Physics

ABSTRACT The growing demand for dynamic electromagnetic wave control has accelerated the development of programmable metasurfaces. However, conventional approaches that rely on active components such as pin diodes, varactor diodes, and liquid crystals often suffer from limited modulation depth, poor scalability of unit cells, complex driving circuitry, and high power consumption, making it challenging to balance hardware cost with precise wavefront manipulation. Here, we propose a novel strategy for large‐scale pixel‐level reconfigurable Pancharatnam–Berry (PB) phase at the subwavelength scale, enabled by dislocation‐sensitive near‐field coupling in bilayer isotropic meta‐disks. To realize this, a progressive optimization algorithm is developed to efficiently encode multiple wavefronts into the local offset parameters of meta‐disks relative to their respective lattice centers. Numerical simulations based on a theoretical simplified model predict up to 18 holographic channels using a 300 × 300 meta‐disk design. Meanwhile, 6‐channel holographic projection with dynamic switching via global translation of one layer at a one‐lattice interval is experimentally validated using a fabricated 82 × 82 meta‐disk sample. Our work outlines a new paradigm in reconfigurable metasurfaces, with broad potential applications in wireless communications, holographic displays, data storage, and information encryption.

ABSTRACT The integration of rapid on‐site screening with precise quantification is critically important for the diagnosis of urinary tract infections (UTIs). However, current detection methods often struggle to balance between screening efficiency and quantitative accuracy. Herein, we first report a colorimetric‐terahertz (THz) dual‐mode sensing platform powered by CeO 2−x /Au nanospheres for pathogenic bacteria in UTIs. The engineered CeO 2−x /Au nanospheres exhibit outstanding peroxidase‐like activity and dielectric response under the strong localized field enhancement of THz metamaterial, establishing a sequential activation dual‐signal output mechanism. Rapid preliminary screening of pathogens is realized via smartphone image recognition by utilizing CeO 2−x /Au nanospheres unbound from bacterial surfaces to catalyze colorimetric reactions. Subsequently, the bacteria‐conjugated nanospheres trigger significant changes in the local dielectric environment, leading to distinct frequency shifts that enable precise quantification in THz mode, with limit of detection (LOD) values for common UTI pathogens ranging from 4.58 to 9.31 × 10 2 CFU/mL. This strategy enables rapid positive/negative discrimination and accurate quantification of bacterial loads in positive samples, achieving outstanding classification (AUC = 0.993) for 75 clinical urine samples. Enabled by CeO 2−x /Au composite nanospheres, the dual‐mode platform with affordability (∼$6.8) and time‐efficiency (<1 h) demonstrates potential for UTI diagnosis across diverse scenarios through a tiered approach.

ABSTRACT Strontium stannate perovskite (SrSnO 3 ) is emerging as a promising material for next‐generation ultra‐wide bandgap (UWBG) semiconductors due to its high electron mobility and optical transparency. However, despite the critical importance of defect analysis to utilize La‐doped SrSnO 3 as a semiconductor channel material, the energy distribution of sub‐gap states has not yet been sufficiently elucidated under bias conditions. In this work, we fabricated La‐doped SrSnO 3 top‐gate metal‐oxide‐semiconductor field‐effect transistors (MOSFETs) and characterized them under multi‐wavelength light ranging from 300–900 nm, quantitatively extracting the trap density over a wide range of energy spectra. The transient decrease in transmittance observed at 400 nm correlates with subthreshold swing degradation, revealing deep donor‐like traps as the dominant trap states. Notably, despite the presence of traps, La‐doped SrSnO 3 exhibits excellent optical durability with minimal threshold voltage fluctuations under multi‐wavelength illumination. The resulting fabricated MOSFETs achieved a high on/off current ratio (∼10 11 ), showing competitive performance and stability compared to previously reported oxide semiconductors. This work establishes an analytical framework for precisely unveiling the trap‐dominated behavior of SrSnO 3 and proposes essential design guidelines for the development of high‐reliability power and optoelectronic devices based on next‐generation UWBG perovskite semiconductors.

ABSTRACT Deep eutectic gel electrolytes (DEEs) based on amide‐Li + Lewis acid‐base coordination are promising for lithium metal batteries, yet they suffer from parasitic hydrogen evolution from reactive N‐H groups, poor interfacial stability, and inherent flammability. Here, we report a rationally designed tertiary amide deep eutectic gel electrolyte (PLDF‐GPE) by replacing conventional primary/secondary amides with N, N‐diethyltrifluoroacetamide and N, N‐dimethylacrylamide, thereby eliminating active N‐H hydrogen atoms, suppressing hydrogen evolution at the Li anode interface while maintaining a robust C═O…Li + coordination network that ensures deep eutectic behavior. The tertiary amide design exhibits a temperature‐responsive solvation structure that dynamically adjusts Li + coordination to lower desolvation barriers, enabling stable operation over a wide temperature range (−20°C to 80°C). Crucially, the fluorine‐ and nitrogen‐rich components preferentially decompose to form a LiF/Li 3 N‐enriched SEI/CEI that enhances interfacial compatibility. Moreover, PLDF‐GPE generates N─C═O• and F• radicals during combustion, which combine with active hydrogen radicals (H•) and impart intrinsic non‐flammability. Consequently, Li||Li symmetric cells achieve 1800 h of stable cycling, Li||NCM811 cells retain 65.7% capacity after 600 cycles at 0.25 C, and Li||LiFePO 4 cells operate reliably at an extreme temperature of 160°C. This molecular design strategy offers a transformative pathway toward safe, wide‐temperature lithium metal batteries.

ABSTRACT Melanin is a ubiquitous pigment that mitigates photoinduced damage in biological systems through light absorption, heat dissipation, and radical scavenging. While these functions have traditionally been considered independent, recent studies suggest that they may be intrinsically coupled, with radical scavenging activity enhanced with light irradiation. However, the underlying photophysical mechanism remains unclear. Here, we present the first comprehensive wavelength‐dependent comparison of representative eumelanin (cephalopod‐ink‐derived melanin and polydopamine) and allomelanin (fresh and oxidized DHN melanins) spanning UV, visible, and near‐infrared excitation regimes. By combining radical scavenging assays, ultrafast transient absorption spectroscopy, and electron paramagnetic resonance spectroscopy, we demonstrate that light‐enhanced radical scavenging is a universal yet strongly excitation‐energy‐dependent behavior across chemically distinct melanin classes. We further identify the breadth of the excited‐state absorption (ESA) manifold and ESA‐to‐bleach ratio, and not excited‐state lifetime nor photoinduced semiquinone‐like radical accumulation, as the photophysical descriptors most closely associated with scavenging enhancement. These findings establish a unified framework linking excited‐state photophysics, photochemical redox activity, and photoprotection functions of melanins.

ABSTRACT Dual‐mode afterglow emission is a notable photoluminescent phenomenon in which materials exhibit prolonged luminescence via thermally activated delayed fluorescence (TADF) and phosphorescence. Developing such dual‐mode materials through a simple preparation process is inherently difficult and presents technical hurdles. Here, we fabricate a series of afterglow hybrids through thermal treatment of dihydrogen phosphates with fluorescein derivatives. A hybrid composed of Al(H 2 PO 4 ) 3 and fluorescein (FL) show visible‐light‐excited green afterglow lasting for 5 s at 298 K and yellow afterglow lasting for 11 s at 243 K. Additionally, introducing heavy atoms into fluorescein induces afterglow hybrids to achieve dual‐mode afterglow emission at room temperature. Notably, the afterglow hybrids exhibit wider singlet‐triplet energy gaps (ΔE ST > 0.3 eV). Various applications such as afterglow thermometers, 7D encryption, model painting, latent fingerprint identification, and gastric mucosal staining can be realized through solution process, driven by the high luminescent intensities, multicolor afterglow, and temperature tunability. Our hybridization strategy not only discovered a novel matrix for preparing afterglow materials but also expanded its applications in bio‐imaging and multi‐stimuli response.

ABSTRACT Highly efficient Eu 2+ ‐activated phosphors are indispensable for solid‐state lighting, yet the parasitic Eu 3+ emission remains a significant efficiency killer. Herein, we report a robust strategy to suppress Eu 3+ formation in Li 2 CaSiO 4 :Eu 2+ via a heterovalent substitution strategy by combining a two‐step sintering process with charge compensation. We effectively promote the Eu 3+ →Eu 2+ reduction, boosting the external quantum efficiency (EQE) from 22% to 60%, and the deep defect levels induced by Si 4+ ‐P 5+ heterovalent substitution impart superior thermal stability to Li 2 CaSi 0.96 P 0.04 O 4 :Eu 2+ (94%@423 K), while retaining a remarkable 98% of its initial intensity after 30 days of water immersion. The as‐fabricated phosphor‐converted light‐emitting diodes achieve a high color rendering index ( R a = 90.6) and a 50% reduction in blue‐light hazard, demonstrating great potential for healthy illumination. Notably, this Eu 2+ stabilization strategy also effectively enhances the emission intensity of Li 2 CaGeO 4 :Eu 2+ and Li 2 MSiO 4 :Eu 2+ (M = Sr, Ba), thus establishing a general paradigm for the rational design of high‐performance phosphors for next‐generation light sources.

ABSTRACT Solid state conversion electrodes are promising for aqueous energy storage but are frequently constrained by sluggish interfacial kinetics, leading to a persistent energy‐power trade‐off and underutilized capacity at high rates. Here we propose a chemical mediation strategy in which dissolved [Fe(CN) 6 ] 4− /[Fe(CN) 6 ] 3− couples continuously regenerate an interfacial oxidant to chemically drive the α‐Co(OH) 2 to CoOOH conversion, thereby rewriting the rate limiting solid state electrochemical step into an electrochemical‐chemical cascade at the electrode/electrolyte interface. Electrochemical analyses and spectroscopy corroborate the spontaneous oxidative phase transformation and the mediator enabled pathway reconstruction beyond simple solid–liquid capacity superposition. To make this capacity boosting strategy practically efficient, we further tune the initial redox composition of the mediator couple to suppress shuttle driven self‐discharge while maintaining fast interfacial conversion kinetics, as quantified by multi‐potential‐step measurement (MPSM) and visualized by in situ Raman mapping. Consequently, the redox‐enhanced alkaline Zn‐Co battery exhibits a remarkable areal capacity of 0.98 mAh cm −2 (a 96% enhancement), while simultaneously retaining a high energy density of 0.92 mWh cm −2 and an ultrahigh‐power density of 75 mW cm −2 . This work highlights a functional electrolyte design route to unlock deep solid state conversion capacity under high‐power operation in aqueous batteries.

In the original version of the Research Article “Simple technologies and diverse food strategies of the Late Pleistocene and Early Holocene at Huaca Prieta, Coastal Peru” by T. Dillehay et al., the radiocarbon date of 10,770 ± 340 BP (AA75326) in Table 1 did not pertain to the Huaca Prieta site. In the Supplementary Materials file, the image of a fragment of reed matting in fig. S9 was incorrect, as the image dates to a later cultural period. The revised version of fig. S9 includes the correct image from the late Pleistocene period at Huaca Prieta. Additionally, text has been revised in the “Artifact assemblage” section to better reflect the findings of fig. S9.

The global energy transition is accelerating the deployment of photovoltaics (PV) as a major source of electricity. Insufficient interfacial regulation over optical and thermal processes still restricts power conversion efficiency (PCE) and long-term reliability. Reflection losses, ineffective spectral utilization, and inadequate heat dissipation limit power generation, while surface contamination undermines long-term outdoor reliability. Although advanced surface materials offer opportunities to mitigate these losses, integrating spectral modulation with self-cleaning remains challenging. This review presents recent progress in PV surface materials from the perspective of integrated spectral modulation and wettability control design. We first summarize the fundamental mechanisms that govern spectral modulation and contaminant removal, emphasizing the synergistic interaction between physical structure design and chemical composition regulation. We then discuss feasible strategies for modulating optical behaviors across different wavelength ranges, alongside approaches for self-cleaning through wettability control. Recent advances in partial-integration strategies are further examined, highlighting the potential impact on PCE enhancement and environmental adaptability. Finally, we discuss the remaining challenges for achieving effective integration of spectral modulation and self-cleaning in surface materials. By positioning full-spectral modulation coupled with durable self-cleaning as a future design target, this review outlines an integrated framework for developing high-performance and durable PV surface materials.

ABSTRACT High‐entropy materials (HEMs), as an emerging multicomponent system, exhibit significant potential in green solar energy conversion owing to their continuously tunable electronic structures. Nevertheless, the complex local chemical environments in HEMs induce significant differences in intermediate adsorption/desorption at metal active sites and complicate photoexcited electron transfer. Herein, we propose a strategy of incorporating heterogeneous transition metal Zn into a high‐entropy oxide (HEO) lattice to precisely tune the spin state of Ni 2+ . Since the spin‐state transition of Ni 2+ does not involve electron transfer from t 2g to e g orbitals, but rather only involves electron redistribution within e g manifold, its electronic structure is particularly sensitive to lattice distortion‐induced variations in crystal‐field strength, thereby enabling selective regulation of Ni 2+ from low‐spin to high‐spin. Field‐dependent magnetization measurements and x‐ray absorption spectroscopy confirm that Zn incorporation effectively modulates the spin state of Ni 2+ . Density functional theory calculations and femtosecond transient absorption spectroscopy reveal that high‐spin Ni 2+ exhibits an upshifted d ‐band center and pronounced spin polarization, which synergistically optimize both *H adsorption and photogenerated charge carrier separation efficiency. Consequently, 0.75%FeCoNi 0.3 MnZn–HEO/Cd 3 (C 3 N 3 S 3 ) 2 (0.75%Ni 0.3 Zn–HEO/CdTMT) exhibits a prominent PHE rate of 47.53 mmol g −1 h −1 . This work opens new paradigms for the rational design of spin‐directed multi‐component HEMs.

ABSTRACT Organic‐inorganic hybrid materials glasses are increasingly recognized as a distinctive class within the broader field of glass science, because they extend the concept of glass formation from rigid atomic or polymeric networks to chemically programmable hybrid solids that integrate organic and inorganic building units. This emerging class of materials offers unusual opportunities for tuning optical, electronic, and structural properties, but its development is fundamentally limited by poor resistance to crystallization and devitrification. Here we report an A‐site cation engineering strategy to develop crystallization‐resistant zero‐dimensional antimony halide hybrid scintillator glasses. Replacing an allyl‐substituted triphenylphosphonium cation with a more conformationally flexible methoxymethyl analogue frustrates ordered packing, weakens directional intermolecular locking, and increases melt viscosity, thereby shifting the competition between crystallization and vitrification toward a persistent glassy state. The resulting transparent (MTPP) 2 SbCl 5 glass exhibits markedly enhanced resistance to thermally induced devitrification, together with efficient and stable luminescence and good irradiation tolerance. It enables centimeter‐scale scintillating monoliths for X‐ray imaging with a spatial resolution of 19.0 lp mm −1 at an MTF of 0.2, and can be further processed into active fibers for proof‐of‐concept remote X‐ray imaging.

ABSTRACT Sorption‐based atmospheric water harvesting (AWH) offers a decentralized strategy to alleviate global water scarcity. However, the trade‐off between high salt loading and structural stability in AWH sorbent materials remains a critical bottleneck. Here, we report a hierarchical composite gel (D‐HKPB@LiCl) that addresses the persistent salt‐leakage challenge while enhancing solar‐thermal efficiency. By integrating sulfated κ‐carrageenan (KC) into a thermoresponsive hydroxypropyl cellulose (HPC) matrix, strong coordination between sulfate groups and lithium ions chemically anchors the hygroscopic salts within the polymer network, endowing the system with exceptional cycling stability. To overcome kinetic limitations, directional freezing vertically aligns polydopamine‐coated hydroxylated boron nitride (PDA@BNO) whiskers, creating anisotropic thermal pathways with through‐plane conductivity of 0.49 W m −1 K −1 along the ice‐growth direction. This architecture, coupled with the photothermally triggered hydrophobic phase transition of HPC, enables a maximum desorption rate of 3.1 kg m −2 h −1 under one Sun illumination. The D‐HKPB@LiCl gel exhibits a water uptake of 0.91–4.32 g g −1 across 30%–90% RH. Outdoor field validation in Lanzhou, China, under challenging winter conditions (average 4.3 °C, <0.5 Sun) using a customized active condensation harvester yields a freshwater output of 0.78 g g −1 , establishing a reliable design framework for high‐performance freshwater generation across diverse climatic conditions.

The escalating prevalence of multidrug-resistant bacterial infections presents a grave global health challenge, highlighting the limitations of traditional antibacterial materials that rely on passive release mechanisms. This paper comprehensively reviews the emerging frontier of stimuli-responsive smart antibacterial fibers (SAFs), which embody a paradigm shift towards on-demand and targeted proactive antimicrobial functionality. Based on response mechanisms, the specific stimuli sensed by SAFs are classified as endogenous infection microenvironments (i.e., pH, dysregulated enzyme activity, and redox potential, etc.) and exogenous physical activation (i.e., light, ultrasound, mechanical force, and magnetic, etc.). Furthermore, this review systematically expounds on the fundamental design principles of SAFs (how to achieve "smartness"), antibacterial mechanisms (how to achieve "antibacterial activity"), and innovative applications in various fields. Subsequently, current challenges are thoroughly discussed, and promising future research directions are outlined. Crucially, artificial intelligence is highlighted as a pivotal enabler for integrating multifunctionality, biomimetic design paradigms, and embedded sensing capabilities, thereby facilitating seamless interoperability with digital health platforms. This review aims to establish a foundational framework inspiring innovation in developing next-generation antibacterial fibers with superior therapeutic precision and functional sophistication.

ABSTRACT Anion exchange membrane water electrolysis (AEMWE) is recognized as a promising technology for green hydrogen production. The development of high‐performance non‐noble‐metal‐based (NNM) electrocatalysts is crucial for its industrial‐scale deployment. However, in alkaline media, they typically face a critical challenge in simultaneously activating water molecular and optimizing hydrogen species adsorption, resulting in sluggish water dissociation kinetics. Herein, we engineer a NiS/Ni 3 S 2 heterojunction with strong interfacial interaction via a facile cathodic polarization method. Theoretical and experimental analyses reveal a synergistic dual‐site mechanism of hydrogen evolution reaction: Ni sites promote H 2 O adsorption through upshifted d‐band center, serving as the primary water dissociation centers; concurrently, S sites optimize the hydrogen binding energy by accepting interfacial charges, facilitating H* adsorption/desorption. This dual‐site mechanism significantly lowers the energy barrier of the Volmer step. Impressively, in AEMWE tests the resultant NiS/Ni 3 S 2 @W requiring only 1.73 and 1.68 V to reach a current density of 1 A cm −2 at 60°C and 80°C, respectively. Furthermore, it can maintain stable operation for over 1 000 h at 1.5 A cm −2 and exhibits robust tolerance under dynamic fluctuating conditions. This work provides a reliable interface engineering strategy for designing efficient electrocatalysts for industrial‐grade water electrolysis.

ABSTRACT Nonuniform Zn 2+ flux, which triggers dendritic growth and accompanying side reactions, severely bottlenecks the practical implementation of aqueous zinc‐ion batteries. While the interfacial electric field governs Zn 2+ flux uniformity, existing modulation strategies rely on static unidirectional fields remains intrinsically decoupled from the bidirectional, field‐reversing dynamics of cyclic Zn deposition/stripping. Herein, we engineer a dynamic dipole‐flipping interlayer (DDL) on Zn anode that generates a switchable molecular‐level electric field to enable uniform Zn 2+ flux regulation during cycling. Specifically, the DDL is constructed from a rationally designed polyamide derivative featuring inherently large amide dipole moments; increased free volume and chain flexibility disrupt dense chain packing and enable rapid, reversible dipole reorientation. During Zn deposition/stripping, the amide dipoles reorient dynamically to generate polarity‐switchable interfacial molecular‑level electric fields, which direct homogeneous Zn 2+ redistribution and suppress preferential nucleation. Beyond electric‑field regulation, fluorinated segments within the DDL impart interfacial hydrophobicity and further suppress side reactions. Consequently, the DDL‐modified Zn anode cycles stably for over 3200 h at 0.5 mA cm −2 , while the Zn||MnO 2 full cell delivers 97.3% capacity retention after 1600 cycles at 1 A g −1 . This work pioneers a versatile paradigm for interfacial electric field regulation by dipole dynamics toward high‐performance aqueous metal‐based batteries.

ABSTRACT Pushing LiCoO 2 to ≥4.5 V causes coupled degradation: electrolyte oxidation and cathode structural collapse, especially at high rates. Here, we propose a triphase synergistic gel‐electrolyte to tackle both failure modes. The system, constructed by in situ thermal polymerization, integrates an ether‐rich crosslinked polymer network, surface‐activated AlN fillers with Lewis acid–base sites, and a fluorinated electrolyte. This design regulates Li + transport, confines free solvent molecules, and reconstructs the solvation sheath. More importantly, it induces a uniform, inorganic‐rich cathode–electrolyte interphase at an early stage. Consequently, LiCoO 2 ‐based quasi‐solid‐state cells deliver exceptional stability: over 1000 cycles at 4.6 V and 5 C with an average decay of only ∼0.03% per cycle, and 85.98% capacity retention after 500 cycles in practical Si–C||LiCoO 2 pouch cells. Operando EIS‐DRT analysis reveals that the triphase electrolyte substantially suppresses the growth and fluctuation of interphase‐related polarization at high voltage, making the remaining impedance evolution more governed by transport/contact processes. This work demonstrates that decoupling interfacial and structural degradation through a synergistic electrolyte design is key to realizing high‐voltage, high‐power, long‐life quasi‐solid‐state batteries.

Nanozymes have emerged as robust and scalable alternatives to natural enzymes, offering high catalytic activity and structural stability. However, reproducing the exquisite selectivity of enzymatic catalysis, particularly their ability to operate with high precision in complex reaction systems, remains a central challenge. Herein, inspired by the heme-pocket architecture and cooperative regulation in cytochrome P450, we report a nanozyme multilevel programming strategy based on a single-atom covalent organic framework (COF) platform constructed from heme-like metal-porphyrin nodes and linkers bearing chiral amino-acid residues, enabling selective editing of metal catalytic centers and enzyme-mimetic pockets to control catalytic activity, chemoselectivity, and stereochemical outcomes. As a proof of concept, we employ a biomimetic chiral cascade that couples methanol dehydrogenase-like alcohol oxidation with a chymopapain‑inspired asymmetric aldol reaction to probe and optimize metal-pocket cooperativity within the nanozyme. The programmed MnPor-Pro-based nanozyme delivers high product yields, excellent chemo- and stereoselectivity, and outstanding recyclability in the cascade reactions, indicating the effectiveness of this strategy. This work provides a rational design insight for engineering highly selective nanozymes capable of addressing complex, multistep transformations, significantly bridging the gap between artificial and natural enzymatic systems.

Abstract The chemical inertness of sulfide ores presents a major challenge for the direct extraction and separation of mineral feedstocks into high-purity metals. Conventional processing therefore relies on high-temperature pyrometallurgy or cyanide-based hydrometallurgy following indirect oxidative pretreatment. Here, we report an alkahest-enabled strategy for direct electrochemical extraction of Cu and Ag from chalcocite (Cu2S) and acanthite (Ag2S) under mild, room-temperature, and acid-free conditions using 2-mercaptoethanol (merc) and ethylenediamine (en). Dissolution in the thiol-amine solvent system generates electrochemically active Cu- and Ag-containing species that can be directly transformed into high-purity metallic films through electrowinning. Cu electrowinning exhibits a Faradaic efficiency of 84% with an electrical energy consumption of 0.41 kWh/kg, while Ag recovery achieves a Faradaic efficiency of 87% with an electrical energy consumption of 0.14 kWh/kg. Beyond individual sulfide systems, water-mediated phase selectivity enables separation of Cu–Ag–S mixtures, yielding isolated Cu and Ag solutions for selective recovery with final metal purities of 99.4% and 99.0%, respectively. These findings establish alkahest-mediated chemistry as a promising framework for direct sulfide-to-metal transformations and selective conversion of multicomponent sulfide minerals into high-purity metals.

Abstract Thermosalient (TS) crystals are a class of dynamic crystalline materials with exceptional thermally responsive mechanical effects and efficient thermomechanical energy conversion capability. Hybrid metal halides serve as excellent carriers for TS crystals owing to their highly tunable structures. In this work, a series of chiral hybrid cadmium halide crystals (R/S-3OHPD)CdX3 (3OHPD = 3-hydroxypiperidinium; X = Cl, Br, I) were synthesized, and their phase transitions, crystal structures, TS behaviors, and intrinsic mechanisms were systematically investigated. The halogen substitution effectively regulates the lattice dimensions, rigidity, phase transition type, and TS performance of the crystals. Specifically, (R-3OHPD)CdCl3 undergoes an irreversible solid–solid phase transition accompanied by explosive fragmentation. Within a certain size range, its TS behavior is significantly enhanced with decreasing crystal size; that is, smaller crystals are more prone to explosive cracking due to stress concentration. The Br analogue exhibits a reversible solid–solid phase transition with moderate fragmentation, which is insensitive to crystal size variation within a certain size range. In contrast, the I analogue directly melts at 340 K without a solid–solid phase transition. Mechanistic studies reveal that anisotropic lattice distortion, cation order–disorder transition, hydrogen-bonding network reorganization, and inorganic chain displacement collectively govern the macroscopic thermally responsive mechanical motions. This work clarifies the effects of halogen substitution on the TS properties in hybrid halide crystals and provides a design strategy for controllable dynamic crystalline materials for intelligent responsive and information confidentiality applications.

Abstract Polyanionic sodium (Na) super ionic conductor (NASICON) cathodes are attractive for sodium-ion batteries owing to their robust 3-dimensional frameworks and fast Na+ transport. Na3V2(PO4)3, the benchmark NASICON material, delivers near-theoretical two-electron capacity but is constrained by vanadium cost/toxicity and limited electronic conductivity. Motivated by employing an earth-abundant, eco-friendly redox center (Fe3+/Fe2+) while retaining V-centered activity, we systematically introduced and tuned Fe in Na3+xFexV2–x(PO4)3 (x = 0.5, 0.75, 1.25, and 1.5) to increase the Na content and access the synergistic redox of Fe and V. We implemented an ex situ electrospinning-templated architecture in which electrospun fibers enabled the formation of an interconnected NFVP network, providing a continuous electron pathway and mechanical integrity. Given the well-documented difficulty of obtaining phase-pure NFVP by direct routes, often yielding secondary phases, this templated synthesis combined with composition control provides an effective path to a phase-pure, V-lean NASICON structure. Among the series, Na3+xFexV2–x(PO4)3 with x = 0.75 shows the optimum electrochemical activity and durability, delivering 78 mAh g–1 at 0.5C and retaining 90.5% after 1000 cycles and 88% after 1500 cycles at 2C. In situ X-ray absorption near-edge structure results show that the Fe and V K-edge energies shift reversibly during Na+ insertion/extraction at different charging/discharging voltage plateaus, respectively, confirming highly reversible Fe2+/Fe3+ and V3+/V4+ redox within the applied potential window. These results demonstrate a V-lean, Fe-rich NASICON cathode optimized by composition tuning, delivering promising electrochemical performance and cycling stability, and offering a stable and cost-efficient SIB cathode.

Abstract Stacking engineering in van der Waals heterostructures offers a powerful route to modulating band alignment and carrier dynamics. Here, we present a theoretical investigation of SiH/GeH van der Waals heterostructures with different stacking configurations. Distinct stacking-dependent band alignments are identified, with the most stable stacking exhibiting a Type-I alignment and the others adopting Type-II alignments. Time-dependent density functional theory combined with regional natural hole/particle orbital analysis demonstrates that strong interlayer coupling between conduction bands enables photoinduced interlayer charge-transfer excitations even in the Type-I alignment. Nonadiabatic molecular dynamics simulations further uncover a pronounced asymmetry between photoelectron and -hole dynamics, leading to ultrafast electron transfer (∼0.5 ps) and long-lived hole localization (∼20 ps). These results reveal a functional charge-separation mechanism in Type-I heterostructures and establish stacking engineering for controlling excited-state dynamics.