Design Of Functional Materials Research Articles

Interface characteristics and performance of additively manufactured steel-titanium bimetals prepared through composition gradient layers

In this study, laser-directed energy deposition (LDED), a powder-feeding laser additive manufacturing technique, was utilized to fabricate bimetals comprising high-strength steel (HSS) and Ti6Al4V (TC4). Through meticulous compositional control, four distinct regions (labeled Areas 1 through 4) comprising Fe-Ti intermetallics with varying sizes and morphologies were obtained at the LDEDed HSS/TC4 interface. These zones exhibited thicknesses of approximately 190 μm, 210 μm, 525 μm, and 205 μm, respectively. The effect of these intermetallics on the performance of LDEDed HSS/TC4 bimetals was investigated. The results indicated that most Fe-Ti intermetallics, characterized by reticular/granular morphologies or fine precipitates, were dispersed at the bonded interfaces (Areas 1, 3, 4). Nevertheless, irregular and long-striped C14_Laves phases were observed in Area 2, indicating the presence of a pure Fe2Ti region. Performance testing revealed that fractures predominantly occurred within a hard and brittle Fe2Ti region (Hardness: 891.5HV) during mechanical grinding or tensile clamping, highlighting the formidable challenge of achieving high-quality LDEDed HSS/TC4 bimetals through a component-regulated building strategy. The difficulty arises from the high Fe content in HSS and high Ti content in TC4, resulting in the formation of a pure Fe2Ti region at the interface. Thermodynamic calculations suggest that the composition-gradient-layer strategy may not be optimal for the integrated laser additive manufacturing of HSS and TC4. These findings provide valuable insights into the design of steel-titanium functional gradient materials and other multi-material components.

Thinking Outside the Energetic Box: Stabilizing and Greening High-Energy Materials with Reticular Chemistry.

ConspectusReticular chemistry has provided intriguing opportunities for systematically designing porous materials with different pores by adjusting the building blocks. Among them, framework materials have demonstrated outstanding performance for the design of new functional materials used in a broad range of fields, including energetic materials. Energetic materials are widely used for rockets, satellites, mining, and tunneling. In terms of energetic materials, explosophores and nitrogen-rich heterocycles are fundamental building blocks for high-energy compounds. However, the traditional strategy of synthesizing HEDMs (high energy density materials) at the molecular level has faced the long-term challenge of balancing energy and stability. Inspired by reticular chemistry, nitrogen-rich heterocycles offer diverse nitrogen sites for designing diversified coordination interactions. Ionic bond interactions exist in a wide range of energetic salts. Furthermore, most metastable explosophores, e.g., nitro, nitramino, and amino groups, can form strong hydrogen-bonding networks. Based on these noncovalent interactions (such as coordination, ionic, and/or hydrogen bonds (HBs)) and/or covalent interactions can determine intermolecular packing/linkage of the energetic fuel and oxidizer components, reticular chemistry provides a new platform evolving from single-molecular design to various energetic frameworks (E of the energetic frameworks with superior comprehensive properties. For example, to achieve coordination with metals or introduce sufficient hydrogen bond donor/acceptor structural units, the host structure of energetic framework materials usually contains less oxygen-rich substituents such as nitro, so the host molecules of the framework, F) at the crystal level, which can enhance the integrated stabilities of EFs.Along with growing concerns about the environment and safety issues, considerable effort has been devoted to pursuing environmentally friendly and insensitive energetic materials. The newly emerging EFs are conducive to introducing explosophores into a green chemical pathway. Benefiting from these cross-disciplinary achievements, taming metastable energetic molecules in specific porous frameworks is a green strategy to desensitize energetic materials while concomitantly retaining excellent energetic properties, which has become one of the most forward and promising investigations. In the past decade, EFs have achieved further results in stabilizing and greening energetic materials using HBs, covalent bonds, and alkaline earth metal-involving coordination bonds to avoid heavy metal toxicity and to employ halogen-free oxidizers. Because this field is still expanding rapidly, it is of great value for researchers and possible users of the work to be able to view all the progress.Through this Account, we intend that more readers will become knowledgeable about EFs, including their definition, history, synthesis, properties, and possible applications. The aim of this Account is to present the latest advances in EFs in recent years and to offer a perspective on the future direction of this field.

Turning coal hydrogenation liquefaction residue into high conductivity carbon black with magnesium citrate-assisted steam activation followed by high temperature treatment

The high conductivity carbon black was prepared using coal hydrogenation liquefaction residue as raw material, through a combination methods of solvent extraction purification, magnesium citrate-assisted carbonization, steam activation, and high-temperature treatment. The effects of carbonization and activation process parameters, heat treatment temperatures, and other factors on the microstructure, specific surface area, degree of graphitization, and conductivity of the carbon black were studied. The coal direct liquefaction residue was firstly purified using a xylene and tetrahydrofuran solution with a volume ratio of 1:1 by centrifugal separation method to obtain coal liquefaction asphalt. Then, the coal liquefaction asphalt was mixed with magnesium citrate in a mass ratio of 3:7 and ball-milled for 90 min. After carbonizing at 950 °C for 120 min, magnesium ions were leached out with hydrochloric acid. The obtained sample was activated with steam at 900 °C for 100 min and then underwent high-temperature treatment at 1500 °C under a N2 atmosphere for 120 min. The microstructure of the conductive carbon black exhibited an irregular blocky structure with an average particle size of 2–10 μm. The specific surface area of carbon material was 579.69 m2/g, with the pore distribution predominantly microporous, accounting for 69.81 % of the total pore volume. It featured a higher degree of graphitization (ID/IG=1.06) and fewer surface oxygen-containing functional groups compared with coal direct liquefaction residue. Electrochemical testing showed that the electrical resistance of the carbon material was only 1.55 Ω, and the reversible capacity under a current density of 1 A/g was 96 mAh/g, which are superior to those of the existing commercial conductive carbon black. The microporous structure and higher degree of graphitization facilitate efficient electron transmission, while the lower content of surface oxygen functional groups effectively reduces electron transfer resistance. This work offers new insights into the structural design and performance enhancement of coal liquefaction residue-derived conductive carbon black functional materials. Furthermore, it has significant implications for the future development of conductive carbon black in energy saving and energy storage.

Controlling lamination and directional growth of β-sheets via hydrophobic interactions: The strategies and insights

The self-assembling morphologies of proteins, nucleic acids, and peptides are well correlated with their functioning in biological systems. In spite of extensive studies for the morphologies regulating, the directional control of the assembly morphology structure for the peptides still remains challenging. Here, the directional structure control of a bola-like peptide Ac-KIIF-CONH2 (KIIF) was realized by introducing different amount of acetonitrile to the system. The morphologies were characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the secondary structure was evaluated by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR). The results demonstrated that the introducing of different amount of acetonitrile has significantly tuned the hydrophobic interactions amongst the side chains, thus affecting the self-assembling morphologies. As acetonitrile content increased, the assemblies changed from nanotubes to helical/twisted ribbons and then to thin fibrils, with a steady decrease in the width. In contrast, the assemblies changed from thin fibrils to helical/twisted ribbons, and then to matured nanotubes, exhibiting a steady increase in the width with peptide concentration increasing. Complementary molecular dynamics (MD) simulations demonstrated the important role of acetonitrile in controlling the hydrophobic interactions, providing microscopic evidence for the structure transition process. We believe such observations provide important insights into the design and fabrication of functional materials with controlled shape and size.

Methods in molecular photocrystallography.

Over the last three decades, the technology that makes it possible to follow chemical processes in the solid state in real time has grown enormously. These studies have important implications for the design of new functional materials for applications in optoelectronics and sensors. Light-matter interactions are of particular importance, and photocrystallography has proved to be an important tool for studying these interactions. In this technique, the three-dimensional structures of light-activated molecules, in their excited states, are determined using single-crystal X-ray crystallography. With advances in the design of high-power lasers, pulsed LEDs and time-gated X-ray detectors, the increased availability of synchrotron facilities, and most recently, the development of XFELs, it is now possible to determine the structures of molecules with lifetimes ranging from minutes down to picoseconds, within a single crystal, using the photocrystallographic technique. This review discusses the procedures for conducting successful photocrystallographic studies and outlines the different methodologies that have been developed to study structures with specific lifetime ranges. The complexity of the methods required increases considerably as the lifetime of the excited state shortens. The discussion is supported by examples of successful photocrystallographic studies across a range of timescales and emphasises the importance of the use of complementary analytical techniques in order to understand the solid-state processes fully.

Modulation Excitation Spectroscopy: A Powerful Tool to Elucidate Active Species and Sites in Catalytic Reactions.

ConspectusA rational design of catalysts requires a knowledge of the active species and sites. Often, catalyst surfaces are dominated by spectators, which do not participate in the reaction, while the catalytically active species and sites are hidden. Modulation-excitation spectroscopy (MES) allows discrimination between active and spectator species by applying a concentration modulation, which is translated into the active (that is, actively responding) species by phase-sensitive detection (PSD).While MES has been known for a while, its combination with infrared spectroscopy (IR-MES) has been applied to the detailed mechanistic analysis of a wide range of supported metal and metal oxide catalysts only recently, used for catalytic reactions such as CO2 hydrogenation, water-gas shift, and CO and selective oxidation. The applicability of IR-MES is not limited to catalysis but has started to expand into other areas of research (e.g., gas sensing).In the context of renewable energy, CO2 hydrogenation has been a matter of intense mechanistic debate, despite its great importance for synthesis gas production and further processing to fuels and chemicals. Applying IR-MES to supported Cu and Au catalysts enabled us to discriminate between redox and associative mechanisms. While CO2 hydrogenation to CO and water follows an associative pathway with sequential H2 activation via hydrides and formation of carbon- and oxygen-containing intermediates, such as carbonates and formates, the reverse reaction, that is, the water-gas shift reaction, was shown to proceed via a redox mechanism including oxygen vacancy formation followed by reoxidation of the catalyst by CO2.Recent IR-MES studies on (supported) metal oxides have provided direct spectroscopic insight into the catalytically active sites during the selective oxidation of alkanes and alcohols. By further expanding the potential of IR-MES by transient isotopic exchange experiments, we were able to resolve the nuclearity-dependent vanadium and adsorbate dynamics of supported vanadia catalysts during oxidative dehydrogenation, highlighting the intimate interplay between the surface vanadia species and the support. The strong influence of the support material (ceria and titania) on the sequence of reaction steps provides an explanation for the different catalytic performance. Based on these mechanistic insights, the rational design of improved catalysts has been possible.Expanding the application of IR-MES to the area of gas sensing, as recently demonstrated for doped SnO2, provides access to enhanced mechanistic insight, including previously undetected surface species. Methodical challenges arising from background features associated with semiconductor metal oxides have been successfully tackled, supporting further expansion of IR-MES in the gas sensing community. Mechanistically, the application of IR-MES allows identification of the actively participating OH groups and adsorbed species (e.g., alkoxy, CO, carbonate) and monitoring of reaction sequences based on their temporal behavior, providing a level of understanding typically not accessible by steady-state methods.As outlined above, the combination of MES/PSD with IR spectroscopy constitutes a powerful approach for the identification of catalytically active species and sites, which is essential for a profound mechanistic understanding of surface reactions, greatly facilitating the rational design of catalysts and other functional materials.

Boosting peroxymonosulfate activation via Fe–Cu bimetallic hollow nanoreactor derived from copper smelting slag for efficient degradation of organics: The dual role of Cu

Valorization of iron-rich metallurgical slags in the construction of Fenton-like catalysts has an appealing potential from the perspective of sustainable development. For the first time, copper smelting slag (CSS) was utilized as the precursor to synthesize hollow sea urchin-like Fe–Cu nanoreactors (Cu1.5Fe1Si) to activate peroxymonosulfate (PMS) for chlortetracycline hydrochloride (CTC) degradation. The hyper-channels and nano-sized cavities were formed in the catalysts owing to the induction and modification of Cu, not only promoting the in-situ growth of silicates and the formation of cavities due to the etching of SiO2 microspheres, but also resulting the generation of nanotubes through the distortion and rotation of the nanosheets. It was found that 100 % CTC degradation rate can be achieved within 10 min for Cu1.5Fe1Si, 75 times higher than that of Cu0Fe1Si (0.0024 up to 0.18 M−1‧min−1). The unique nanoconfined microenvironment structure could enrich reactants in the catalyst cavities, prolong the residence time of molecules, and increase the utilization efficiency of active species. Density functional theory (DFT) calculations show that Cu1.5Fe1Si has strong adsorption energy and excellent electron transport capacity for PMS, and Fe-Fe sites are mainly responsible for the activation of PMS, while Cu assists in accelerating the Fe(II)/Fe(Ⅲ) cycle and promotes the catalytic efficiency. The excellent mineralization rate (83.32 % within 10 min) and efficient treatment of CTC in consecutive trials corroborated the high activity and stability of the Cu1.5Fe1Si. This work provides a new idea for the rational design of solid waste-based eco-friendly functional materials, aiming at consolidating their practical application in advanced wastewater treatment.

In-situ halloysite functionalization of anionic hybrid gels possessing easily implemented site-specific (alkyl)amide and carboxyl groups

Design of functional materials with tunable properties based on anionically-modified copolymer network of poly (N-isopropyl acrylamide-co-methacrylic acid) P(NIPA-co-MA) containing linear polyacrylamide and various amounts of Halloysite nanotubes (Hal) was presented using a facile route of solution casting. The organic/inorganic nanostructures based on thermo-responsive PNIPA were constructed to create hybrid materials via in situ polymerization with different Hal-loading and then used for the removal of cationic methylene blue (MB) dye from aqueous solutions. To achieve the desired mechanical property, the optimum composition of hybrids was determined following a simple and cost-effective synthesis procedure. In situ one-pot polymerization was promoted by semi-IPN formation, following a much simpler route than traditional preparation approaches for stable cross-linked hybrid formation. The swelling of hybrids decreased by 2.9-fold with loading of 5.40 % Hal, confirming the hydrogen bonding interactions between Hal and PAAm/P(NIPA-co-MA) network. The mechanical properties of Hal-doped hybrid gels showed an increase–decrease tendency with increase of Hal-content from 0.80 to 5.40 % (w/v) due to the high aspect ratio of Hal and strong secondary interactions between Hal and PAAm/P(NIPA-co-MA) chains. The effective cross-link density for Hal-doped hybrids was expressed by a cubic polynomial as a function of Hal concentration. Temperature-sensitive swelling results showed that the advantage of sustained release property of Hal can be combined with excellent controllability of PNIPA-based network. Adsorption results of MB onto Hal-doped hybrids bearing methacrylic acid moieties demonstrated their potential as efficient adsorbents for the removal of cationic dyes. A new route offered by the proposed procedure for design of hybrids containing “green” one-dimensional nanofillers creates an innovative perspective on robust hybrid structures for practical applications.

Pore engineering of Porous Materials: Effects and Applications.

Porous materials, characterized by their controllable pore size, high specific surface area, and controlled space functionality, have become cross-scale structures with microenvironment effects and multiple functions and have gained tremendous attention in the fields of catalysis, energy storage, and biomedicine. They have evolved from initial nanopores to multiscale pore-cavity designs with yolk-shell, multishells, or asymmetric structures, such as bottle-shaped, multichambered, and branching architectures. Various synthesis strategies have been developed for the interfacial engineering of porous structures, including bottom-up approaches by using liquid-liquid or liquid-solid interfaces "templating" and top-down approaches toward chemical tailoring of polymers with different cross-linking degrees, as well as interface transformation using the Oswald ripening, Kirkendall effect, or atomic diffusion and rearrangement methods. These techniques permit the design of functional porous materials with diverse microenvironment effects, such as the pore size effect, pore enrichment effect, pore isolation and synergistic effect, and pore local field enhancement effect, for enhanced applications. In this review, we delve into the bottom-up and top-down interfacial-oriented synthesis approaches of porous structures with advanced structures and microenvironment effects. We also discuss the recent progress in the applications of these collaborative effects and structure-activity relationships in the areas of catalysis, energy storage, electrochemical conversion, and biomedicine. Finally, we outline the persisting obstacles and prospective avenues in terms of controlled synthesis and functionalization of porous engineering. The perspectives proposed in this paper may contribute to promote wider applications in various interdisciplinary fields within the confined dimensions of porous structures.

AsTe3: A novel crystalline semiconductor with ultralow thermal conductivity obtained by congruent crystallization from parent glass

The synthesis of novel narrow-band-gap semiconductors with ultralow thermal conductivity opens a pathway to the design of functional materials with high thermoelectric performance or with interesting optical sensitivity in the infrared range. Here, we report on the discovery of the novel crystalline binary AsTe3 (c-AsTe3) prepared by spark plasma sintering (SPS) from full and congruent crystallization of amorphous AsTe3 (a-AsTe3) previously prepared by twin roller quenching. X-ray diffraction suggests that the structure of c-AsTe3 can be described as a superstructure of elementary Te with a specific distribution of As and Te atoms. More specifically, it appears as an intergrowth of a Te subunit (3 atoms) and As2Te5 subunit (6 As + 15 Te atoms) separated with interlayer spaces. The optical transmittance measured on both crystalline and amorphous AsTe3 indicates a maximum transmittance of 22 % over the infrared range 10–25 µm. Transport properties measurements, performed between 5 and 375 K, reveal that AsTe3 behaves as a lightly doped, p-type semiconductor. The complex crystal structure combined with a small-grain-size microstructure of the sample yields extremely low lattice thermal conductivity values of 0.35 W m−1 K−1 near 300 K. This poor ability to conduct heat is the main property that gives rise to an estimated dimensionless thermoelectric figure of merit ZT of ∼0.3 at 375 K. These findings show that the recrystallization of amorphous phases by SPS provides an effective approach for stabilizing novel phases with interesting functional properties.

Gem-Difluoroalkylation of Cyclic Ethers Enabled by Cobalt-Catalyzed C(sp3)-H Oxidation under Mild Conditions.

Fluorinated rings have emerged as privileged structural modules in the fields of drug discovery and materials research. The incorporation of fluorine atoms into aromatic rings or heterocycles can lead to significant improvements in the physicochemical and biological properties of small molecules, making them valuable components in the design of new drugs and functional materials. Herein, we presented a cobalt-catalyzed C-H oxidation/gem-difluorination cascade reaction of readily available cyclic ethers with difluoroenoxysilanes, affording a series of gem-difluorinated analogues with moderate to high yields. The obtained products as versatile fluoroalkyl building blocks were showcased through divergent-oriented transformations.

An orbital strategy for regulating the Jahn-Teller effect.

The Jahn-Teller effect (JTE) arising from lattice-electron coupling is a fascinating phenomenon that profoundly affects important physical properties in a number of transition-metal compounds. Controlling JT distortions and their corresponding electronic structures is highly desirable to tailor the functionalities of materials. Here, we propose a local coordinate strategy to regulate the JTE through quantifying occupancy in the [Formula: see text] and [Formula: see text] orbitals of Mn and scrutinizing the symmetries of the ligand oxygen atoms in MnO6 octahedra in LiMn2O4 and Li0.5Mn2O4. The effectiveness of such a strategy has been demonstrated by constructing P2-type NaLi x Mn1 - x O2 oxides with different Li/Mn ordering schemes. In addition, this strategy is also tenable for most 3d transition-metal compounds in spinel and perovskite frameworks, indicating the universality of local coordinate strategy and the tunability of the lattice-orbital coupling in transition-metal oxides. This work demonstrates a useful strategy to regulate JT distortion and provides useful guidelines for future design of functional materials with specific physical properties.

Accessing a Diverse Set of Functional Red-Light Photoswitches by Selective Copper-Catalyzed Indigo N-Arylation.

The ability to correlate the structure of a molecule with its properties is the key to the rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of the metastable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The lack of synthetic techniques to derivatize the abundant parent dye and a thorough understanding of the impact of structural factors on the photochemical and thermal properties hinder broad applications of this emerging photoswitch class. Herein, we report an efficient copper-catalyzed indigo N-arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for monoarylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N-aryl-N'-alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N-aryl substituents, while the N'-alkyl groups enable the independent attachment of functional moieties without affecting the photochromic properties. A strong correlation between the structure of the N-aryl moiety and the thermal stability of the photogenerated Z-isomers was achieved by multivariate linear regression models obtained through a data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules.

Independent Configuration and Reprogramming of Porous Characters in Macroporous Hydrogel Enabled by the Orthogonal Dynamic Network.

Macroporous hydrogels have attracted much attention in both industry and academia, where the morphological characteristics of pores are essential. Despite significant improvements on regulating porous structures, the independent configuration and reprogramming of porosity and pore size still remain challenging owing to the lack of a chemical design to decouple the mechanism for adjusting each characteristic. Here, we report a strategy to adaptively control porous features relying on an orthogonal dynamic network. Disulfide bonds are employed to relax polymer chains during freezing via UV irradiation, thus, generating pores in hydrogels. On such a basis, the porosity is continuously switched from 0 to 75% by controlling network relaxation ratios. Subsequently, the pore size is further reversibly manipulated through the association or dissociation of dynamic metallic coordination. As a result, the porosity and pore size achieved independent configurations. Meanwhile, the dynamic nature of the network makes it possible to reprogram the porous character of a prepared hydrogel. Beyond these, the photopatterning of pores represents the capability to regulate the third feature. Our strategy provides an effective way to arbitrarily manipulate porous morphologies, which can inspire the design of future functional porous materials.

Cu(II)-chelated ovalbumin mimicking the active centre of superoxide dismutase: Structure, antioxidant and antibacterial properties for food preservation application

Enzymatic browning and microbial contamination of food threaten food sensory and safety. With the development of green and healthy concepts, there is a greater need for efficient, low-carbon antioxidant and antimicrobial strategies. In this study, we designed a nano-enzyme with antioxidant activities and biocompatibility. By mimicking the active center of the natural SOD enzyme, copper (Cu) and ovalbumin (OVA) were self-assembled to form Cu-nano-polymerised sheet (Cu-NPS), in which OVA as a scaffold carries cofactors to create the active sites, making the nanoenzymes compatible with the antioxidant activity and antimicrobial properties of Cu, and at the same time possessing good stability and biocompatibility. These properties enable Cu-NPS to have a broader application range, for removing reactive oxygen species (ROS) and broad-spectrum sterilization. Subsequently, Cu-NPS was doped into carrageenan (Carr) to form a nanocomposite film, effectively inhibiting enzymatic browning and microbial contamination. In this work, protein-based mimetic enzymes as artificial nanoenzymes have advantages over natural enzymes, and the Cu-NPS with simple synthesis, high stability, and diverse properties, provides new ideas for the design of functional materials.

Recycling Clay Waste from Excavation, Demolition, and Construction: Trends and Challenges

The recycling of clay waste from construction debris highly depends on the chemical and mineralogical composition of the waste. Clays and clay minerals are known to be among marginal construction waste, representing an interesting opportunity and platform to produce other low-cost and low-carbon materials due to their possibilities for functional material design, such as adsorbents, drug delivery, catalysts and photocatalysts, and nanocomposites. The present review analyzes a wide variety of mechanisms for encapsulating organic and inorganic species between the layers of clay minerals. Through the compilation of advances in acid activation, exchange of inorganic cations, intercalation, and pillarization, new applications for clay materials are generated, paving the way to a nanometric world with functional, magnetic, adsorption, and catalytic capabilities. New trends are consolidated in the reuse of recycled clays in infrastructure projects, such as hydraulic concrete, water purification, soil fertility, pigments and paints, food packaging and storage, and ceramic appliances. It is concluded that clay waste is suitable to reuse in many industrial products and construction materials, enabling a reduction in the consumption of raw materials.

One-pot preparation of one-dimensional hierarchically porous carbon@SnO2 nanocomposites for flexible fabric-based supercapacitor electrodes

The design of functional energy storage materials with superior performances has become the focus topic with the growing energy crisis in recent years. Herein, porous carbon nanofibers@tin dioxide (PCNFs@SnO2) composites are prepared by one-pot electrospinning and followed by carbonization. The PCNFs@SnO2 possesses a hierarchically porous structure containing mesopores and micropores. The specific surface area is as high as ∼ 559.4 m2 g−1, and the total pore volume can reach 0.28 cm3 g−1. Meanwhile, the nonwoven fabric surface is coated with a silver layer through the screen printing technique to obtain silver-coated nonwoven fabric (SNF). Importantly, PCNFs@SnO2 and SNF are combined to obtain flexible fabric-based functional materials. As a primary energy application, the prepared PCNFs@SnO2/SNF electrode has a high mass specific capacitance of 583.1 F g−1 at 1 A g−1, a high area specific capacitance of 933 mF cm−2 at 1 mA cm−2, and a good rate capability (70 % at 10 A g−1). The supercapacitor device with two PCNFs@SnO2/SNF electrodes also shows outstanding cycling durability, capacitor retention is as high as ∼ 91.52 %, after 10000 charging/discharging cycles. In brief, our study may provide an innovative route for designing hierarchically porous one-dimensional carbon nanocomposites for supercapacitors with high performances.

Integrated Framework to Model Microstructure Evolution and Decipher the Microstructure-Property Relationship in Polymeric Porous Materials.

Unraveling the microstructure-property relationship is crucial for improving material performance and advancing the design of next-generation structural and functional materials. However, this is inherently challenging because it requires both the comprehensive quantification of microstructural features and the accurate assessment of corresponding properties. To meet these requirements, we developed an efficient and comprehensive integrated modeling framework, using polymeric porous materials as a representative model system. Our framework generates microstructures using a physics-based phase-field model, characterizes them using various average and localized microstructural features, and evaluates microstructure-aware properties, such as effective diffusivity, using an efficient Fourier-based perturbation numerical scheme. Additionally, the framework incorporates machine learning methods to decipher the intricate microstructure-property relationships. Our findings indicate that the connectivity of phase channels is the most critical microstructural descriptor for determining effective diffusivity, followed by the domain shape represented by curvature distribution, while the domain size has a minor impact. This comprehensive approach offers a novel framework for assessing microstructure-property relationships in polymer-based porous materials, paving the way for the development of advanced materials for diverse applications.

Thermodynamic modeling of Bi2Te3 in the defect energy formalism

Bi2Te3 is a promising thermoelectric material that is often touted as one of the best-performing low-temperature thermoelectric materials. As a result, it has been widely used commercially, both for clean energy generation and in cooling devices. Like many other thermoelectric materials, defects play a key role in the performance of Bi2Te3. As a result, numerous studies have attempted to experimentally and computationally map out the dominant defects in the phase, these include efforts to determine the dominant defect, estimate defect energies, and predict their concentration. The computer coupling of phase diagrams and thermochemistry (CALPHAD) is one of many tools under the auspices of the materials genome initiative (MGI) that enables the rapid design of new functional materials with improved properties. The Defect energy formalism (DEF) with a charged sublattice, an offshoot of the Compound energy formalism (CEF), provides a way to directly include first-principle defect energy calculations into CALPHAD descriptions of solid phases. The introduction of the charge sublattice enables the estimation of the free carrier concentrations in the phase. Here we apply the DEF to the Bi2Te3 system, emphasizing the robustness of the DEF in describing meaningful endmembers and the elimination of fitting parameters. Unlike previous assessments using the Wagner–Schottky defect model, we include the description of the charged defects in our assessment. The DEF with a charged sublattice provides a good prediction of the non-stoichiometry of the phase when compared with experimental data and also predicts a thermodynamic defect concentration at low temperature that is physically reasonable.

Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles.

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with the intricate structure of biopolymers, generating versatile biomimetic materials. The mobility of polymer chain segments at length scales similar to secondary structural elements in proteins is critical to SCNP structure and thus function. However, the influence of noncovalent interactions used to form SCNPs (e.g., hydrogen-bonding and biomimetic secondary-like structure) on these conformational dynamics is challenging to quantitatively assess. To isolate the effects of noncovalent interactions on SCNP structure and conformational dynamics, we synthesized a series of amphiphilic copolymers containing dimethylacrylamide and monomers capable of forming these different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine acrylamide that forms hydrogen-bonds but lacks a defined local structure, and (3) benzyl acrylamide that has the lowest propensity for hydrogen-bonding. Each SCNP formed folded structures comparable to those of intrinsically disordered proteins, as observed by size exclusion chromatography and small angle neutron scattering. The dynamics of these polymers, as characterized by a combination of dynamic light scattering and neutron spin echo spectroscopy, was well described using the Zimm with internal friction (ZIF) model, highlighting the role of each noncovalent interaction to additively restrict the internal relaxations of SCNPs. These results demonstrate the utility of local scale interactions to control SCNP polymer dynamics, guiding the design of functional biomimetic materials with refined binding sites and tunable kinetics.