Ammonium dinitramide (ADN) is a promising halogen-free ionic energetic oxidizer for advanced solid propellants. Its dissolution involves ion-pair dissociation, competitive cation/anion solvation, and local solvent-stabilized ion-pair structures. However, solubility studies of energetic materials have mainly focused on molecular compounds, leaving the solvent-dependent dissolution mechanism of ionic energetic salts insufficiently understood. In this work, the solid–liquid equilibrium solubility of ADN was measured in nine pure organic solvents, including methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, acetone, acetonitrile, and tetrahydrofuran (THF), from 283.15 K to 323.15 K. The experimental data were correlated using the van’t Hoff, modified Apelblat, Buchowski–Ksiazczak λ-h, and NRTL models, followed by apparent thermodynamic analysis. To clarify the molecular origin of the solvent effect beyond conventional solubility correlation, an integrated multiscale computational strategy combining continuum-solvation calculations, alchemical free-energy perturbation, electrostatic potential analysis, explicit-solvent molecular dynamics simulations, and MD-derived cluster DFT calculations was constructed for ADN. This framework evaluates solvent effects from complementary perspectives, including continuum electrostatic stabilization, single-ion solvation, local ion-pairing behavior, first-shell solvation structure, and finite-cluster electronic stability. The results showed that single-ion solvation or continuum electrostatic descriptors alone are insufficient to reproduce the experimental solubility trend, highlighting the necessity of explicit local solvation and ion-pair structural analysis. These findings establish a molecular-level link between macroscopic ADN solubility and local ion-pairing/solvation structures, providing a basis for solvent screening and crystallization process design of ADN and related ionic energetic salts.

The crystallization separation of biomass chemical crystals in high-viscosity aqueous solutions has long been a major challenge in the field of biomass refining. Inappropriate crystallization strategies render the prepared biomass prone to caking and subsequent deterioration. To address this challenge, a tailored model-based two-stage crystallization strategy for viscous systems was developed for anti-caking bio-based derivative crystal production. The first stage focused on nucleation to prepare seed crystals with good dispersion in viscous solutions, while the second stage inhibits nucleation to design the crystal product size. Meanwhile, a temperature-governed crystallization kinetic model and a humidity-driven caking model were coupled to develop a crystallization-caking feedback regulation framework, enabling direct generation of optimal crystallization trajectories based on predefined anti-caking targets. In the crystallization of glucono delta-lactone (GDL), compared with the previous anti-caking crystallization strategies, the crystal D50 obtained by the crystallization strategy for viscous systems developed in this study increased from 414 to 486 μm, and the deviation of crystal products from the target particle size decreased from 17.2% to 2.8%. While the anti-caking performance has improved from 27 to 48 days, the design efficiency has also increased by an order of magnitude.

Solar driven photocatalytic water splitting, which mimics plant photosynthesis, is regarded as the prevailing and realistic technology for sustainable future development. One category of photocatalysts is heterojunction photocatalysts, which are formed by two distinct semiconductor materials. In this study, a photocatalyst featuring a heterojunction between a sandwich-like CdZnS (CZS) coated carbon hollow sphere and nano TiO2 has been proposed and successfully synthesized through a hydrothermal process. The carbon nano sphere works not only as supporting structural materials to enlarge photocatalyst surface area, but also as charge conducting intermediate. The CdZnS is capable of generating electron-hole pairs under visible-light excitation. Upon forming a heterojunction with TiO2, the hydrogen generation performance is significantly enhanced. The photocatalytic hydrogen generation performance of the samples with and without heterojunction was 9.29 mmol g−1 h−1 and 18.5 mmol g−1 h−1 under visible light illumination, respectively. Through the assistance of various characterization techniques and detailed analysis, a possible photocatalytic mechanism has been proposed. Consequently, this novel heterostructure is expected to inspire future designs for hydrogen evolution photocatalysts.

As one of the essential amino acids, l-isoleucine tends to crystallize in flaky crystals, yielding low bulk density and poor flowability, hindering downstream processing. While previous studies utilized hydroxypropyl methylcellulose (HPMC) to induce spherulitic growth of l-isoleucine by adsorbing onto its dominant crystal face, there is still significant potential for improvement in the bulk density and sphericity of the prepared spherulites. In this work, we systematically screened a series of amino acids (small molecules) and cellulose derivatives (polymeric molecules) as additives based on their differences in molecular functional groups. The results of scanning electron microscopy, atomic force microscopy, and specific surface area tests indicated that under the same additive type, strong hydrophilic groups and larger molecular volumes were conducive to the roughening of the dominant hydrophilic (001) crystal face of l-isoleucine and promoted the formation of dense spherulites through non-crystallographic branching. Molecular dynamics simulations further demonstrated that the changes in solution viscosity caused by polymeric additives also significantly affected the spherulitic growth of l-isoleucine. By rationally selecting additives, the bulk density of l-isoleucine spherulites was increased to 0.573 g mL-1, which is 39.8% higher than what has been reported, and the sphericity reached 0.894. This study reveals the mechanism of the molecular structure of additives on the spherulitic growth of l-isoleucine, which is conducive to guiding the spherulite design of flaky organic molecular crystals.

Magnesium citrate nonahydrate (MCN) is a highly effective magnesium supplement that has gained significant popularity in the food and pharmaceutical industries. This is highly attributable to its distinctive chemical structure and its high degree of biocompatibility. In contrast, the utilization of commercial MCN is constrained by its irregular morphology and particle size distribution. In this study, MCN particles were successfully produced. In accordance with the principles of Lifshitz-van der Waals acid-base theory, the adhesion free energy of MCN in water, ethanol, and formamide systems was calculated. Based on the result, water-based solvents were selected as the solvent system for spherical agglomeration. Subsequent analysis elucidated the agglomeration mechanism of MCN in aqueous systems. Furthermore, the crystallization process of MCN were systematically investigated. The optimal process parameters were determined, including seed loading, seed size, initial concentration, stirring rate and temperature. The MCN products exhibited a 20% decrease in the angle of repose, a 39% reduction in the coefficient of variation, and a 60% decline in caking-ratio, thereby substantiating their enhanced quality. This study provides valuable data support and novel insights for the production of high-quality MCN crystals.

ABSTRACT Circularly polarized luminescence (CPL) has emerged as a cornerstone technology for next‐generation chiral photonic applications. However, a fundamental trade‐off between the luminescence dissymmetry factor ( g lum ) and photoluminescence quantum yield (PLQY) has remained the primary bottleneck preventing the widespread practical deployment of CPL materials. Herein, we report a breakthrough solution to this long‐standing problem through a rational synergistic design that combines highly emissive copper(I) iodide clusters with chiral cellulose nanocrystal (CNC) photonic templates. The synthesized Cu 4 I 4 (2,5‐DMePi) 2 clusters exhibit an ultrahigh PLQY of 97.20% and excellent stability, allowing their facile integration into flexible polymer films. By constructing a bilayer architecture consisting of the emissive Cu–I cluster film and a left‐handed chiral nematic CNC template, we achieve the CPL performance that simultaneously delivers a near‐unity PLQY and a large g lum value of −0.9421. Most strikingly, the CPL sign can be reversibly switched between −0.9421 and 0.1021 simply by changing the observation direction. These direction‐tunable bilayer films with multimodal optical features are ideal for advanced optical anti‐counterfeiting. Collectively, this work not only breaks the fundamental g lum factor‐PLQY trade‐off but also provides a generalizable strategy for the design of next‐generation high‐performance CPL materials.

Ammonium dinitramide (ADN) is a high-energy green oxidizer that holds significant promise for application in solid propellants with low signature; however, its practical application is limited by strong hygroscopicity. Preparing spherical particles is generally considered the prior method for ADN anti-hygroscopic modification and its scale-up preparation. Conventional techniques of preparing spherical ADN typically involve high-temperature melting processes, which entail considerable operational risks. In this study, ADN spherical particles with high sphericity, good powder properties, and adjustable particle size distribution were successfully prepared using a quasi-emulsion solvent diffusion spherical crystallization technology. The spherical products exhibit 47.6 % lower saturated moisture absorption ratio at 25 degrees C with a relative humidity of 53 % and 96.1 % lower caking strength after one week of storage under low-humidity conditions compared to the raw materials of ADN, which confirms the improved anti-hygroscopic performance and anti-caking ability. More importantly, the operating temperature of this process can be substantially reduced to 25 degrees C, representing a 73.1 % decrease compared to the melting temperature of ADN (93 degrees C). This work presented a novel technique for the safe production of highquality ADN spherical particles, laying a foundation for their potential application in solid propellants.

The widespread adoption of electric vehicles is critically constrained by the limited energy density and cycle life of lithium-ion batteries. Nickel-rich layered oxides (NRLOs) are promising cathodes due to their high specific capacity, yet increasing nickel content introduces severe bulk structural instability and interfacial degradation that hinder practical deployment. To overcome this stability-capacity trade-off, this study proposes a high-entropy rock-salt (HERS) strategy. By introducing trace amounts of high-valence cations (Zr4+, V5+ and W6+), a self-limiting, ultra-thin (2 nm) HERS layer is engineered on the surface of spherical polycrystalline LiNi0.83Co0.11Mn0.06O2 (NCM83) while maintaining a high nickel content. In-situ characterization and theoretical calculations confirm that the HERS layer enhances structural stability by improving the reversibility of the H2-H3 phase transition and suppressing lattice oxygen loss, thereby mitigating microcrack formation and alleviating electrolyte corrosion, ultimately leading to improved electrochemical stability. Consequently, the modified NCM83 delivers an initial discharge capacity of 212.9 mA h g−1 at 0.1 C, retaining 78.0% capacity after 500 cycles at 5 C. Remarkably, it preserves 59.3% of its capacity after 1000 cycles, corresponding to a 63.8% improvement and nearly double the final specific discharge capacity compared to unmodified NCM. With excellent rate capability and cycle stability, this entropy-driven epitaxial reconstruction offers an effective route to combining high capacity with long-term durability in nickel-rich cathodes, offering new insights for the design of next-generation high-energy lithium-ion batteries.

In high-temperature and high-humidity environments, microelectronic chips are inevitably subjected to both electrochemical corrosion and electromigration. The coupling between electromigration and electrochemical corrosion, and how they contribute to the failure of microelectronic interconnects, remains poorly understood. This paper presents a unified phase-field model that incorporates the combined effects of electromigration and electrochemical corrosion, along with electro-thermo-mechanical factors such as stress corrosion cracking, Joule heating and stress-induced migration. Using this model, the evolution of semicircular and triangular notches in interconnects under electrical and mechanical loads is systematically studied. A comparative analysis under uniaxial tension and compression reveals that, under tensile loading, the failure rate due to crack propagation in the coupled model is significantly higher than the sum of the failure rates from pure electromigration and electrochemical corrosion. In contrast, under compressive loading, the failure rate in the coupled model is predominantly governed by electromigration. These findings reveal the key role of stress in regulating the coupling between the electromigration and electrochemical corrosion.

Sorption-induced deformation is widely observed in nanoporous materials. However, the fundamental mechanisms that govern this behavior remain only partially elucidated, and a generally accepted predictive modeling framework is still lacking. In this review, we synthesize the current state of knowledge by examining experimental findings, theoretical formulations, and numerical simulation techniques relevant to sorption-induced deformation in porous media. To begin with, experimental studies on both mesoporous and microporous systems are summarized, revealing that the deformation response strongly depends on pore size, thereby pointing to distinct physical mechanisms operating at different scales. Subsequently, theoretical approaches that have been developed to rationalize sorption-induced deformation are considered. These models aim to describe adsorption-induced stresses originating from a variety of microscopic processes and to incorporate them into macroscopic constitutive relations capable of predicting the resulting deformations. Furthermore, numerical strategies devised to simulate this coupled phenomenon are outlined, encompassing methodologies that vary according to the scale of the pores and the level of material description. Ultimately, by assessing the current achievements and limitations, the review highlights persisting knowledge gaps and identifies critical directions for future research into sorption-induced deformation.

Macallisterite, a functional material with excellent properties, is widely used in industries. However, the rapid synthesis of high-purity macallisterite with both high yield and uniform morphology remains challenging due to the complex polymerization of borate species during the production process. Herein, we propose a novel magnesium ion-induced strategy for the efficient synthesis of macallisterite by combining sonochemistry assistance and additive method. The polymerization mechanism of borate species under excess magnesium salts was investigated using Raman spectroscopy and DFT. It has been shown that chloride magnesium is the optimal inducer for the macallisterite synthesis as Cl- exhibits lower electrostatic interaction and spatial steric hindrance than SO42- and NO3-. Sonochemical assistance significantly accelerated the nucleation and crystallization of macallisterite through kinetic conditions created by cavitation effects. Accordingly, the crystallization is promoted achieving a maximum yield of 97.92%. Raman and DFT study revealed that Mg2+ ions can effectively induce the formation of the stable neutral complex cluster [Mg(H2O)4(B6O7(OH)6)] in the supersaturated solution, which lowers the reaction activation energy through charge transfer and coordination. Furthermore, dense macallisterite spherulites with uniform morphology and high purity can also be achieved by using sodium dodecyl sulfonate (SDS) as additive. Based on these findings, this study not only elucidates a metal ion-induced crystallization mechanism but also establishes an efficient, green, and scalable synthetic route for high-quality macallisterite.

The interlaminar tensile strength (ILTS) is one of the most crucial mechanical properties regulating the performance of ceramic matrix composites (CMC). In this study, we propose a novel method for measuring ILTS based on three-point bending tests, which is validated through finite element (FE) simulations. The method involves bonding stacked laminates to achieve a composite beam, effectively avoiding the difficulty arising from manufacturing thick laminates. By employing this innovative approach, the ILTS of CMC reinforced by carbon fiber is successfully measured. In addition, scanning electron microscopy (SEM) and acoustic emission (AE) systems are utilized to investigate the failure patterns and processes. The results show that the ILTS values obtained through the developed method are both accurate and reliable, offering a practical approach for ILTS measurement. Besides, the study reveals that the failure in CMC laminates is primarily driven by delamination, which is attributed to the debonding between the fibers and the matrix. The damage is mainly characterized by cracking of the ceramic matrix, while the carbon fibers remain largely undamaged.

Customized production of high-end functional sugars is greatly limited due to the lack of quantitative correlation between the content of homologous impurities in impure syrup and the optimized crystallization operating profiles. Using alpha-Anhydrous Glucose as the model substance, this work presents a crystallization size control model considering the presence of impurity, aiming to generate an optimized cooling trajectory to achieve the design of custom-sized sugar crystals. Validation and comparison experiments showed that the glucose of target size with an advantage in anti-compression and anti-caking during the storage and transport process can be obtained through cooling trajectory generated by the proposed model. This model-based control strategy can provide an opportunity to find optimal cooling trajectory by balancing the relationship between cooling time and seed loading to meet demands of both product functionality and human manufacturability.

Copper(I) iodide clusters are emerging as a new generation of multi-color circularly polarized luminescence (CPL) materials due to their exceptional luminescent properties and tunable electronic characteristics. However, the substantial decrease in photoluminescence quantum yield (PLQY) during emission color tuning has remained a major challenge for developing high-performance CPL materials. Herein, diverging from conventional ligand-involved charge-transfer mechanisms for color tuning, we employ structurally related aliphatic ligands to reduce ligand-involved contributions and promote cluster-centered emission mainly associated with the inorganic [Cu4I4] core. Subtle ligand modifications preserve the rigid [Cu4I4] cluster framework while reinforcing hydrogen-bonding networks, inducing variable compression of Cu-Cu distances, enabling continuous emission tuning from green (550 nm) to red (633 nm) while maintaining ultrahigh, near-unity PLQY. Moreover, the introduction of chiral ligands induces CPL activity with a luminescence dissymmetry factor (glum) reaching 2.3 × 10- 3. These remarkable performances render these Cu-I clusters promising for anticounterfeiting and encryption applications. Overall, this work demonstrates the integration of near-unity PLQY with tunable CPL in metal hybrid clusters, providing a new strategy for high-performance multicolor CPL materials.

The combination of porous polymeric materials with nanodrugs is a promising approach for oral hydrophobic drug delivery. This study aims to establish a novel method for preparing composite hydrogels laden with drug nanocrystals using oiling-out crystallization, eliminating the need for organic solvents and overcoming limitations of traditional methods such as harsh operating conditions and high solvent residues. Using fenofibrate as model drug, a composite hydrogel with fenofibrate crystal size of 960 nm and drug loading of 58 % was prepared. Compared to commercial powders, the composite hydrogel reduced the dissolution time required for 70 % cumulative release by 89.17 % and exhibited excellent controlled-release performance across various pH environments. Unlike traditional organic solvent-based method, which leave anisole residues exceeding safety limits by over 3.5-fold, this method avoids the use of biohazardous solvents, saving at least 1.25 mL/g of fenofibrate produced. In addition, the method was successfully extended to nimodipine to demonstrate its universality.

In this paper, the defect evolution caused by electromigration induced surface diffusion in interconnects is investigated using a newly-developed electro-thermo-mechanical coupling phase-field model. The Joule heat and its resulting thermomigration are included into the phase-field model. The governing equation of the phase-field is solved by semi-implicit spectral methods and the accompanied governing equations of applied physics fields are solved by finite volume methods. Comparative investigation into defect evolution with and without the influence of Joule heating is conducted. It is deduced that thermomigration facilitates local elongation of the defect in the “current crowding” region and exerts a substantial influence on the defect morphological evolution. Subsequently, the effect of the inclination angle of the electric field on the void morphology evolution and crack propagation is discussed. We find that the defect achieves the largest characteristic length when the electric field direction is perpendicular to the uniaxial tension direction, implying a higher threat to the circuit safety. This study may help to deepen people's understanding of how the thermal effect functions in electromigration process and sheds light on different modes of defect evolution in interconnects.

Polymeric carbon nitride (C3N4) has emerged as a promising candidate for hydrogen peroxide (H2O2) photosynthesis due to its excellent physicochemical stability, facile synthesis procedure, and favorable electronic structure. Nevertheless, the photocatalytic activity of pristine C3N4 is severely limited by poor carrier transport capability and sluggish catalytic reaction kinetics. Herein, an in-situ co-modification strategy was developed to synthesize a highly active C3N4 catalyst with phosphorus/potassium (P/K) co-doping and cyano (CN) group functionalization. The intercalated K+ ions form strong K-N bonds that bridge the adjacent melon chain-like frameworks, thus enhancing the crystallinity of C3N4, which promotes exciton dissociation and facilitates the separation and transport of photogenerated charge carriers. Moreover, the induced CN groups serve as active sites that effectively enhance the pi*-pi* coupling between *OOH and the C3N4 substrate, thus accelerating the reaction kinetics of the *OOH -> *H2O2 step during the oxygen reduction reaction (ORR). More importantly, the synergistic effect of the P-induced gap state and the geometric distortion caused by K+ ions facilitates strong pi*-pi* coupling between the *OO intermediate and the substrate, thereby promoting the injection of photoexcited electrons into O2. This significantly improves the conversion efficiency of *OO to *OOH (the rate-determining step of the ORR), thereby substantially enhancing the overall photocatalytic activity. Consequently, the modified C3N4 catalyst exhibits a 7.5-fold higher photocatalytic H2O2 production rate than that of pristine C3N4.

The inadequate understanding of multisource water migration during the drying of wet hydrate crystals often results in the loss of the anti-caking function. Taking glucose monohydrate as a case, this work traced the water migration of wet hydrate crystals during the drying process, elucidated the essential relationship between water migration and the caking resistance of products and put forward the optimal drying scheme based on the caking behavior. Experiments and simulations indicate that the free water on the crystal surface escapes first, resulting in high caking resistance. Subsequently, the remaining free water and crystal lattice water escape, collapsing the crystal. While physically destroying the crystal morphology, the crystal form also changes. Both of them can accelerate caking. Based on the understanding of water migration and caking behavior, the optimal drying scheme for wet glucose monohydrate crystals was proposed as drying at 60 degrees C for 25 minutes to control the total water content close to the theoretical crystal water content (9.09 wt%). The knowledge obtained can guide the design of drying schemes for retaining the anti-caking function and competitive marketability of hydrate crystals.

Metal sulfides are promising anode candidates for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their practical application is limited by significant volume extension and sluggish Na+ diffusion during cycling, which lead to rapid capacity degradation and poor long-term stability. In this work, we report the rational design of a hollow triple-shelled high-entropy sulfide (NaFeZnCoNiMn)9S8, synthesized through sequential templating method under hydrothermal conditions. Transmission electron microscopy confirms its well-defined three-shelled architecture. The inter-shell voids effectively buffer Na+ insertion/desertion-induced volume extension, while the tailored high-entropy matrix enhances electronic conductivity and accelerates Na+ transport. This synergistic design yields outstanding performance, including a high initial Coulombic efficiency (ICE) of 94.1% at 0.1 A g-1, low charge-transfer resistance (0.32~2.54 Ω), fast Na+ diffusion efficiency (10-8.5-10-10.5 cm2 s-1), and reversible capacity of 582.6 mAh g-1 after 1600 cycles at 1 A g-1 with 91.2% capacity retention. These results demonstrate the potential of high-entropy, multi-shelled architectures as a robust platform for next-generation durable SIB anodes.