Design Of Materials Research Articles

Clarifying the four core effects of high-entropy materials.

High-entropy materials emerged as a field of research in 2004, when the first research on high-entropy alloys was published. The scope was soon expanded from high-entropy alloys to medium-entropy alloys, as well as to ceramics, polymers and composite materials. A fundamental understanding on high-entropy materials was proposed in 2006 by the 'four core effects' - high-entropy, severe-lattice-distortion, sluggish-diffusion and cocktail effects - which are often used to describe and explain the mechanisms of various peculiar phenomena associated with high-entropy materials. Throughout the years, the effects have been examined rigorously, and their validity has been affirmed. This Perspective discusses the fundamental understanding of the four core effects in high-entropy materials and gives further insights to strengthen the understanding for these effects. All these clarifications are believed to be helpful in understanding low-to-high-entropy materials as well as to aid the design of materials when studying new compositions or pursuing their use in applications.

Ultrasound-Controlled Prodrug Activation: Emerging Strategies in Polymer Mechanochemistry and Sonodynamic Therapy.

Ultrasound has gained prominence in biomedical applications due to its noninvasive nature and ability to penetrate deep tissue with spatial and temporal resolution. The burgeoning field of ultrasound-responsive prodrug systems exploits the mechanical and chemical effects of ultrasonication for the controlled activation of prodrugs. In polymer mechanochemistry, materials scientists exploit the sonomechanical effect of acoustic cavitation to mechanochemically activate force-sensitive prodrugs. On the other hand, researchers in the field of sonodynamic therapy adopt fundamentally distinct methodologies, utilizing the sonochemical effect (e.g., generation of reactive oxygen species) of ultrasound in the presence of sonosensitizers to induce chemical transformations that activate prodrugs. This cross-disciplinary review comprehensively examines these two divergent yet interrelated approaches, both of which originated from acoustic cavitation. It highlights molecular and materials design strategies and potential applications in diverse therapeutic contexts, from chemotherapy to immunotherapy and gene therapy methods, and discusses future directions in this rapidly advancing domain.

Synergistic Cathode Design for High-Performance Dual-Salt Magnesium/Lithium-Ion Batteries Using 2D/2D 1T/2H-MoS2@Ti3C2Tx MXene Nanocomposite.

Magnesium-ion batteries (MIBs) and dual-salt magnesium/lithium-ion batteries (MLIBs) have emerged as promising contenders for next-generation energy storage. In contrast to lithium metal anode in lithium metal batteries, magnesium metal anode in MIBs and MLIBs presents a safer alternative due to the limited dendrite growth and higher volumetric capacity, along with higher natural abundance. This study explores a MLIB configuration with a novel cathode design by employing a 2D/2D nanocomposite of 1T/2H mixed phase MoS2 and delaminated Ti3C2Tx MXene (1T/2H-MoS2@MXene) to address challenges associated with slow kinetics of magnesium ions during cathode interactions. This cathode design takes advantage of the high electrical conductivity of Ti3C2Tx MXene and the expanded interlayer spacing with enhanced conductivity of the 1T metallic phase in 1T/2H mixed phase MoS2. Through a designed synthesis method, the resulting nanocomposite cathode maintains structural integrity, enabling the stable and reversible storage of dual Mg2+ and Li+ ions. The nanocomposite cathode demonstrates superior performance in MLIBs compared to individual components (253 mAh g-1 at 50 mA g-1, and 36% of capacity retention at 1,000 mA g-1), showcasing short ion transport paths and fast ion storage kinetics. This work represents a significant advancement in cathode material design for cost-effective and safeMLIBs.

Inverse design of irregular architected materials with programmable stiffness based on deep learning

Incorporating biological materials-inspired irregularity into architected materials is potential to unfold a wider property or new function space, while the inverse design of irregular architected materials (IAMs) for targeted properties is still challenging, owing to the intricate structure–property bidirectional relationships. Accordingly, here, a data-driven framework is originally developed to design new irregular architected materials with programmable stiffness. In detail, a robust dataset of IAMs, which are constructed from diverse stretch- and bending-dominated building blocks, is created by a randomized strategy, and an end-to-end deep learning model is established, including a forward and an inverse network. The forward predictions reveal that IAMs exactly achieve a wide space of programmable stiffness, especially, including extremely high or low dominant elastic stiffness C11, C22 and C66. More importantly, the deep learning-driven inverse design flexibly and precisely realizes the generation of IAMs, fulfilling the customized stiffness targets. Especially, various stiffness tensors, including isotropic, orthotropic, and anisotropic types, are successfully achieved. The remarkable advantage of the inverse design is that solely through adjusting the frequency hints of building blocks, without mandatory geometrical symmetry, IAMs present the exclusive ability to hit the targeted stiffness. Overall, this work fills the gap in the inverse design of irregular architected materials with programmable stiffness and paves the way for material design via deep learning.

Multidimensional and hierarchical design of biomass-derived carbon nanofiber networks for efficient microwave absorption

Carbon materials have gained significant attention for their potential as highly efficient microwave absorbers. However, it remains a challenge to attain a perfect integration of thin thickness, wide frequency bandwidth, lightweight and strong absorption through structural design of carbon materials. Herein, we design multidimensional and hierarchical carbon nanofiber networks consisting of core-shell carbon nanofibers wrapped by hollow carbon nanoparticles, named CPDA@RCNFs. CPDA@RCNFs which are derived from cellulose and polydopamine (PDA) were prepared by electrostatic spinning, deacetylation, self-polymerization, and carbonization, successively. Thanks to the cooperation of three-dimensional conductive networks, core-shell/hollow/porous structures, as well as doped nitrogen and oxygen heteroatoms, CPDA@RCNFs exhibit excellent comprehensive microwave absorption performance. Specifically, an ultra-strong reflection loss value of -63.31dB and a wide frequency bandwidth of 5.60GHz (12.32-17.92GHz) are achieved at a very thin thickness of 1.8mm with an ultra-low filler loading of 5wt%. This work provides a new insight into the structural design of advanced high-performance microwave absorption carbon materials.

Maximizing photovoltaic performance of all-inorganic perovskite CsSnI3-xBrx solar cells through bandgap grading and material design

In the modern era of technology, worldwide paradigms have been shifted toward the utilization of green energy. Sun energy is the most astonishing eco-friendly resource of energy and can be harnessed with the help of photovoltaic cells. Hybrid (Organic-Inorganic) perovskite solar cells (PSCs) are emerged with incredible photovoltaic (PV) performance. Nevertheless, a significant challenge lies in their lower stability under diverse environmental conditions. To deal with this challenge, all inorganic cesium-based PSC has been studied and analyzed, results improved stability in comparison to hybrid PSC. However, the noxious nature of lead is deleterious to the environment. So, this work primarily aimed, to study lead-free all inorganic tin-based perovskite compound CsSnI3-xBrx, as the main light absorber layer. Further, to elevate the PV performance of PSC, bandgap grading is performed on CsSnI3-xBrx by varying bromide concentration x from 0 to 3. Bandgap grading encourages the absorption of a wide range of the light spectrum, by modulating bandgap (Eg) / affinity(χ) through the distance of the CsSnI3-xBrx layer. Additionally, it enhances light-generated charge carrier separation and collection by end electrodes. In this work, two different strategies have been adopted, linear and parabolic. During linear grading, the impact of variation in x (0 to 3) has been analyzed over the thickness 50–––500 nm in 10 linear steps for CsSnI3-xBrx. The highest PCE fetched from linearly graded layered FTO / CeO2 / CsSnI3-xBrx / CFTS / Gold PSC is 21.68 %. Similarly, in the parabolic graded absorber layer, the influence of change in the bowing factor (0 to 1), has been analyzed relative to different values of x (0 to 3). With improvement in PV performance, the maximum PCE delivered by parabolic-graded PSC is 23.61 %. Additionally, this work extends to check the compatibility of distinct electron transport layers (ETLs) and hole transport layers (HTLs). Upon analysis, it has been found that the best PV performance was obtained while selecting SnO2 / PEDOT as ETL / HTL respectively.

How to transform microporous organic polymers for membrane-based separation: A review

Microporous organic polymers (MOPs) are ideal candidates for designing highly efficient and precise molecular sieving separation membranes due to their exceptional porosity, rigid pore structure, pore size designability, and ease of functionalization. These materials encompass COFs, POCs, PAFs, PIMs, CMPs, and HCPs. However, the path to utilizing MOPs as separation membrane applications has encountered obstacles. Several studies have been conducted to fully exploit the exceptional properties of these polymers. The better application of MOPs materials should be considered in terms of material design and synthesis, membrane formation, and membrane task-specific applications. This review objectively reclassifies MOPs materials based on the latest research and material ordering and provides a systematic summary of MOPs material synthesis and design, MOPs-based membrane fabrication difficulties, and current novel MOPs-based membrane design. Additionally, it introduces in detail the preparation of different types of MOPs-based membranes. The applications of MOPs-based membranes in separation applications are also thoroughly summarized. Finally, this review summarizes the challenges of current MOPs-based membrane development, proposes future opportunities and potential applications in the separation and purification field.

Enhanced PMS activation and NSAID degradation selectivity by hydrophobic microenvironment regulation on Fe3+@Cu-MOF

In this study, the activation of peroxymonosulfate (PMS) and selective degradation of nonsteroidal anti-inflammatory drugs were investigated using hydrophobically modified Fe3+@Cu-MOF. The Fe3+@Cu-MOF-CTAB/PMS system demonstrated high-efficiency, achieving near-complete degradation of diclofenac within 120min. The degradation rate constants for diclofenac, ibuprofen, and naproxen were 0.0048, 0.00103, and 0.00046min-1, respectively, positively correlated with their hydrophobicity. Longer hydrophobic surfactant chains in Fe3+@Cu-MOFs lead to greater initial adsorption of diclofenac, enhancing degradation efficiency upon the introduction of PMS. The Fe3+@Cu-MOF-CTAB/PMS system removes over 80% of diclofenac in various water matrices, showing optimal efficiency in acidic environments but reduced effectiveness with competing anions. Post-degradation changes in the oxidation states of copper and iron in the MOF structure indicated a synergistic redox mechanism essential for PMS activation. The hydroxylation and C-N bond cleavage in diclofenac were key degradation pathways. This study highlights the potential of hydrophobically modified Fe3+@Cu-MOFs in water treatment, providing insights into the interplay between material design, hydrophobic interactions, and catalytic performance.

From health supplement to versatile monomer: Radical ring-opening polymerization and depolymerization of α-lipoic acid

The radical ring-opening polymerization (rROP) of α-lipoic acid (LA) and its derivatives represents a synthetically accessible, efficient, and scalable strategy to impart degradability into functional copolymers. This review highlights recent advances in the design of sustainable materials containing LA through rROP driven by heat and/or light.

Scaling factor of dispersion force interaction between dyes and corn cobs in water

Obtaining the interaction between two substances in liquid through their molecular structures can promote the design and preparation of new functional materials. When multiple types of intermolecular forces coexist, whether the contribution terms generated by each type of intermolecular force have the same scaling factor is a key consideration. In this paper, an empirical equation for calculating the total intermolecular interaction is proposed. The required molecular property parameters for calculation can be obtained through quantum–chemical calculation. For the experiments of removing eight ionic dyes in water by using corn cobs as adsorbents, linear correlation was found between the removal percentage and the total interaction calculated from the proposed equation. When the scaling factors of polar and hydrogen bond interaction terms are 1, the scaling factor of dispersion force interaction term in the equation is greater than 2.5.

Nano-porous structure architectonics of MoS2 nanosheets with flexible electrode membrane for designing ultrastable sodium-ion hybrid capacitor

In the realm of large-scale energy storage, sodium-ion hybrid capacitors (SICs) have emerged as promising contenders due to their impressive fusion of high energy density and power density. However, the challenge lied in addressing the slow reaction kinetics of the Faraday battery-type anode, which was difficult to match with the capacitive-type cathode. In this work, the porous structure architecture was designed by chemically bonding retiform MoS2 nanosheets onto the interpenetrating network electrode membrane (EM) in-situ, creating an integrated electrode (CM@MoS2). The structural synergy between MoS2 and EM facilitated the optimal environment for Na+ transportation and storage, greatly enhancing the reaction kinetics. As the Faraday battery-type anodes, a remarkable reversible capacity retention rate of 94.2% was achieved even after undergoing 1000 cycles at 0.2 A g−1. Matching with capacitive-type cathode of activated carbon (AC), the assembling CM@MoS2//AC SICs also exhibited an impressive reversible capacity retention rate of 87.7% even after 10,000 cycles at 1 A g−1, and achieving 117 Wh kg−1 of the energy density at a power density of 100 W kg−1, showcasing outstanding dual-function features. The application of architectonics to Faraday battery-type anodes holds promised for providing insights and concepts for the future rational design of sodium storage materials with enhanced electrochemical properties in SICs.

O, P, Se, and Cl-doped monolayer MoS2: a new chapter in Co adsorption properties - an exploration based on first principles

This work uses a first-principles approach to thoroughly examine the impact of O, P, Se, and Cl doping of MoS2 on Co adsorption characteristics. Through structure optimization, formation energy calculations, differential charge analysis, and calculations of energy band structure and density of states, we find that P and Cl doping significantly enhances the adsorption capacity of Co on monolayer MoS2, while O and Se doping has a comparatively minor impact. This result reveals that P and Cl doping can significantly improve the adsorption stability of Co through the formation of stronger chemical bonding, which provides a theoretical basis for the design of 2D materials in adsorption applications.

The evolution of intergranular networks during grain growth and its effect on percolation behavior

Triple junctions (TJs) are line defects in three-dimensional (3D) polycrystalline materials where three grains meet. Transport along the TJs depends on the connectivity between them. Here, we investigate the connectivity of more than 6000 TJs in a 3D microstructure of pure iron (Fe) through the lens of bond percolation. Our efforts are made possible by synchrotron-based x-ray diffraction tomography, which allows us to resolve the TJ network both temporally and spatially, during grain growth. In the framework of standard percolation theory, we determine a percolation threshold of the TJs, above which there exists a continuous pathway of TJs that travels infinitely far. Our experimental results indicate a surprisingly different percolation threshold (by 16%) compared to models and theories. The reason for the discrepancy is that the real TJ network has a topological disorder that is not present in the idealized microstructures considered in prevailing models and theories. Leveraging the wealth of time-resolved data we trace the origin of this disorder by following the topological transitions that accompany grain growth. Overall, the insights obtained in this study can help guide the design of polycrystalline materials via defect engineering.

Synthesis of nanosheet-like α-Ni(OH)2/g-C3N4 hybrid anode material with enhanced lithium storage performance

Nickel hydroxide (Ni(OH)2) has been recognized as a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity, cost-effectiveness, and simple synthesis method. However, the application of Ni(OH)2 is hampered by its volume effect and poor electrical conductivity. To address these challenges, herein, a α-Ni(OH)2/g-C3N4 composite is prepared by a hydrothermal approach. The composite possesses a hierarchical nanosheet-like morphology with fibrous nanostructures on the surface. Due to the unique hybrid nanostructure and the synergistic effect of α-Ni(OH)2 and g-C3N4 components, the α-Ni(OH)2/g-C3N4 composite exhibits significantly enhanced lithium storage performance in terms of electrochemical activity, cyclability, and kinetics than the bare α-Ni(OH)2 counterpart. Specifically, the α-Ni(OH)2/g-C3N4 achieves a remarkable capacity of 696 mA h g−1 after 400 cycles at 0.5 A g−1, far larger than the corresponding value (96 mA h g−1) of pure α-Ni(OH)2. CV and GITT analysis demonstrate the α-Ni(OH)2/g-C3N4 composite has an obvious pseudocapacitance behavior and a much smaller polarization effect than the bare α-Ni(OH)2 during cycling. This work could provide clues for the structural design and performance improvement of nickel hydroxide-based anode materials for LIBs.

Comparative experimental study on photothermal conversion and shape memory properties of MF-based flexible composite phase change materials loaded with carbon nanotubes and polydopamine

Efficient use of solar energy can effectively alleviate the problem of energy shortages. Currently, extensive researches have been carried out on photothermal conversion materials. However, factors such as photothermal conversion and thermal conductivity limit the practical implementation of photothermal materials. In this research, a novel flexible composite phase change material (CPCM) with melamine foam (MF) as the supporting skeleton, carbon nanotube (MWCNT)/polydopamine (PDA) as the light-absorbing coating and polyethylene glycol (PEG) as the energy storage material was successfully prepared. The results show that the MF-based CPCMs have good shape stability with a leakage of only 0.9 %, and high phase change enthalpies, the melting enthalpy was above 172.0 J/g. In addition, the thermal conductivity was improved due to the introduction of light-absorbing coatings into the CPCMs. Compared with MF/PEG, MWCNT/MF/PEG, and PDA/MF/PEG, MWCNT/PDA/MF/PEG were improved by 35.21 %, 8.6 % and 29.46 %, respectively. Finally, the average charging efficiency of MWCNT/PDA/MF/PEG is 96.26 %, which is 62.33 % and 20.1 % higher than that of MWCNT/MF/PEG and PDA/MF/PEG respectively, indicating that MWCNT and PDA nanofillers played a synergistic role in enhancing the performance of CPCMs. This study provides new and innovative ways for the design of photothermal materials.

Experimental determination and thermodynamic optimization of the Nb–V–Zr system

A comprehensive thermodynamic description for each phase is essential for designing of the novel Zr-based nuclear materials. The construction of the experimental liquidus surface projection and isothermal section of the Nb–V–Zr system was established through analyzing solidification microstructures and phase constituents. The stability of the τ phase with C14-structure was established by investigating the composition range of Nb in τ, which was measured to be between 19.8 and 40.5 at. % at 1473 K. The solubility of Nb in λ2 with the C15-type was ∼ 16.9 at. % at 1473 K. The liquidus surface projection showed primary solidification areas of bcc(Nb,V,Zr), λ2 and τ. The thermodynamic parameters were derived combining the CALPHAD method with experimental results from phase diagram data in this work and the literatures. Solution phases, including liquid, bcc, and hcp, were regarded as substitutional solutions. Considering the crystal structures and solid solubility of intermetallic compounds, λ2 and τ were modeled as (Nb,V,Zr)2(Nb,V,Zr) using two-sublattice model. A set of self-consistent thermodynamic parameters of the Nb–V–Zr system was obtained, which will provide theoretical guidance for the design of Zr-based nuclear materials.

Numerical simulation and optimization of Pervaporation process based on Heat-Mass-Flow coupling

Pervaporation (PV) has the advantages of low energy consumption and high separation efficiency, but the trade-off effect between flux and separation factor restricts its large-scale application. Based on the conservation equations of mass, momentum and heat, a transient model of the whole PV process coupled with heat-mass-flow was established in this paper. The effects of feed temperature, feed concentration and feed flow rate on heat and mass transfer in PV process were analyzed. TEOS crosslinked PDMS/PTFE-PVDF membrane was prepared by scraping coating method. The reliability of the model was verified by taking n-butanol/water separation system as an example. The concentration polarization and temperature boundary layer under different operating conditions are discussed. The effect of operating conditions on the separation performance was evaluated by response surface method, and the optimal operating conditions are obtained. The results show that the concentration polarization of the membrane surface becomes more obvious with the increase of feed concentration. The temperature boundary layer decreases with the increase of feed flow rate. Surprisedly, there is a significant temperature gradient in the membrane, and the maximum temperature difference between the two sides of the membrane is as high as 1.02 K. Diffusion in the membrane is the rate controlling factor of PV process. The contribution of operating conditions to the separation performance is in the order of feed temperature > feed concentration > feed flow rate. The best operating conditions are: feed temperature 350.2 K, feed concentration 3.8 % n-butanol/water and feed flow rate 23.6L/h. This work provides a theoretical basis for the design of PV membrane materials and the optimization of PV operating conditions.

Ultra-long room temperature phosphorescent materials based on tetraphenylethylene derivatives for anti-counterfeiting and encryption applications

Stimuli-responsive room temperature phosphorescent materials have been the subject of considerable research activity in recent years. In this study, the tetraphenylethylene group was selected in combination with arylboronic acid (TIPE-BOH) and used to dope a rigid polyvinyl alcohol (PVA) matrix to generate a film material (TIPE-BOH-PVA) that exhibited an aggregation-induced emission (AIE) effect. The prepared film exhibits excellent room temperature phosphorescence (RTP) performance, with an enhanced emission wavelength and an afterglow time of up to 12 s. The triplet-to-singlet Förster resonance energy transfer (TS-FRET) has been utilized to modify the afterglow color by adding butyl rhodamine B (BRhB) and rhodamine 6G (R6G), employing a water phase without the use of organic solvents. The resultant material exhibits stimulus responsiveness; the RTP properties disappear when the material is exposed to water vapor, but are restored following thermal treatment. The material has potential applications in information encryption and erasure, double anti-counterfeiting ink, and fingerprint acquisition systems. This work offers a new strategy for the design of stimuli-responsive ultra-long RTP materials with far-ranging end applications.

A conductive flexible carbon nanoyarns embedded with VN quantum dots for highly Kinetics-Compatible Li-Ion capacitors

Lithium-ion capacitors (LICs) with high energy and power density has gained widespread attention. However, the kinetics mismatch between the anode and cathode of LICs limits its further development. Vanadium nitride (VN) with high electrical conductivity is a suitable anode to reduce the kinetic gap between the two electrodes of LICs, but the VN usually undergoes severe volume changes (～240 %) during the electrochemical reaction. Herein, the VN@N-PCYS-0.4 films that ultrafine VN quantum dots uniformly embedded in polyacrylonitrile-derived carbon (PAN-DC) nanoyarns were synthesized by a simple sacrificial silica template-assisted electrostatic spinning technique. Ultra-small particle size of VN (∼1 nm) mitigates the volume expansion and enriches the active sites. The super loose porous structure of PAN-DC nanoyarns shortens ions/electrons diffusion pathways and enhances electrolyte penetration. Correspondingly, on the basis of such free-standing VN@N-PCYS-0.4 anode, a LICs was assembled by matching activated carbon (AC) cathode, which exhibits a high energy density of 99.7 Wh kg−1 and a high power density of 24.0 kW kg−1. Such rational design for carbon-based material can surmount kinetics incompatibility between anode and cathode of LIC and provides a perspective to enhance the electrochemical properties of LIC anode in terms of volume expansion suppression and charge transfer resistance reduction.

Enhancing microwave absorption via ion exchange-regulated metal elemental-alloy transition behavior

Metal-organic frameworks (MOFs) are considered as suitable candidates for excellent microwave absorption (MA) materials. However, the influence of the transition behavior from metal to alloy dominated by the metal ion ratio and the accompanying multi-phase coexistence model on the MA mechanism is unclear. This study successfully prepared a series of porous electromagnetic composite materials through ion-exchange in-situ pyrolysis synergistic strategy. The results indicate that the modulation of the Fe/Co ion ratio can easily manipulate the phase transition from Co metal to FeCo alloy-cobalt ferrite and the crystal defects within. The state of metal/alloy coexistence obtained at a low ion exchange degree has the highest concentration of vacancies, which is conducive to wideband absorption (6.03 GHz) and efficient loss (−67.44 dB) of MA performance. In contrast, the MA performance of samples at medium/high ion exchange degrees is not ideal. In addition, the application prospects of this material were demonstrated by simulating the actual absorption situation using radar cross-section. In summary, this work reveals the intrinsic relationship between the phase evolution behavior determined by the ion exchange degree in MOF derivatives and the electromagnetic performance, as well as the MA mechanism, providing a new reference for the preparation and design of outstanding MA materials.