Design Of Materials Research Articles

Modulating Ti coordination environment in Ti-containing materials by sulfation for synergizing with Au sites to facilitate propylene epoxidation

Modulating the coordination environment of Ti sites in Ti-containing materials to synergize with Au sites is a crucial issue to boost the process of propylene epoxidation with H2 and O2 to produce propylene oxide (i.e., HOPO), but still remains a great challenge. Herein, we report a facile strategy to tailor the coordination states and electronic properties of Ti sites. The sulfur-decorated Ti-SiO2 (i.e., Ti sites anchored onto silica) with moderate sulfur loading (Ti-SiO2-S-M) can synergize well with Au sites for the HOPO process with high activity, propylene oxide (PO) selectivity, and H2 efficiency, which are superior to those achieved on the referenced Ti-SiO2 synergizing with Au sites. Multiple characterizations, in-situ diffuse reflectance infrared Fourier transform spectroscopy of propylene and PO, PO conversion experiment, and kinetics behaviors demonstrate that the superior advantages of Ti-SiO2-S-M against Ti-SiO2 result from the increased Ti binding energy, improved hydrophobicity, and weakened acidity, which simultaneously facilitate the adsorption of propylene and promote the desorption of PO. This insight reported here could guide the rational design and optimization of Ti-containing materials to synergize with Au catalysts for propylene epoxidation.

Novel high-temperature thermochromic polydiacetylene material and its application as thermal indicator

The design and synthesis of organic high-temperature reversible thermochromic materials is one of the difficult issues in the field of organic chromic materials. In this paper, four diacetylene monomers named DBA-PCDA, TBA-PCDA, DBE-PCDA and TBE-PCDA, each containing multiple diacetylene units, were synthesized from 10,12-pentacosadiynoic acid (PCDA) through the amidation or esterification reactions, using 4,4′-diaminobiphenyl, 1,3,5-tris(4-aminophenyl)benzene, 4,4′-dihydroxybiphenyl, and 1,3,5-tris(4-hydroxyphenyl)benzene as bridging units. The effects of functional groups that can form hydrogen bond and π-π interactions on the solid-state polymerization properties of monomers and the thermochromic properties of the corresponding PDAs were investigated. The results show that only DBA-PCDA and TBA-PCDA, which contain functional groups that can form hydrogen bonding interactions, can be polymerized under 254-nm UV irradiation. The corresponding poly(DBA-PCDA) exhibits reversible thermochromic property even heated up to 200 oC, showing a potential application in the field of high-temperature thermal indicator above 100 °C. This work provides a new perspective to the development of PDA with high-temperature reversible thermochromic property.

Spread of infectious diseases by microorganisms present in fomites

Fomites, inanimate objects that can carry infectious agents, play a critical role in the spread of infectious diseases. Despite advances in sanitation and hygiene practices, fomites remain a significant vector for the transmission of various pathogens, particularly in healthcare settings and densely populated environments. This paper reviews the mechanisms by which microorganisms are transmitted through fomites, the types of diseases commonly spread in this way and the factors that influence fomite-based transmission. Strategies for mitigating the risk of fomite-based disease spread are also discussed, highlighting the importance of targeted hygiene interventions, material design and environmental decontamination.

Silk Proteins: Designs from Nature with Multipurpose Utility and Infinite Future Possibilities.

This is a Perspective on nature as a story-teller, where inputs of evolution drove the remarkable protein designs found in silks. This selection process has resulted in silk materials with novel chemistry and properties to support organism survival in nature, yet with newfound utility in everything from comic books and automobiles to medicine. With growing global concerns related to environmental health, silks also serve as an invaluable instructional guide to the future of sustainable material designs.

Triarylmethanol Derivatives with Ultralong Organic Room-Temperature Phosphorescence.

Triphenylmethyl-based compounds such as rhodamines and fluoresceine representing an old and well-known class of triphenylmethane dyes, are widely used in fluorescent labeling of bioimaging. Inspired by ultralong room temperature phosphorescence of triphenylphosphine derivatives, herein we report a methoxy substituted triarylmethanol ((4-methoxyphenyl)diphenylmethanol, LJW-1) exhibits ultralong room temperature phosphorescence (RTP) under ambient condition with afterglows of about 7 seconds. Its multiple C-H···π intermolecular interactions, C-H···O intermolecular interactions, hydrogen bond and π-π interactions are beneficial for forming rigid environment in the aggregated state which is evidently an important factor in the appearance of excellent RTP. Different substituents on triarylmethanol result in compounds with different lifetimes varying from 7 µs to 818 ms. The substituent effects on the phosphorescence of triarylmethanol derivatives provide an efficient method for the design of organic RTP materials and may be enlightening the phosphorescence research of triarylmethanol derivatives.

Benchmarking luminescent properties of the arylvinylpyrimidine scaffold.

The exploration of the photophysical properties of push-pull molecules incorporating pyrimidine rings as electron-attracting moieties in their structure continues to be a fascinating area of investigation. A thorough examination of these properties not only contributes to fundamental knowledge but also provides crucial insights for the rational design of emissive materials in prospective applications. In this context, this work conducts an in-depth analysis of four families of 4,6-bis(arylvinyl)pyrimidines, evaluating the influence of substituents on both the aryl groups and position 2 of the pyrimidine ring. While previous research has primarily focused on solution studies, this work emphasizes the importance of examining solid-state photophysics. Through a multidisciplinary approach encompassing optical techniques, x-ray diffraction, and quantum chemical calculations, a comprehensive understanding of the structure-property relationships is achieved. This study underscores the intricate interplay between molecular structure, aggregation, and fluorescence behavior in pyrimidines, offering valuable insights with broader implications beyond academic realms.

A computational study and analysis of Variational Quantum Eigensolver over multiple parameters for molecules and ions

AbstractMaterial discovery is a phenomenon practiced since the evolution of the world. The discovery of materials has led to significant development in varied fields such as Science, Engineering and Technology. Computationally simulating molecules has been an area of interest in the industry as well as academia. However, simulating large molecules can be computationally expensive in terms of computing power and complexity. Quantum computing is a recent development that can improve the efficiency in predicting properties of atoms and molecules which will be useful for material design. The Variational Quantum Eigensolver (VQE) is one such quantum algorithm used to calculate the ground state energy of molecules or ions. In this study, we have done a comparative analysis of the parameters that constitute the VQE algorithm. This includes components such as basis, qubit mapping, ansatz, and optimizers used. We have also developed a database consisting of 79 single atoms and their variations of oxidation states and 33 molecules with the data of their Hamiltonian and ground state energy and dipole moment.

Developing Practical Catalysts for High‐Current‐Density Water Electrolysis

AbstractHigh‐current‐density water electrolysis is considered a promising technology for industrial‐scale green hydrogen production, which is of significant value to energy decarbonization and numerous sustainable industrial applications. To date, substantial research advancements are achieved in catalyst design for laboratory‐based water electrolysis. While the designed catalysts demonstrate remarkable performance at laboratory‐based low current densities, they suffer from marked deteriorations in both activity and long‐term stability under industrial‐level high‐current‐density operations. To provide a timely assessment that helps bridge the gap between laboratory‐scale fundamental research and industrial‐scale practical water electrolysis technology, here the current advancements in various commercial water electrolyzers are first systematically analyzed, then the key parameters including work temperature, current density, lifetime of stacks, cell efficiency, and capital cost of stacks are critically evaluated. In addition, the impact of high current density on the electrocatalytic behavior of catalysts, including intrinsic activity, long‐term stability, and mass transfer, is discussed to advance the catalyst design. Therefore, by covering a range of critical issues from fundamental material design principles to industrial‐scale performance parameters, here the future research directions in the development of highly efficient and low‐cost catalysts are presented and a procedure for screening laboratory‐designed catalysts for industrial‐scale water electrolysis is outlined.

Synthesis and antimicrobial activity of yttrium-doped cerium oxide nano-composite against wound pathogen

Abstract Nanocomposite materials have attracted considerable interest in several disciplines owing to their distinctive characteristics and possible uses. The primary objective of this study was to synthesize and characterize a nanocomposite material consisting of cerium that has been doped with yttrium. The shape, structure, and properties of the synthesized nanocomposite was characterized using various characterization techniques including ultraviolet spectrophotometry, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray diffraction (XRD), zeta potential measurements, dynamic light scattering (DLS), and Fourier-transform infrared spectroscopy (FTIR).The antibacterial activity of the nanocomposite was assessed against a range of pathogenic bacteria including Gram-positive bacteria - Enterococcus faecalis, Staphylococcus aureus, and Gram-negative bacteria- Escherichia coli, Pseudomonas aeruginosa using standard microbiological techniques. The results indicate that the nanocomposite possesses strong antibacterial properties against a wide range of microorganisms, showcasing its potential as a highly effective antimicrobial agent for diverse applications in the biological, environmental, and industrial fields. Hemolysis is the process of red blood cell destruction, resulting in the release of hemoglobin into the surrounding fluid. In this study, 0.7:0.3M nanocomposite had showed effective biocompatibility with less than 5%. Furthermore, this particular composite remained identical in different time intervals, while other composites would normally fluctuate. Research has shown that meticulous material design and surface modification can reduce the harmful effects on red blood cells, hence improving the safety of nanocomposite for therapeutic purposes. In summary, this study offers valuable information on the creation, analysis, and assessment of nanocomposite materials with antimicrobial properties.

Antibonding valence states induce low lattice thermal conductivity in metal halide semiconductors

Reduction of phonon mediated thermal transport properties, i.e., lattice thermal conductivity (κL), of semiconductors can strongly affect the performance of thermoelectrics and optoelectronics. Although extrinsic routes to reduce κL have been achieved through selective scattering of phonons via doping, alloying, and hierarchical nano-structuring, semiconductors with intrinsically low κL have recently gained widespread attention due to their ability to decouple electronic and phonon transports. While innate low κL in crystalline semiconductors is a desired requirement to achieve high performance thermoelectrics, the solar upconversion efficiency of photovoltaics based on metal halide perovskites (MHPs) have been shown to increase due to their ultralow κL through the hot-phonon bottleneck effect. Therefore, understanding the microscopic mechanisms underlying ultralow κL in crystalline semiconductors is extremely important. Several structural factors that are intrinsic to a material have been shown to strongly influence the reduction of κL. Among them, the presence of rattling atoms, lone-pair electrons, and large lattice anharmonicity have been widely studied. Here, we bring out yet another largely unexplored intrinsic characteristic of materials related to the filled antibonding valence states (AVS) near the Fermi level, which are shown to induce low κL in crystalline compounds. We focus our review on an emerging class of compounds–metal halide semiconductors including MHPs and investigate the interplay between structures, chemical bonding and κL, carefully curating from literature a list of 33 compounds having different structure dimensionality with known κL. We established a universal connection between the elastic moduli, speeds of sound, and κL with the presence of AVS just below the Fermi level. We found that large peak in the AVS correlates positively with lower values of elastic moduli, speeds of sound, and κL, providing antibonding states based design criteria of low-κL compounds. Furthermore, we discuss different synthesis strategies, which are crucial for experimental realization of ultralow κL through structure manipulation. Additionally, we outline how chemical bonding data can be utilized in machine learning models for predictive modeling of κL. We hope that our approach of understanding low-κL through the viewpoint of chemical bonding theory would encourage exploration of phonon transport properties in other families of materials having filled AVS that can provide further insights on the structure-bonding-property relationships aiding novel materials design approaches.

2D Transition Metal Chalcogenides (TMDs) for Electrocatalytic Hydrogen Evolution Reaction: A Review.

Since the MoS2 synthesis, the family of two-dimensional transition metal chalcogenides (TMDs) have been intensively explored theoretically and experimentally. TMDs endowed with adjustable electronic, physical and chemical properties lead to increasing interest in the application of energy storage, molecule detection and catalysis. In the mini review, we present a forward-looking summary of 2D TMDs in hydrogen evolution electrocatalysis, including synthesis methods, hydrogen evolution performance, and optimization strategies. This review will deepen the fundamental understanding of the physical-chemical properties of TMDs with different phases and contribute unveil the universal principle among electronic configuration, atomic arrangement, physical and chemical property for the material design.

Optimizing Room‐Temperature Thermoelectric and Magnetocaloric Performance via Constructing Multi‐Scale Interfacial Phases in LaFeSi/BiSbTe Thermo‐Electro‐Magnetic Refrigeration Materials

AbstractFabricating a thermo‐electro‐magnetic material that exhibits simultaneously excellent magnetocaloric (MC) and thermoelectric (TE) performance is challenging since the interfacial reaction causes severe deterioration of MC and TE performance. In this work, a construction of multi‐scale interfaces in LaFe10.4Co0.8Si1.8/Bi0.5Sb1.5Te3 (LFS/BST) composites is realized by adopting a low‐temperature high‐pressure sintering strategy. It is revealed in the atomic‐scale that the interfacial reaction between LFS and BST leads to the formation of (Fe,Co)(Sb,Te)2 micro‐grains and LaTe2 nano‐grains, and the latter form low‐mismatch phase boundaries with LFS matrix. Benefiting from the multi‐scale interfacial phases, excellent MC performance of LFS is preserved alongside a minor impact on TE properties, e.g., a peak zT of 1.04 and a small decrease of 3.0% in relative cooling power are achieved in the 2%LFS/BST composite. Compared with other thermo‐electro‐magnetic materials, a good trade‐off between MC and TE performance is realized in LFS/BST composites with simultaneously high MC and TE performance. The 20%LFS/BST composite exhibits a room‐temperature zT of 0.46 with large maximum magnetic entropy change and relative cooling power of 0.81 J kg−1 K−1 and 44.83 J kg−1, respectively. This work provides an effective material design for developing the all‐solid‐state MC/TE hybrid refrigeration technique.

Boosting Photoluminescence of Rare-Earth-Based Double Perovskites by Isoelectronic Doping of ns2 Metal Ions.

Doping of ns2 metal ions as an energy transfer (ET) bridge can significantly elevate the photoluminescence properties. Nonetheless, the fundamental influence of ns2 metal ions on the local lattice structures remains unclear, hindering the advancement of functional materials. Herein, Sb3+ doped rare earth double perovskites is employed as a typical case to demonstrate this issue. It is found that the isoelectronic doping of Sb3+ ions not only enhances the ET efficiency but also changes their localized electronic and lattice structures. Both density functional theory (DFT) and Judd-Ofelt (J-O) theory calculations provide unambiguous evidence that the isoelectronic doping of Sb3+ ions enables a more localized charge density in the [LnCl6]3- (Ln: Lanthanide) octahedron and reduces the symmetry of the environment around the Ln3+, facilitating the radiative transition rates of Ln3+ while enhancing their ET efficiency. Compared with Cs2NaScCl6:Ln3+, the ET efficiency of Cs2NaScCl6:Sb3+/Ln3+ is enhanced by 1.5-fold, reaching up to 98.3%. To the best of available knowledge, this work is the first to unravel the intrinsic mechanism of enhanced ET process enabled by isoelectronic doping via DFT and J-O theory. This research sheds light on understanding the mechanism of photophysics and rational design of the functional perovskite materials.

Integration of facial expression detection into the design and assessment of programming teaching materials

Integration of facial expression detection into the design and assessment of programming teaching materials

Super-Resolution Microscopy as a Versatile Tool in Probing Molecular Assembly

Molecular assembly is promising in the construction of advanced materials, obtaining structures with specific functions. In-depth investigation of the relationships between the formation, dynamics, structure, and functionality of the specific molecular assemblies is one of the greatest challenges in nanotechnology and chemistry, which is essential in the rational design and development of functional materials for a variety of applications. Super-resolution microscopy (SRM) has been used as a versatile tool for investigating and elucidating the structures of individual molecular assemblies with its nanometric resolution, multicolor ability, and minimal invasiveness, which are also complementary to conventional optical or electronic techniques that provide the direct observation. In this review, we will provide an overview of the representative studies that utilize SRM to probe molecular assemblies, mainly focusing on the imaging of biomolecular assemblies (lipid-based, peptide-based, protein-based, and DNA-based), organic–inorganic hybrid assemblies, and polymer assemblies. This review will provide guidelines for the evaluation of the dynamics of molecular assemblies, assembly and disassembly processes with distinct dynamic behaviors, and multicomponent assembly through the application of these advanced imaging techniques. We believe that this review will inspire new ideas and propel the development of structural analyses of molecular assemblies to promote the exploitation of new-generation functional materials.

What can machine learning help with microstructure-informed materials modeling and design?

AbstractMachine learning (ML) techniques have been widely employed as effective tools in addressing various engineering challenges in recent years, particularly for the challenging task of microstructure-informed materials modeling. This work provides a comprehensive review of the current ML-assisted and data-driven advancements in this field, including microstructure characterization and reconstruction, multiscale simulation, correlations among process, microstructure, and properties, as well as microstructure optimization and inverse design. It outlines the achievements of existing research through best practices and suggests potential avenues for future investigations. Moreover, it prepares the readers with educative instructions of basic knowledge and an overview on ML, microstructure descriptors, and ML-assisted material modeling, lowering the interdisciplinary hurdles. It should help to stimulate and attract more research attention to the rapidly growing field of ML-based modeling and design of microstructured materials. Graphical abstract

Comparative visual performance of ultraviolet light-filtering and violet light-filtering monofocal intraocular lenses of the same material and basic design

We compared the visual performance of ZCB00 ultraviolet light-filtering and ZCB00V violet light-filtering monofocal intraocular lenses (IOLs) (both Johnson & Johnson Surgical Vision) with the same materials and basic design in cataract patients treated from 2011 to 2020. The evaluations were performed 10 weeks after the last surgery for implantation of bilateral lenses ≤ 3 months apart. The ZCB00 and ZCB00V groups included 904 eyes from 452 patients (age 72.3 ± 6.8 y; women/men, 268/184) and 1374 eyes from 687 patients (age 73.0 ± 7.4 y; women/men, 415/272), respectively. Statistical validity was confirmed using a linear mixed-effects model with binocular data and adjustments for age, sex, subjective refraction cylinder, subjective refraction spherical equivalent, corneal astigmatism, axial length, pupil diameter, and corneal higher-order aberrations. ZCB00 showed slightly but significantly better results (p < 0.05, Wald) for uncorrected intermediate/near visual acuity, corrected near visual acuity, and components of the 25-item Visual Function Questionnaire (VFQ-25) (Role_Limitation, Mental_Health, Social_Function, Distance_Vision, Color_Vision). Additionally, ZCB00V showed significantly better contrast sensitivity with glare (visual angle of target: 6.3°/4.0°/0.7°; p < 0.00068, Wald); slightly but significantly better contrast sensitivity without glare (4.0°/2.5°/1.6°) and with glare (2.5°/1.6°/1.0°), VFQ-25 General_Health scores, and near spectacle independence; and slightly but significantly smaller higher-order aberrations (internal, scaled to a 6-mm pupil; Wavefront_6_post_I_Trefoil) (p < 0.05, Wald).

Atomic Layer Processing (ALP): Ubi es et Quo Vadis?

AbstractAtomic Layer Processing (ALP) techniques have transformed materials engineering by enabling atomic/molecular‐level control over composition, fidelity in structure replication, and properties. Tracing its origins to pioneering molecular layering and atomic layer deposition work in the mid‐20th century, this multifaceted field has remarkably diversified to include molecular layer deposition (MLD), atomic layer etching (ALE), area‐selective deposition (ASD), and vapor‐phase infiltration (VPI) processes. ALP is making great impacts across diverse disciplines – facilitating semiconductor miniaturization through ultrathin dielectric films, improving battery materials and engineering catalysts for energy applications, creating bioactive surfaces for advanced biomaterials, and promoting sustainable membranes for environmental remediation. As ALP techniques continue evolving through integration with additive manufacturing, machine learning, and in situ diagnostics, new frontiers in materials design are emerging, driven by the growing focus on environmental considerations like renewable precursors, energy‐efficient processes, and waste minimization. This perspective article examines ALP's historical development, highlights current state‐of‐the‐art applications across selected fields, and provides insights into the anticipated future trajectory, emerging application domains, and the pivotal role of academic‐industry‐research laboratory collaborations in catalyzing ALP innovations and facilitating its widespread adoption as a transformative manufacturing platform.

Construction of Asymmetric Filler Density Mixed-Matrix MOF Membranes via Liquid-Phase Ion Activation for Advanced Oxidation Processes.

Mixed-matrix membrane (MMM) reactors incorporating metal-organic framework (MOF) fillers have significant applications in fields such as separation, catalysis, and chiral resolution. However, the traditional method of directly mixing MOF fillers with polymers results in a symmetric structure where most of the MOF fillers are uniformly distributed across the membrane reactor's cross-section. During usage, this leads to a pronounced trade-off between flux and efficiency and the waste of the MOF, as the rich pore characteristics and active sites of MOFs are not fully utilized. In this study, we propose a liquid-phase ion activation strategy that enables the in situ formation of a uniform and densely packed MOF shell layer on the membrane surface during the phase inversion process of MMM fabrication. This asymmetric density distribution of the MOF-based MMM reactor selectively induces the generation of considerable nonradical 1O2 in the peroxomonosulfate (PMS) system, demonstrating superior catalytic degradation performance against antibiotics like TC and dye molecules (with a flux of 1880 L m-2 h-1 and a Kapp value of 648 min-1), as well as outstanding cycling stability and environmental tolerance. This discovery sheds light on the design and engineering of composite membrane materials and applications for advanced oxidation processes in water purification.

Review on polymer electrolytes for lithium‐sulfurized polyacrylonitrile batteries

AbstractLithium‐sulfur (Li‐S) batteries are deemed as the next generation of energy storage devices due to high theoretical specific capacity (1675 mAh g−1) and energy density (2600 Wh kg−1). However, the commercial application has always been constrained by lithium polysulfide (LiPSs) shuttling effects and still has a long way to go. Sulfurized polyacrylonitrile (SPAN) is a promising alternative candidate to replace traditional sulfur cathode and is conducive to eliminating LiPSs by realizing “solid‐solid” direct conversion in conventional carbonate electrolytes. However, an over 25% irreversible capacity loss is exhibited inevitably in the first discharge process, the inherent structure of SPAN and the related reaction mechanism remain unclear. In this review, the structure characteristics and electrochemical behaviors of SPAN are summarized for better interpreting current knowledge and favoring the design of high performance materials. In the past few decades, many problems in traditional Li‐S batteries have been solved by improving electrolytes. Polymer electrolytes (PEs) have been widely used due to structural designability, multi‐functionality, exceptional chemical stability, and excellent processability. Surprisingly, the relevant researches on PEs compatible with SPAN remains limited currently. Therefore, the recent modification strategies of gel polymer electrolytes and solid polymer electrolytes in Li‐SPAN batteries are introduced in terms of Li+ transfer and interface engineering, the design principles are concluded, the specific challenges encountered by polymer‐based electrolytes are summarized and the instructive directions for future research on PEs are demonstrated, facilitating the commercialization of Li‐SPAN batteries.