or an improved stability of CdS nanoparticles within the micellar core. Overall, we demonstrate that double hydrophilic BCP can be an interesting platform for the formation of photocatalytically active micellar nanostructures, leading to materials with potential relevance for photocatalysis.

Exciton Dynamics in Droplet Epitaxial Quantum Dots Grown on (311)A-Oriented Substrates.

Droplet epitaxy allows the efficient fabrication of a plethora of 3D, III–V-based nanostructures on different crystalline orientations. Quantum dots grown on a (311)A-oriented surface are obtained with record surface density, with or without a wetting layer. These are appealing features for quantum dot lasing, thanks to the large density of quantum emitters and a truly 3D lateral confinement. However, the intimate photophysics of this class of nanostructures has not yet been investigated. Here, we address the main optical and electronic properties of s-shell excitons in individual quantum dots grown on (311)A substrates with photoluminescence spectroscopy experiments. We show the presence of neutral exciton and biexciton as well as positive and negative charged excitons. We investigate the origins of spectral broadening, identifying them in spectral diffusion at low temperature and phonon interaction at higher temperature, the presence of fine interactions between electron and hole spin, and a relevant heavy-hole/light-hole mixing. We interpret the level filling with a simple Poissonian model reproducing the power excitation dependence of the s-shell excitons. These results are relevant for the further improvement of this class of quantum emitters and their exploitation as single-photon sources for low-density samples as well as for efficient lasers for high-density samples.

Anomalous Long-Range Attraction in Colloidal Binary Mixtures at Fluid–Fluid Interfaces

The properties of binary colloidal systems have gained the interest of researchers because they have much richer structures than their one-component counterpart. Continuing efforts are being made on the theoretical side on binary colloidal systems, while many issues remained unsolved for the lack of solid experimental supports, especially for study in the field of two-dimensional (2D) binary colloids system. Oil–water interfaces can serve as a good stringent 2D confinement for colloidal particles and can avoid anomalous problems caused by the quasi-two-dimensional environment in previous experimental reports. In this work, we conduct experimental research of binary colloids system in an oil–water interface to revisit theoretical predication. We measure an ultra-long-range attraction and discuss the possible mechanism of this attraction by comparing the experimental result with existing model and theory. This study could contribute more understanding of the binary colloidal system in both experimental aspects and theoretical aspects.

3D Microwell Platforms for Control of Single Cell 3D Geometry and Intracellular Organization.

Cell structure and migration is impacted by the mechanical properties and geometry of the cell adhesive environment. Most studies to date investigating the effects of 3D environments on cells have not controlled geometry at the single-cell level, making it difficult to understand the influence of 3D environmental cues on single cells. Here, we developed microwell platforms to investigate the effects of 2D vs. 3D geometries on single-cell F-actin and nuclear organization. We used microfabrication techniques to fabricate three polyacrylamide platforms: 3D microwells with a 3D adhesive environment (3D/3D), 3D microwells with 2D adhesive areas at the bottom only (3D/2D), and flat 2D gels with 2D patterned adhesive areas (2D/2D). We measured geometric swelling and Young's modulus of the platforms. We then cultured C2C12 myoblasts on each platform and evaluated the effects of the engineered microenvironments on F-actin structure and nuclear shape. We tuned the mechanical characteristics of the microfabricated platforms by manipulating the gel formulation. Crosslinker ratio strongly influenced geometric swelling whereas total polymer content primarily affected Young's modulus. When comparing cells in these platforms, we found significant effects on F-actin and nuclear structures. Our analysis showed that a 3D/3D environment was necessary to increase actin and nuclear height. A 3D/2D environment was sufficient to increase actin alignment and nuclear aspect ratio compared to a 2D/2D environment. Using our novel polyacrylamide platforms, we were able to decouple the effects of 3D confinement and adhesive environment, finding that both influenced actin and nuclear structure.