Tunable Density Research Articles

CsPbBr3 microarrays with tunable periodicity, optoelectronic and field emission properties using self-assembled polystyrene template and co-evaporation method.

The booming growth of all inorganic cesium lead halide perovskites in optoelectronic applications has prompted extensive research interest in the fabrication of ordered nanostructures or microarrays for enhanced device performances. However, the high cost and complexity of commercial lithographic approaches impede the facile fabrication of perovskite microarrays. Herein, CsPbBr3 microarrays with tunable periodicities have been fabricated using a self-assembled polystyrene nanosphere template and a co-evaporation method. The periodicity of CsPbBr3 microarrays is precisely manipulated by simply modifying the size of polystyrene nanospheres. These microarrays are beneficial for light harvesting, leading to better light absorption ability and prolonged photoinduced carrier lifetime. The longest average carrier lifetime of 58.3 ns is obtained for CsPbBr3 microarrays with a periodicity of 1.0 μm. More importantly, the periodic structures of CsPbBr3 microarrays result in a tunable density of emitter tips in field emission devices. Compared to compact CsPbBr3 films, a 68.2% decrease of the turn-on field is observed for CsPbBr3 microarrays when the periodicity is 150 nm. The higher density of emitter tips leads to larger local field enhancement, and hence the largest field enhancement factor of 3346.6. Finally, a good emission current stability for CsPbBr3 microarray-based field emission devices has been demonstrated.

Quantum variational optimization: The role of entanglement and problem hardness

Quantum variational optimization has been posed as an alternative to solve optimization problems faster and at a larger scale than what classical methods allow. In this paper we study systematically the role of entanglement, the structure of the variational quantum circuit, and the structure of the optimization problem, in the success and efficiency of these algorithms. For this purpose, our study focuses on the variational quantum eigensolver (VQE) algorithm, as applied to quadratic unconstrained binary optimization (QUBO) problems on random graphs with tunable density. Our numerical results indicate an advantage in adapting the distribution of entangling gates to the problem's topology, specially for problems defined on low-dimensional graphs. Furthermore, we find evidence that applying conditional value at risk type cost functions improves the optimization, increasing the probability of overlap with the optimal solutions. However, these techniques also improve the performance of Ans\"atze based on product states (no entanglement), suggesting that a new classical optimization method based on these could outperform existing NISQ architectures in certain regimes. Finally, our study also reveals a correlation between the hardness of a problem and the Hamming distance between the ground- and first-excited state, an idea that can be used to engineer benchmarks and understand the performance bottlenecks of optimization methods.

Enhanced thermal conductivity and adsorption rate of zeolite 13X adsorbent by compression-induced molding method for sorption thermal battery

Sorption thermal battery is an effective thermal energy storage technology for solar energy utilization and waste heat recovery. However, the low thermal conductivity and packing density of loose particle adsorbents are the common drawbacks for realizing high energy-density and power-density sorption thermal battery. Herein, we propose a compression-induced molding method for preparing high-performance modular adsorbents with high thermal conductivity and packing density by compacting loose particle adsorbents with tunable packing densities and thicknesses. The experimental results showed that the thermal conductivity and packing density of modular adsorbents can be enhanced by 3 times and 2 times, respectively, when compared to that of particle adsorbents. The water adsorption rate can be also improved by this method at an optimized compression pressure of 10 MPa and thickness of 2 mm. Furthermore, we constructed a sorption thermal battery by employing the modular adsorbents to realizing high-efficient thermal charging/discharging processes. The experimental results demonstrate the maximum volumetric power density is as high as 145 kW/m3 and the maximum volumetric energy density up to 75 kWh/m3, which are 1.61 times and 1.27 times higher than those of pristine particle adsorbent, respectively. Therefore, it is verified that the sorption thermal battery with modular adsorbent is more powerful and compact than using conventional particle adsorbent.

Solid-Liquid-Vapor Triphase Gel.

Gels are soft functional materials with solid networks and open pores filled with solvents (for wet gels) or air (for aerogels), displaying broad applications in tissue engineering, catalysis, environmental remediation, energy storage, etc. However, currently known gels feature only a single (either solid-liquid or solid-vapor) interface, largely limiting their application territories. Therefore, it is both fundamentally intriguing and practically significant to develop conceptually new gel materials that possess solid-liquid-vapor multiple interfaces. Herein, we demonstrate a unique solid-liquid-vapor triphase gel, named as aerohydrogel, by gelling of a poly(vinyl alcohol) aqueous solution with glutaraldehyde in the presence of superhydrophobic silica aerogel microparticles. Owing to its continuous solid, liquid, and vapor phases, the resultant aerohydrogel simultaneously displays solid-liquid, solid-vapor, and liquid-vapor interfaces, leading to excellent properties including tunable density (down to 0.43 g·cm-3), considerable hydrophobicity, and excellent elasticity (compressive ratio of up to 80%). As a proof-of-concept application, the aerohydrogel exhibits a higher evaporative cooling efficiency than its hydrogel counterpart and a better cooling capability than the commercial phase change cooling film, respectively, showing promising performance in cooling various devices. Moreover, the resulting aerohydrogel could be facilely tailored with specific (e.g., magnetic) properties for emerging applications such as solar steam generation. This work extends biphase gel (hydrogel or aerogel) to solid-liquid-vapor triphase gel, as well as provides a promising strategy for designing more aerohydrogels serving as soft functional materials for applications in various emerging fields.

Synergistic desulfurization over graphitic N and enzyme-like Fe-N sites of Fe-N-C

By coupling P450 enzyme-like single-atom Fe-N center and graphitic N into N-doped carbon matrix, we precisely fabricated a robust Fe-N-C adsorbent for efficient, stable and reversible desulfurization, notably exceeding the counterparts of commercial carbon black, iron porphyrin and its hybrid. Our results disclosed that the adsorptive desulfurization mainly occurred in the atomic Fe-N and graphitic N sites via the formation of Fe-S bond between Fe3d and S3p orbitals, and N/S electrostatic interaction, respectively. The excellent desulfurization capability (34.03 mg S/g) of Fe-N-C not only originated from its effective adsorption sites, large surface area and abundant porosity, but also relied on the moderate binding strength between adsorption sites and organosulfur, which could be well optimized by modulating the pyrrolic/pyridinic N and graphitization structure, enabling its outstanding recyclability via a feasible cleavage of formed Fe-S and N-S bonds without obvious loss of activity. Moreover, Fe-N-C still maintained the 91.20% and 84.56% desulfurization selectivity, even in the presence of the interfacing substrates such as thiophene and 4,6-dimethyldibenzothiophene, respectively. This work would provide a new opportunity to metal-N-C with tunable site configuration and density for various selective adsorption and separation.

Functionalized organic nanotubes with highly tunable crosslinking site density for mechanical enhancement and pH-controlled drug release of nanocomposite hydrogels

Functionalized organic nanotubes with highly tunable crosslinking site density for mechanical enhancement and pH-controlled drug release of nanocomposite hydrogels

On the foundation of thermal “Switching”: The culture substrate governs the phase transition mechanism of thermoresponsive brushes and their performance in cell sheet fabrication

Thermally “switchable” poly(glycidyl ether) (PGE) brushes constitute effective coatings for the temperature-triggered harvest of confluent cell sheets. Based on a simple “grafting-to” approach, such coatings can be tethered to various applied plastic culture substrate materials. Herein, we elucidate the self-assembly of PGE brushes with tunable grafting densities up to 0.12 and 0.22 chains nm−2 on polystyrene (PS) and tissue culture PS (TCPS), respectively. In terms of temperature-dependent wettability and protein adsorption, we found that brushes exhibit distinct grafting density-dependent properties which correlate with their cell sheet fabrication performance. In addition, temperature-ramped quartz-crystal microbalance with dissipation (QCM-D) measurements revealed marked substrate-specific PGE phase transitions which allowed us to deduce comprehensive switching mechanisms. Thus, we demonstrate that brushes tethered to hydrophilic TCPS (contact angle (CA) ∼ 60°) undergo a “cushioned” transition comprising a non-switchable, hydrated basal layer as well as a switchable top layer which regulates cell sheet detachment. In contrast, PGE brushes tethered to PS undergo a “grounded” transition which is substantially influenced by the dehydrating effect of the less hydrophilic PS substrate (CA ∼ 90°). These divergent phase transition mechanisms give rise to a broad scope in cell sheet fabrication performance, yielding staggered detachment times within a 30 min to 3 h range. Hence, we emphasize the importance of a detailed knowledge on the effect of applied culture substrates on the thermal switchability and phase transition characteristics of thermoresponsive brush coatings to accomplish an optimized design for functional cell culture dishes. Statement of significanceAs the first comparative study of its kind, we elucidate the substrate-dependent thermal switchability of thermoresponsive brush coatings and evaluate their grafting density-dependent phase transition mechanism and its effect on cell sheet fabrication performance.

Thermoresponsive Fluorescence Switches Based on Au@pNIPAM Nanoparticles.

Despite numerous studies emphasizing the plasmonic impact on fluorescence, the design of a dynamic system allowing on-demand fluorescence switching in a single nanostructure remains challenging. The reversibility of fluorescence switching and the versatility of the approach, in particular its compatibility with a wide range of nanoparticles and fluorophores, are among the main experimental difficulties. In this work, we achieve reversible fluorescence switching by coupling metal nanoparticles with fluorophores through stimuli-responsive organic linkers. As a proof of concept, we link gold nanoparticles with fluorescein through thermoresponsive poly(N-isopropylacrylamide) at a tunable grafting density and characterize their size and optical response by dynamic light scattering, absorption, and fluorescence spectroscopies. We show that the fluorescence emission of these hybrid nanostructures can be switched on-demand using the thermoresponsive properties of poly(N-isopropylacrylamide). The described system presents a general strategy for the design of nanointerfaces, exhibiting reversible fluorescence switching via external control of metal nanoparticle/fluorophore distance.

Tunable Band-Edge Potentials and Charge Storage in Colloidal Tin-Doped Indium Oxide (ITO) Nanocrystals.

Degenerately doped metal-oxide nanocrystals (NCs) show localized surface plasmon resonances (LSPRs) that are tunable via their tunable excess charge-carrier densities. Modulation of excess charge carriers has also been used to control magnetism in colloidal doped metal-oxide NCs. The addition of excess delocalized conduction-band (CB) electrons can be achieved through aliovalent doping or by postsynthetic techniques such as electrochemistry or photodoping. Here, we examine the influence of charge-compensating aliovalent dopants on the potentials of excess CB electrons in free-standing colloidal degenerately doped oxide NCs, both experimentally and through modeling. Taking Sn4+:In2O3 (ITO) NCs as a model system, we use spectroelectrochemical techniques to examine differences between aliovalent doping and photodoping. We demonstrate that whereas photodoping introduces excess CB electrons by raising the Fermi level relative to the CB edge, aliovalent impurity substitution introduces excess CB electrons by stabilizing the CB edge relative to an externally defined Fermi level. Significant differences are thus observed electrochemically between spectroscopically similar delocalized CB electrons compensated by aliovalent dopants and those compensated by surface cations (e.g., protons) during photodoping. Theoretical modeling illustrates the very different potentials that arise from charge compensation via aliovalent substitution and surface charge compensation. Spectroelectrochemical titrations allow the ITO NC band-edge stabilization as a function of Sn4+ doping to be quantified. Extremely large capacitances are observed in both In2O3 and ITO NCs, making these NCs attractive for reversible charge-storage applications.

Non-cell adhesive hexanoyl glycol chitosan hydrogels for stable and efficient formation of 3D cell spheroids with tunable size and density

Three-dimensional (3D) culture systems that provide a more physiologically similar environment than conventional two-dimensional (2D) cultures have been extensively developed. Previously we have provided a facile method for the formation of 3D spheroids using non-adhesive N-hexanoyl glycol chitosan (HGC) hydrogel-coated dishes, but with limitations such as low gel stability and weak mechanical properties. In this study, chemically crosslinked hydrogels were prepared by photocrosslinking of methacrylated HGCs (M-HGCs), and their spheroid-forming abilities were evaluated for long-term 3D cell cultures. The M-HGC hydrogels demonstrated not only enhanced gel stability, but also good spheroid-forming abilities. Furthermore, the M-HGC-coated dishes were effective in generating spheroids of larger size and higher cell density depending on the crosslinking density of the M-HGCs. These results indicate that our hydrogel-coated dish system could be widely applied as an effective technique to produce cell spheroids with customized sizes and densities that are essential for tissue engineering and drug screening.

Superhydrophobic leached carbon Black/Poly(vinyl) alcohol aerogel for selective removal of oils and organic compounds from water

The remediation of oil spills and treatment of oily wastewater remains challenging to cope with nowadays. This has caused a surge in demand on adsorbent materials with multi-functionalities to effectively separate oils and nonpolar solvents from water. A superhydrophobic composite aerogel prepared from industrial waste-derived leached carbon black waste (LCBW) and polyvinyl alcohol (PVA) was developed in this work via conventional freeze-casting followed by surface coating. The composite aerogel was ultralight and porous with porosity >85% and tunable density ranging between 0.015 and 0.065 g/cm3. It was found that the embedded LCBW in the PVA network is crucial to impart superhydrophobicity and superoleophilicity to the aerogel as it enhances the surface roughness. Wettability test showed that composite aerogel prepared from 0.5 wt% PVA at PVA/LCBW ratio of 1 exhibited the highest water contact angle (156.7 ± 2.9°). LCBW also improved the thermal stability of the composite aerogel. With its superior selectivity, PVA/LCBW aerogel was used as selective adsorbent for a variety of oils and organic solvents. The adsorption test showed that the composite aerogel exhibited an adsorption capacity up to 35 times its original weight and could be reused repeatedly and easily recovered through a simple drying method.

Hydrogen-Bonded and Halogen-Bonded: Orthogonal Interactions for the Chloride Anion of a Pyrazolium Salt.

In the hydrochloride of a pyrazolyl-substituted acetylacetone, the chloride anion is hydrogen-bonded to the protonated pyrazolyl moiety. Equimolar co-crystallization with tetrafluorodiiodobenzene (TFDIB) leads to a supramolecular aggregate in which TFDIB is situated on a crystallographic center of inversion. The iodine atom in the asymmetric unit acts as halogen bond donor, and the chloride acceptor approaches the -hole of this TFDIB iodine subtending an almost linear halogen bond, with Cl···I = Å and Cl···I–C = 179.32(6)°. This contact is roughly orthogonal to the N–H···Cl hydrogen bond. An analysis of the electron density according to Bader’s Quantum Theory of Atoms in Molecules confirms bond critical points (bcps) for both short contacts, with = 0.129 for the halogen and e for the hydrogen bond. Our halogen-bonded adduct represents the prototype for a future class of co-crystals with tunable electron density distribution about the -hole contact.

Additive-Manufactured Stochastic Polyimide Foams for Low Relative Permittivity, Lightweight Electronic Architectures.

Polyimides are widely utilized engineering polymers due to their excellent balance of mechanical, dielectric, and thermal properties. However, the manufacturing of polyimides into complex multifunctional designs can be hindered by dimensional shrinkage of the polymer upon imidization and post processing methods and inability to tailor electronic or mechanical properties. In this work, we developed methods to three-dimensional (3D) direct ink write polyimide closed-cell stochastic foams with tunable densities. These polyimide structures preserve the geometrical fidelity of 3D design with a linear shrinkage value of <10% and displayed microscale porosity ranging from 25 to 35%. This unique balance of morphology and direct-write compatibility was enabled by polymer phase inversion behavior without the need of conventional post-print cross-linking, imidization, or pore-inducing freeze processing. The manufacturability, thermal stability, and dielectric properties of the 3D polyimide stochastic foams reported here serve as enablers for the exploration of hierarchical, lightweight, high-temperature, high-power electronics.

Rapidly Adaptive All-covalent Nanoparticle Surface Engineering.

Emerging nanotechnologies demand the manipulation of nanoscale components with the same predictability and programmability as is taken for granted in molecular synthetic methodologies. Yet installing appropriately reactive chemical functionality on nanomaterial surfaces has previously entailed compromises in terms of reactivity scope, functionalization density, or both. Here, we introduce an idealized dynamic covalent nanoparticle building block for divergent and adaptive post‐synthesis modification of colloidal nanomaterials. Acetal‐protected monolayer‐stabilized gold nanoparticles are prepared via operationally simple protocols and are stable to long‐term storage. Tunable surface densities of reactive aldehyde functionalities are revealed on‐demand, leading to a wide range of adaptive surface engineering options from one nanoscale synthon. Analytically tractable with molecular precision, interfacial reaction kinetics and dynamic surface constitutions can be probed in situ at the ensemble level. High functionalization densities combined with rapid equilibration kinetics enable environmentally adaptive surface constitutions and rapid nanoparticle property switching in response to simple chemical effectors.

Hierarchical build-up of bio-based nanofibrous materials with tunable metal–organic framework biofunctionality

Multifunctional, light-weight, responsive materials show promise in a range of applications including soft robotics, therapeutic delivery, advanced diagnostics and charge storage. This paper presents a novel, scalable, efficient and sustainable approach for the preparation of cellulose nanofibril-based aerogels via a facile ice-templating, solvent exchange and air-drying procedure, which could replace existing inefficient drying processes. These ambient-dried aerogels (∼99% porosity) exhibit a high specific compressive modulus (26.8 ± 6.1 kPa m3 kg−1, approaching equivalence of carbon-nanotube-reinforced aerogels), wet stability and shape recovery (80–90%), favorable specific surface area (90 m2 g−1) and tunable densities (2–20 kg m−3). The aerogels provide an ideal nanofibrillar substrate for in-situ growth of metal–organic frameworks (MOFs), via co-assembly of MOF precursors with proteins in aqueous solutions. The resulting hybrid aerogels show a nine-fold increase in surface area (810 m2g−1), with preserved wet stability and additional protein biofunctionality. The hybrid aerogels facilitate a pH-controlled release of immobilized proteins, following a concomitant disassembly of the surface grown MOFs, demonstrating their use in controlled delivery systems. The colorimetric protein binding assay of the biofunctionalized hybrid aerogel also demonstrates the potential of the material as a novel 3D bioassay platform, which could potentially be an alternative to plate-based enzyme-linked immunosorbent assay.

Strong interlayer charge transfer due to exciton condensation in an electrically isolated GaAs quantum well bilayer

We introduce a design of electrically isolated “floating” bilayer GaAs quantum wells (QW), in which application of a large gating voltage controllably and highly reproducibly induces charges that remain trapped in the bilayer after removal of the gating voltage. At smaller gate voltages, the bilayer is fully electrically isolated from external electrodes by thick insulating barriers. This design permits full control of the total and differential densities of two coupled 2D electron systems. The floating bilayer design provides a unique approach for studying systems inaccessible by simple transport measurements. It also provides the ability to measure the charge transfer between the layers, even when the in-plane resistivities of the 2D systems diverge. We measure the capacitance and inter-layer tunneling spectra of the QW bilayer with independent control of the top and bottom layer electron densities. Our measurements display strongly enhanced inter-layer tunneling current at vT=1, a signature of exciton condensation of a strongly interlayer-correlated bilayer system. With fully tunable densities of individual layers, the floating bilayer QW system provides a versatile platform to access previously unavailable information on the quantum phases in electron bilayer systems.

Recent Advances in the Design of Novel β‐Titanium Alloys Using Integrated Theory, Computer Simulation, and Advanced Characterization

Metastable β‐titanium (β‐Ti) alloys, because of their combination of high specific strength, superior corrosion resistance, and excellent biocompatibility, have found increasingly widespread application in aerospace, automobile, biomedical, and chemical industries. Many different pathways, available for phase transformation and deformation between a high‐temperature β and a low‐temperature α phase, provide ample opportunities to engineer the desired microstructure through thermal mechanical processing for optimal properties targeting specific applications. Based on an integrated approach (theory, crystallography, multiscale modeling, and advanced characterization), recent studies have obtained fundamental insights in both designing strategies by exploring a variety of nonconventional solid‐state phase transformation and deformation pathways, including 1) pseudospinodal decomposition; 2) precursory ω‐phase‐assisted α precipitation with a wide range of tunable size scales and number densities; and 3) abnormal high‐index deformation twinning modes. Herein, the revolutionary new concepts for alloy development and deployment and the underlying physical mechanisms are reviewed in detail. Perspectives on the future research directions in the development of metastable β‐Ti alloys are also offered. The mechanisms and alloy design concepts as well as the advantage of using state‐of‐the‐art computational and characterization tools in a correlative manner for alloy design are applicable to a wide range of metallic materials beyond Ti alloys.

Non-Monotonic Evolution of Carrier Density and Mobility under Thermal Cycling Treatments in Dirac Semimetal Cd3As2 MicrobeltsSupported by the National Key Research and Development Program of China (Grant No. 2016YFA0401003), and the National Natural Science Foundation of China (Grant Nos. 11804340, 11774353, U19A2093, and U1732274), and the CAS/SAFEA International Partnership Program for Creative Research Teams of China.

Tunable carrier density plays a key role in the investigation of novel transport properties in three-dimensional topological semimetals. We demonstrate that the carrier density, as well as the mobility, of Dirac semimetal Cd3As2 nanoplates can be effectively tuned via in situ thermal treatment at 350 K for one hour, resulting in non-monotonic evolution by virtue of the thermal cycling treatments. The upward shift of Fermi level relative to the Dirac nodes blurs the surface Fermi-arc states, accompanied by an anomalous phase shift in the oscillations of bulk states, due to a change in the topology of the electrons. Meanwhile, the oscillation peaks of bulk longitudinal magnetoresistivity shift at high fields, due to their coupling to the oscillations of the surface Fermi-arc states. Our work provides a thermal control mechanism for the manipulation of quantum states in Dirac semimetal Cd3As2 at high temperatures, via their carrier density.

The Double-Faced Electrostatic Behavior of PNIPAm Microgels.

PNIPAm microgels synthesized via free radical polymerization (FRP) are often considered as neutral colloids in aqueous media, although it is well known, since the pioneering works of Pelton and coworkers, that the vanishing electrophoretic mobility characterizing swollen microgels largely increases above the lower critical solution temperature (LCST) of PNIPAm, at which microgels partially collapse. The presence of an electric charge has been attributed to the ionic initiators that are employed when FRP is performed in water and that stay anchored to microgel particles. Combining dynamic light scattering (DLS), electrophoresis, transmission electron microscopy (TEM) and atomic force microscopy (AFM) experiments, we show that collapsed ionic PNIPAm microgels undergo large mobility reversal and reentrant condensation when they are co-suspended with oppositely charged polyelectrolytes (PE) or nanoparticles (NP), while their stability remains unaffected by PE or NP addition at lower temperatures, where microgels are swollen and their charge density is low. Our results highlight a somehow double-faced electrostatic behavior of PNIPAm microgels due to their tunable charge density: they behave as quasi-neutral colloids at temperature below LCST, while they strongly interact with oppositely charged species when they are in their collapsed state. The very similar phenomenology encountered when microgels are surrounded by polylysine chains and silica nanoparticles points to the general character of this twofold behavior of PNIPAm-based colloids in water.

Electrostatic-modulated interfacial polymerization toward ultra-permselective nanofiltration membranes

SummaryInterfacial polymerization (IP) is a platform technology for ultrathin membranes. However, most efforts in regulating the IP process have been focused on short-range H-bond interaction, often leading to low-permselective membranes. Herein, we report an electrostatic-modulated interfacial polymerization (eIP) via supercharged phosphate-rich substrates toward ultra-permselective polyamide membranes. Phytate, a natural strongly charged organophosphate, confers high-density long-range electrostatic attraction to aqueous monomers and affords tunable charge density by flexible metal-organophosphate coordination. The electrostatic attraction spatially enriches amine monomers and temporally decelerates their diffusion into organic phase to be polymerized with acyl chloride monomers, triggering membrane sealing and inhibiting membrane growth, thus generating polyamide membranes with reduced thickness and enhanced cross-linking. The optimized nearly 10-nm-thick and highly cross-linked polyamide membrane displays superior water permeance and ionic selectivity. This eIP approach is applicable to the majority of conventional IP processes and can be extended to fabricate a variety of advanced membranes from polymers, supermolecules, and organic framework materials.