Structural Engineering of Carbon Host Derived from Organic Pigment toward Physicochemically Confinement and Efficient Conversion of Polysulfide for Lithium-Sulfur Batteries.

Lithium-Sulfur Batteries (LSBs) have attracted significant attention as promising next-generation energy storage systems. However, the commercial viability of LSBs have been hindered due to lithium polysulfides (LiPSs) shuttle effect, resulting in poor cycling stability and low sulfur utilization. To address this issue, herein, the study prepares a sulfur host consisting of micro/mesopore-enriched activated carbonaceous materials with ultrahigh surface area using organic pigment via facile one-step activation. By varying the proportion of chemical agent, the pore size and volume of the activated carbonaceous materials are manipulated and their capabilities on the mitigation of LiPSs shuttle effect are investigated. Through the electrochemical measurements and spectroscopic analysis, it is verified that structural engineering of carbon hosts plays a pivotal role in effective physical confinement of LiPSs, leading to the mitigation of LiPSs shuttle effect and sulfur utilization. Additionally, nitrogen and oxygen-containing functional groups originated from PR show electrocatalytic activation sites, facilitating LiPSs conversion kinetics. The approach can reveal that rational design of carbon microstructures can improve trapping and suppression of LiPSs and shuttle effect, enhancing electrochemical performance of LSBs.

Liquid-metal-based three-dimensional microelectrode arrays integrated with implantable ultrathin retinal prosthesis for vision restoration.

Electronic retinal prostheses for stimulating retinal neurons are promising for vision restoration. However, the rigid electrodes of conventional retinal implants can inflict damage on the soft retina tissue. They also have limited selectivity due to their poor proximity to target cells in the degenerative retina. Here we present a soft artificial retina (thickness, 10 µm) where flexible ultrathin photosensitive transistors are integrated with three-dimensional stimulation electrodes of eutectic gallium-indium alloy. Platinum nanoclusters locally coated only on the tip of these three-dimensional liquid-metal electrodes show advantages in reducing the impedance of the stimulation electrodes. These microelectrodes can enhance the proximity to the target retinal ganglion cells and provide effective charge injections (72.84 mC cm-2) to elicit neural responses in the retina. Their low Young's modulus (234 kPa), owing to their liquid form, can minimize damage to the retina. Furthermore, we used an unsupervised machine learning approach to effectively identify the evoked spikes to grade neural activities within the retinal ganglion cells. Results from in vivo experiments on a retinal degeneration mouse model reveal that the spatiotemporal distribution of neural responses on their retina can be mapped under selective localized illumination areas of light, suggesting the restoration of their vision.

Ion trap and release dynamics enables nonintrusive tactile augmentation in monolithic sensory neuron.

An iontronic-based artificial tactile nerve is a promising technology for emulating the tactile recognition and learning of human skin with low power consumption. However, its weak tactile memory and complex integration structure remain challenging. We present an ion trap and release dynamics (iTRD)-driven, neuro-inspired monolithic artificial tactile neuron (NeuroMAT) that can achieve tactile perception and memory consolidation in a single device. Through the tactile-driven release of ions initially trapped within iTRD-iongel, NeuroMAT only generates nonintrusive synaptic memory signals when mechanical stress is applied under voltage stimulation. The induced tactile memory is augmented by auxiliary voltage pulses independent of tactile sensing signals. We integrate NeuroMAT with an anthropomorphic robotic hand system to imitate memory-based human motion; the robust tactile memory of NeuroMAT enables the hand to consistently perform reliable gripping motion.

Investigation of Effect of Platinum Nanoparticle Shape on Oxygen Transport in PEMFC Catalyst Layer Using Molecular Dynamics Simulation.

For the widespread adoption of polymer electrolyte membrane fuel cells, it is compelling to investigate the influence of the Pt nanoparticle shapes on the electrocatalytic activity. In this study, a catalyst layer was modeled by incorporating four types of Pt nanoparticles: tetrahedron, cube, octahedron, and truncated octahedron, to investigate the relationship between the shapes of the nanoparticles and their impact on the oxygen transport properties using molecular dynamics simulations. The results of our study reveal that the free volume, which has a substantial impact on the oxygen transport properties, exhibited higher values in the sequence of the tetrahedron, cube, octahedron, and truncated octahedron model. The difference in free volume following the formation of less dense ionomers was also related to the surface adsorption of Pt nanoparticles. Consequently, this led to an improved facilitation of oxygen transport. To clarify the dependence of the oxygen transport on the shape of the Pt nanoparticles in detail, we analyzed the structural properties of different Pt shapes by dividing the Pt nanoparticle regions into corners, edges, and facets. Examination of the structural properties showed that the structure of the ionomer depended not only on the shape of the Pt nanoparticles but also on the number of corners and edges in the upper and side regions of the Pt nanoparticles.

Pyrolyzed Organic Pigment as Efficient Surface-Dominated Alkali-Ion Storage Anodes.

Carbonaceous materials have attracted as prospective anodes for rechargeable alkali-ion batteries. In this study, C.I. Pigment Violet 19 (PV19) was utilized as a carbon precursor to fabricate the anodes for alkali-ion batteries. During thermal treatment, the generation of gases from the PV19 precursor triggered a structural rearrangement into nitrogen- and oxygen-containing porous microstructures. The anode materials fabricated from pyrolyzed PV19 at 600 °C (PV19-600) showed outstanding rate performance and stable cycling behavior (554 mAh g-1 over 900 cycles at a current density of 1.0 A g-1) in lithium-ion batteries (LIBs). In addition, PV19-600 anodes exhibited reasonable rate capability and good cycling behavior (200 mAh g-1 after 200 cycles at 0.1 A g-1) in sodium-ion batteries (SIBs). To define the enhanced electrochemical performance of PV19-600 anodes, spectroscopic analyses were employed to reveal the storage mechanism and kinetics of the alkali ions in pyrolyzed PV19 anodes. A surface-dominant process in nitrogen- and oxygen-containing porous structures was found to promote the alkali-ion storage ability of the battery.

Addressing diffusion behavior and impact in an epoxy-amine cure system using molecular dynamics simulations.

To deepen understanding of diffusion-controlled crosslinking, molecular dynamics (MD) simulations are carried out by taking the diffusion image of 3,3'-diamino diphenyl sulfone (3,3'-DDS) and polyethersulfone (PES) with epoxy resin varying temperatures from 393.15 to 473.15 K over crosslinking conversion of 0-85%. The diffusion of PES and 3,3'-DDS into the bulk increased with increasing the temperature as a result of enhanced mobility of the molecules when the difference between the glass-transition temperature (Tg) and the curing temperature. Beyond the onset points of the converged crosslinking conversion ratio of 3,3'-DDS and PES, their diffusion properties are obviously restricted with crosslinking conversion ratio. At low crosslinking conversion ratios (> 10%), the diffusion coefficients of triglycidyl p-aminophenol (TGAP) were 1.1 times higher than those of diglycidyl ether of bisphenol F (DGEBF) because of the lower molecular weight of TGAP. On the other hand, the diffusion coefficients of TGAP decreased when the crosslinking ratio was up to ~ 60% because, compared with DGEBF, it had more functional groups available to react with the curing agent. At higher crosslinking ratios, the diffusion coefficients of both resins converged to zero as a result of their highly crosslinked structures.

Predicting the Properties of High-Performance Epoxy Resin by Machine Learning Using Molecular Dynamics Simulations.

Epoxy resin is an of the most widely used adhesives for various applications owing to its outstanding properties. The performance of epoxy systems varies significantly depending on the composition of the base resin and curing agent. However, there are limitations in exploring numerous formulations of epoxy resins to optimize adhesive properties because of the expense and time-consuming nature of the trial-and-error process. Herein, molecular dynamics (MD) simulations and machine learning (ML) methods were used to overcome these challenges and predict the adhesive properties of epoxy resin. Datasets for diverse epoxy adhesive formulations were constructed by considering the degree of crosslinking, density, free volume, cohesive energy density, modulus, and glass transition temperature. A linear correlation analysis demonstrated that the content of the curing agents, especially dicyandiamide (DICY), had the greatest correlation with the cohesive energy density. Moreover, the content of tetraglycidyl methylene dianiline (TGMDA) had the highest correlation with the modulus, and the content of diglycidyl ether of bisphenol A (DGEBA) had the highest correlation with the glass transition temperature. An optimized artificial neural network (ANN) model was constructed using test sets divided from MD datasets through error and linear regression analyses. The root mean square error (RMSE) and correlation coefficient (R2) showed the potential of each model in predicting epoxy properties, with high linear correlations (0.835-0.986). This technique can be extended for optimizing the composition of other epoxy resin systems.

Near-Infrared Absorption Properties of Neutral Bis(1,2-dithiolene) Platinum(II) Complexes Using Density Functional Theory.

Small metal complexes are highly interesting for bioimaging because of their excellent near-infrared (NIR) absorption properties. In this study, neutral complexes of platinum(II) connected to two monoreduced 1,3-diisopropylimidazoline-2,4,5-trithione ligands-namely, [Pt(iPr2timdt)2]-were investigated. Theoretical studies using the density functional theory (DFT) and GW-BSE approximation verified the effects of the geometry of the isopropyl moieties on the NIR absorption spectra. The calculated absorption spectra showed excellent correspondence with the experimental results. The geometry of the isopropyl groups considerably influenced the electronic structures of the metal complexes, which altered the absorption profiles of the respective geometries, as demonstrated in this research.

Multiscale simulation approach to investigate the binder distribution in catalyst layers of high-temperature polymer electrolyte membrane fuel cells.

A multiscale approach involving both density functional theory (DFT) and molecular dynamics (MD) simulations was used to deduce an appropriate binder for Pt/C in the catalyst layers of high-temperature polymer electrolyte membrane fuel cells. The DFT calculations showed that the sulfonic acid (SO3-) group has higher adsorption energy than the other functional groups of the binders, as indicated by its normalized adsorption area on Pt (- 0.1078 eV/Å2) and carbon (- 0.0608 eV/Å2) surfaces. Consequently, MD simulations were performed with Nafion binders as well as polytetrafluoroethylene (PTFE) binders at binder contents ranging from 14.2 to 25.0 wt% on a Pt/C model with H3PO4 at room temperature (298.15 K) and operating temperature (433.15 K). The pair correlation function analysis showed that the intensity of phosphorus atoms in phosphoric acid around Pt ([Formula: see text]) increased with increasing temperature because of the greater mobility and miscibility of H3PO4 at 433.15 K than at 298.15 K. The coordination numbers (CNs) of Pt-P(H3PO4) gradually decreased with increasing ratio of the Nafion binders until the Nafion binder ratio reached 50%, indicating that the adsorption of H3PO4 onto the Pt surface decreased because of the high adsorption energy of SO3- groups with Pt. However, the CNs of Pt-P(H3PO4) gradually increased when the Nafion binder ratio was greater than 50% because excess Nafion binder agglomerated with itself via its SO3- groups. Surface coverage analysis showed that the carbon surface coverage by H3PO4 decreased as the overall binder content was increased to 20.0 wt% at both 298.15 and 433.15 K. The Pt surface coverage by H3PO4 at 433.15 K reached its lowest value when the PTFE and Nafion binders were present in equal ratios and at an overall binder content of 25.0 wt%. At the Pt (lower part) surface covered by H3PO4 at 433.15 K, an overall binder content of at least 20.0 wt% and equal proportions of PTFE and Nafion binder are needed to minimize H3PO4 contact with the Pt.

Single-Step Fabrication of Polymeric Composite Membrane via Centrifugal Colloidal Casting for Fuel Cell Applications.

Recent interest in polymer electrolyte membranes (PEMs) for fuel cell systems has spurred the development of infiltration technology by which to insert ionomers into mechanically robust reinforcement structures by solution casting in order to produce a cost effective and highly efficient electrolyte. However, the results of the fabrication process often continue to present challenges related to the structural complexity and self-assembly dynamics between the hydrophobic and hydrophilic parts of the constituents which in turn, necessitates additional processing steps and increases production costs. Here, a single-step process is reported for highly compact polymeric composite membranes (PCMs), fabricated using a centrifugal colloidal casting (C3) method. Combined structural analyses as well as coarse-grained molecular dynamics simulations are employed to determine the micro-/macroscopic structural characteristics of the fabricated PCMs. These findings indicate that the C3 method is capable of forming highly dense ionomer matrix-reinforcement composites consisting of microphase-separated ionomer structures with tailored crystallinity and ionic cluster sizes. An outcome that is very unlikely with the single-step coating steps in conventional methods. These structural attributes ensure PCMs with better proton conductivity, greater strain stability, and lower gas crossover properties compared to commercial pristine membranes, expanding their possible range of applicability to PEMs.

Organic Dye-Derived N, S Co-Doped Porous Carbon Hosts for Effective Lithium Polysulfide Confinement in Lithium-Sulfur Batteries.

Lithium-sulfur batteries are considered as attractive candidates for next-generation energy storage systems originating from their high theoretical capacity and energy density. However, the severe shuttling of behavior caused by the dissolution of lithium polysulfide intermediates during cycling remains a challenge for practical applications. Herein, porous carbon materials co-doped with nitrogen and sulfur atoms were prepared through a facile hydrothermal reaction of graphene oxide and methylene blue to obtain a suitable host structure for regulating the lithium polysulfide shuttling behavior. Experimental results demonstrated that the abundant heteroatom-containing moieties in the carbon frameworks not only generated favorable active sites for capturing lithium polysulfide but also enhanced redox reaction kinetics of lithium polysulfide intermediates. Consequently, the corresponding sulfur composite electrodes exhibited excellent rate performance and cycling stability along with high Columbic efficiency. This work highlights the approach for the preparation of nitrogen and sulfur co-doped carbon materials derived from organic dye compounds for high performance energy storage systems.

Permeability of a Zinc-Methacrylate-Based Self-Polishing Copolymer for Use in Antifouling Coating Materials by Molecular Dynamics Simulations.

Molecular dynamics simulations were used to investigate the solubility and permeability of H2O in a self-polishing copolymer (SPC) with two zinc methacrylate (ZMA) contents (Z2: 2 mol% ZMA; Z16: 16 mol% ZMA) and ethyl acrylate, methyl methacrylate, 2-methoxyethyl acrylate, and butyl acrylate as antifouling agents. Water was found to be more soluble in hydrated Z16 than Z2 because ZMA interacts strongly with H2O. In contrast, the diffusion coefficient of H2O in Z16 is lower than that of Z2 because H2O molecules are more constrained in the former due to strong ZMA/H2O interactions. Z16 was found to be significantly more permeable than Z2 over time. The SPC hydrated region in Z2 tends to expand toward the SPC region, while the analogous region in Z16 swelled toward both the SPC and H2O regions to leach SPC owing to the higher permeation of H2O into the SPC. These results reveal that H2O permeability can be controlled by adjusting the ZMA content, which provides insight into antifouling performance.

Optical and Electronic Properties of Organic NIR-II Fluorophores by Time-Dependent Density Functional Theory and Many-Body Perturbation Theory: GW-BSE Approaches.

Organic-molecule fluorophores with emission wavelengths in the second near-infrared window (NIR-II, 1000-1700 nm) have attracted substantial attention in the life sciences and in biomedical applications because of their excellent resolution and sensitivity. However, adequate theoretical levels to provide efficient and accurate estimations of the optical and electronic properties of organic NIR-II fluorophores are lacking. The standard approach for these calculations has been time-dependent density functional theory (TDDFT). However, the size and large excitonic energies of these compounds pose challenges with respect to computational cost and time. In this study, we used the GW approximation combined with the Bethe-Salpeter equation (GW-BSE) implemented in many-body perturbation theory approaches based on density functional theory. This method was used to perform calculations of the excited states of two NIR molecular fluorophores (BTC980 and BTC1070), going beyond TDDFT. In this study, the optical absorption spectra and frontier molecular orbitals of these compounds were compared using TDDFT and GW-BSE calculations. The GW-BSE estimates showed excellent agreement with previously reported experimental results.

Visco-Poroelastic Electrochemiluminescence Skin with Piezo-Ionic Effect.

Following early research efforts devoted to achieving excellent sensitivity of electronic skins, recent design schemes for these devices have focused on strategies for transduction of spatially resolved sensing data into straightforward user-adaptive visual signals. Here, a material platform capable of transducing mechanical stimuli into visual readout is presented. The material layer comprises a mixture of an ionic transition metal complex luminophore and an ionic liquid (capable of producing electrochemiluminescence (ECL)) within a thermoplastic polyurethane matrix. The proposed material platform shows visco-poroelastic response to mechanical stress, which induces a change in the distribution of the ionic luminophore in the film, which is referred to as the piezo-ionic effect. This piezo-ionic effect is exploited to develop a simple device containing the composite layer sandwiched between two electrodes, which is termed "ECL skin". Emission from the ECL skin is examined, which increases with the applied normal/tensile stress. Additionally, locally applied stress to the ECL skin is spatially resolved and visualized without the use of spatially distributed arrays of pressure sensors. The simple fabrication and unique operation of the demonstrated ECL skin are expected to provide new insights into the design of materials for human-machine interactive electronic skins.

Effects of Calcination Temperature on the Phase Composition, Photocatalytic Degradation, and Virucidal Activities of TiO2 Nanoparticles.

The application of TiO2 nanoparticles in the photocatalytic treatment of chemically or biologically contaminated water is an attractive, albeit unoptimized, method for environmental remediation. Here, TiO2 nanoparticles with mixed brookite/rutile phases were synthesized and calcined at 300-1100 °C to investigate trends in photocatalytic performance. The crystallinity, crystallite size, and particle size of the calcined materials increased with calcination temperature, while the specific surface area declined significantly. The TiO2 phase composition varied: at 300 °C, mixed brookite/rutile phases were observed, whereas a brookite-to-anatase phase transformation occurred above 500 °C, reaching complete conversion at 700 °C. Above 700 °C, the anatase-to-rutile phase transformation began, with pure rutile attained at 1100 °C. The optical band gaps of the calcined TiO2 nanoparticles decreased with rising calcination temperature. The mixed anatase/rutile phase TiO2 nanoparticles calcined at 700 °C performed best in the photocatalytic degradation of methylene blue owing to the synergistic effect of the crystallinity and phase structure. The photocatalytic virus inactivation test demonstrated excellent performance against the MS2 bacteriophage, murine norovirus, and influenza virus. Therefore, the mixed anatase/rutile phase TiO2 nanoparticles calcined at 700 °C may be considered as potential candidates for environmental applications, such as water purification and virus inactivation.

Prediction of Lap Shear Strength and Impact Peel Strength of Epoxy Adhesive by Machine Learning Approach.

In this study, an artificial neural network (ANN), which is a machine learning (ML) method, is used to predict the adhesion strength of structural epoxy adhesives. The data sets were obtained by testing the lap shear strength at room temperature and the impact peel strength at -40 °C for specimens of various epoxy adhesive formulations. The linear correlation analysis showed that the content of the catalyst, flexibilizer, and the curing agent in the epoxy formulation exhibited the highest correlation with the lap shear strength. Using the analyzed data sets, we constructed an ANN model and optimized it with the selection set and training set divided from the data sets. The obtained root mean square error (RMSE) and R2 values confirmed that each model was a suitable predictive model. The change of the lap shear strength and impact peel strength was predicted according to the change in the content of components shown to have a high linear correlation with the lap shear strength and the impact peel strength. Consequently, the contents of the formulation components that resulted in the optimum adhesive strength of epoxy were obtained by our prediction model.

Molecular dynamics simulation study on the effect of perfluorosulfonic acid side chains on oxygen permeation in hydrated ionomers of PEMFCs.

We prepared two types of perfluorosulfonic acid (PFSA) ionomers with Aquivion (short side chain) and Nafion (long side chain) on a Pt surface and varied their water contents (2.92 ≤ λ ≤ 13.83) to calculate the solubility and permeability of O2 in hydrated PFSA ionomers on a Pt surface using full atomistic molecular dynamics (MD) simulations. The solubility and permeability of O2 molecules in hydrated Nafion ionomers were greater than those of O2 molecules in hydrated Aquivion ionomers at the same water content, indicating that the permeation of O2 molecules in the ionomers is affected not only by the diffusion coefficient of O2 but also by the solubility of O2. Notably, O2 molecules are more densely distributed in regions where water and hydronium ions have a lower density in hydrated Pt/PFSA ionomers. Radial distribution function (RDF) analysis was performed to investigate where O2 molecules preferentially dissolve in PFSA ionomers on a Pt surface. The results showed that O2 molecules preferentially dissolved between hydrophilic and hydrophobic regions in a hydrated ionomer. The RDF analysis was performed to provide details of the O2 location in hydrated PFSA ionomers on a Pt surface to evaluate the influence of O2 solubility in ionomers with side chains of different lengths. The coordination number of C(center)-O(O2) and O(side chain)-O(O2) pairs in hydrated Nafion ionomers was higher than that of the same pairs in hydrated Aquivion ionomers with the same water content. Our investigation provides detailed information about the properties of O2 molecules in different PFSA ionomers on a Pt surface and with various water contents, potentially enabling the design of better-performing PFSA ionomers for use in polymer electrolyte membrane fuel cells.

Defect structure evolution of polyacrylonitrile and single wall carbon nanotube nanocomposites: a molecular dynamics simulation approach.

In this study, molecular dynamics simulations were performed to understand the defect structure development of polyacrylonitrile-single wall carbon nanotube (PAN-SWNT) nanocomposites. Three different models (control PAN, PAN-SWNT(5,5), and PAN-SWNT(10,10)) with a SWNT concentration of 5 wt% for the nanocomposites were tested to study under large extensional deformation to the strain of 100% to study the corresponding mechanical properties. Upon deformation, the higher stress was observed in both nanocomposite systems as compared to the control PAN, indicating effective reinforcement. The higher Young's (4.76 ± 0.24 GPa) and bulk (4.19 ± 0.25 GPa) moduli were observed when the smaller-diameter SWNT(5,5) was used, suggesting that SWNT(5,5) resists stress better. The void structure formation was clearly observed in PAN-SWNT(10,10), while the nanocomposite with smaller diameter SWNT(5,5) did not show the development of such a defect structure. In addition, the voids at the end of SWNT(10,10) became larger in the drawing direction with increasing deformation.

Do HOMO-LUMO Energy Levels and Band Gaps Provide Sufficient Understanding of Dye-Sensitizer Activity Trends for Water Purification?

A dye-sensitized solar cell assembly can be used to harvest solar energy, while suitable dye sensitizers can be used to purify water. Here, we characterized the activity trends of four dye sensitizers, namely, PORPC-1, PORPC-2, PORPC-3, and PORPC-4, for water purification applications using density functional theory (DFT) with the Perdew-Burke-Ernzerhof (PBE), B3LYP, and PBE0 functionals, ΔSCF, time-dependent DFT (TD-DFT), and quasiparticle Green's function (GW) methods. The energy levels of the highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) were calculated using gas-phase and aqueous-phase methods in order to understand charge-injection abilities and the dye regeneration processes. PBE, B3LYP, PBE0, and TD-DFT methods failed to predict PORPC-4 to be the best sensitizer, while PORPC-2 and PORPC-4 were predicted to be the best sensitizers using ΔSCF coupled with the implicit solvation method, and HOMO-LUMO energies were corrected for the aqueous environment in the GW calculations. However, none of these methods accurately predicted the performance trend of all four dye sensitizers. Consequently, we used the aggregation assembly patterns of the dye molecules in an aqueous environment to further probe the activity trends and found that PORPC-3 and PORPC-4 prefer J-aggregated assembly patterns, whereas PROPC-1 and PORPC-2 prefer to be H-aggregated. Therefore, the performance of these dye molecules can be determined by combining HOMO-LUMO energy levels with aggregate-assembly patterns, with the activity trend predicted to be PORPC-4 > PORPC-2 > PORPC-3 > PORPC-1, which is in good agreement with experimental findings.