Carbon molecular sieves (CMSs) offer a promising alternative to energy-intensive cryogenic distillation for gas separations such as C3H6/C3H8. However, they suffer from physical aging that reduces gas permeability and from a trade-off between size-sieving capability and mechanical stability. Herein, we address both challenges by engineering robust nanoporous carbons via an integrated low-temperature carbonization and vapor-phase infiltration (VPI) strategy. A 6FDA-DAM polyimide is carbonized at 500 degrees C to form mechanically resilient carbons and then subjected to VPI treatment to generate sub-nanometer aluminum oxyfluoride onto internal pore walls. The inorganic coating rigidifies carbon nanostructures, enhancing their resistance to physical aging, and narrows pore sizes, thereby increasing size-sieving ability. 6-Cycle VPI treatment of a CMS increases C3H6/C3H8 selectivity from 16 to 43 with stable separation properties over 90 days, outperforming most leading CMSs and polymers. The VPI process enables atom-by-atom tuning of micropores and provides a scalable route to enhance membrane separation efficiency.

Small-angle X-ray scattering (SAXS) is a powerful high-throughput characterization tool for probing nanoscale structure in native sample environments, providing real-time morphological information such as nanoparticle size and shape during synthesis. However, automated SAXS data analysis for extracting meaningful structural parameters is non-trivial and remains a bottleneck in closed-loop experimentation towards autonomous materials discovery, which demands fast, reliable, and uncertainty-aware data analysis. Here, we develop a machine-learning approach for automated SAXS analysis tailored to closed-loop nanoparticle synthesis. A Random Forest (RF) regression model is trained on 100,000 synthetic SAXS curves generated from polydisperse spherical nanoparticles with realistic background contributions. Using normalized one-dimensional SAXS intensity profiles as input, the RF model directly predicts nanoparticle radius, size polydispersity, and background parameters, while the ensemble standard deviation across trees provides built-in uncertainty quantification (UQ). On synthetic data, we show that combining fit-quality metrics (R2, MAE) with thresholds on prediction uncertainty reliably identifies accurate parameter estimates without access to ground truth. We then apply the trained model to 365 experimental SAXS profiles of citrate-reduced gold nanoparticles synthesized using an automated droplet-flow microreactor with in situ SAXS at a synchrotron beamline, classifying the results into high- and low-confidence subsets based on UQ metrics. Finally, we integrate RF-based SAXS analysis into a simulated closed-loop optimization campaign using Gaussian process Bayesian optimization to minimize nanoparticle polydispersity, benchmarking against conventional automated Levenberg-Marquardt fitting. The RF-guided campaign exhibits substantially faster convergence and lower relative opportunity cost (∼0.07 vs ∼0.3), demonstrating that uncertainty-aware machine-learning SAXS analysis significantly enhances the efficiency and robustness of autonomous nanomaterials synthesis workflows.

The morphology of DNA is strongly influenced by its surrounding environment, including factors such as pH, salt type and valency, and the presence of polymers. Inorganic salts are known to reduce the DNA chain length through mechanisms like electrostatic screening and ion bridging. In contrast, ionic liquids, a new class of organic salts, have previously been found to increase the DNA chain length, indicating a distinct mode of interaction between the ionic liquid and DNA chains. This study utilizes self-assembled DNA-AuNPs as a model system to examine changes in the DNA chain morphology and the nanoscale interaction mechanisms in an ionic liquid environment. The DNA chain lengths are measured in solution using X-ray scattering measurements at varying concentrations of two imidazolium ([ B M I M $BMIM$ ] acetate and [ E M I M $EMIM$ ] acetate) based ionic liquids. Additionally, Molecular Dynamics (MD) simulations are performed mimicking the experimental system. Our results suggest an interplay of electrostatic and groove-binding interactions governing the DNA chain morphology, which depends on IL concentration and the composition of the DNA chains. It has been found that for DNA chains with majority ssDNA, electrostatic interaction dominate, however with increasing composition of double strands, the DNA chains exhibit compaction due to a non-electrostatic hydrophobic groove-binding mechanism.

Growing energy demands and renewable integration are stressing the aging power grid infrastructure. Lignocellulosic oil-impregnated paper is widely used in power transformers but suffers from critical limitations, such as low dielectric strength, mechanical strength, and thermal conductivity, causing premature transformer failures. Here, we demonstrate a superior electrically insulating oil-impregnated paper design using the naturally anisotropic structure of densified wood veneer to achieve nanosized channels of oil that efficiently disrupt electrical breakdown pathways. The developed oil-impregnated densified wood (ODW) creates aligned cellulose fibers with 166 ± 87-nanometer oil nanochannels, achieving record dielectric strength of 105 kilovolts per millimeter. The structure also delivers a mechanical strength of up to 384 megapascals and a thermal conductivity of 0.33 watts per meter per kelvin, enabling enhanced longevity upon thermal aging tests. The ODW could replace conventional transformer insulation to enhance power transformer performance and improve lifetime. Moreover, its anisotropic oil-filled nanochannel design offers a general strategy for hybrid dielectrics in medium- and high-voltage applications.

Maximizing iridium utilization while maintaining high oxygen evolution reaction (OER) performance remains a persistent challenge in acidic water electrolysis. Immobilizing Ir on conductive, acid-stable supports is promising, yet simultaneously achieving sub-nanometer size, high area coverage, and strong electronic coupling is difficult. Here, we report a sequential surface synthesis on titanium nitride (TiN) that yields uniformly distributed sub-nanometer Ir arrays (similar to 0.7 nm). Our method uses ethylenediaminetetraacetic acid (EDTA) as a temporal scaffold: it chemisorbs to TiN to install dense chelating sites, captures Ir3+ ions, and confines Ir cluster growth. A subsequent thermal treatment at 500 degrees C in a reducing atmosphere removes the ligand shell, while preserving ultrasmall particle size and establishing direct Ir-TiN electronic coupling. The optimized catalyst exhibits mixed Ir0/Irx+ coordination with low charge-transfer resistance (Rct = 19.2 Omega), delivering a mass activity of 342 A gIr-1 at 1.54 V in acidic electrolyte. In situ X-ray absorption spectroscopy reveals irreversible surface oxidation as the primary stability-limiting factor. This stepwise strategy provides a general framework for supported catalysts that maximize precious metal utilization via sub-nanometer dispersion.

Chiral organic-inorganic metal halide semiconductors (MHSs) have emerged as promising materials for chiroptoelectronics, spintronics and ferroelectrics. However, commonly used chiral cations with nonconductive aliphatic and aromatic structures exhibit large energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) relative to those of the inorganic frameworks. This energy mismatch between the chiral spacer and the inorganic sublattice creates a barrier that hinders charge-carrier transport, leading to inefficient out-of-plane charge mobility and strong quantum confinement effects. To address this challenge, we design and synthesize chiral n-type naphthalenediimide (NDI)-based cations, (R)-2-(7-ethyl-1,3,6,8-tetraoxo-3,6,7,8-tetrahydrobenzo[lmn][3,8]phenanthrolin-2(1H)-yl)propan-1-aminium ((R)-NDIEPA+). We successfully tune the LUMO level of (R)-NDIEPA+ to align with that of the inorganic sublattice, and the resulting chiral one-dimensional (1D) (R-NDIEPA)PbI3 MHS demonstrates a type II band alignment that facilitates charge separation, as evidenced by quenched photoluminescence and transient absorption dynamics indicative of ultrafast charge transfer across the organic-inorganic interface. As a result, these materials demonstrate an approximately 7-fold enhancement in electron mobility compared to the chiral 1D MHS incorporating nonconductive aromatic cations. (R-NDIEPA)PbI3 also exhibits a strong circular dichroism (CD) signal, confirming effective chirality transfer from the organic cation to the inorganic framework. These findings underscore the importance of leveraging the electronic properties of chiral organic cations while preserving strong chiroptical activity, highlighting the potential of (R-NDIEPA)PbI3 for chiroptoelectronic applications such as circularly polarized light photodetectors and other spintronic devices.

Tracking the structural evolution of colloidal nanocrystals (NCs) facilitates the mechanistic studies of their materials chemistry. NC engineering via phase transformation reveals the chemical and physical determinants that drive lattice-scale dynamic processes such as cation exchange. Here we employed NCs to demonstrate the cation exchange process from Cu3As to InAs and GaAs within nanocubes. The symmetry conversion in unit cells from cubic Cu3As to hexagonal InAs and GaAs can be described using a schematic cellular automaton model, which suggests a simplified cube-to-sphere transition. The strong covalent characteristics of III-V materials highlight the kinetic control that navigates the tailorable transformation through either an isotropic trajectory, leading to hollow structures, or a topotaxial trajectory, with abundant stacking faults. The reconstruction of complex covalent bonds is envisioned as the foundation for the synthesis of NCs.

Polymer-based solid-state electrolytes are promising for next-generation lithium metal batteries, yet their limited ionic conductivity and mechanical stability at ambient conditions remain key challenges. Herein, we report a novel gradient crosslinked polymer electrolyte (PU/PUA/PU) synthesized via a sequential in situ UV-curing process that integrates a mechanically robust polyurethane acrylate (PUA) core with soft linear polyurethane (PU) interfaces. This all-solid membrane operates without any liquid plasticizer and the interfacial PU layers ensure low interfacial resistance and intimate electrode contact, while the PUA core provides enhanced dimensional stability and dendrite suppression. As a result, the gradient electrolyte delivers an impressive similar to 2.6 & times; 10(-4) S cm(-1) ionic conductivity at 25 degrees C (two orders of magnitude higher than conventional PEO) and remains electrochemically stable >5 V (vs Li+/Li). Structural analysis confirms the formation of a well-defined crosslinked network with suppressed crystallinity and expanded interchain spacing. Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) further validate these properties. When applied in a Li||NMC811 cell, the PU/PUA/PU electrolyte delivers stable cycling with high capacity at both 60 degrees C and 25 degrees C, demonstrating its potential for room-temperature solid-state battery applications without reliance on plasticizers or heating. This gradient design offers a practical path toward ambient-condition operation of solid-state lithium batteries, providing a paradigm for overcoming the traditional trade-off between ionic conductivity and mechanical robustness.

PEO-PPO-PEO block copolymers, particularly commercially available Pluronic (R) F127 and Pluronic (R) P123, exhibit thermoresponsive self-assembly, forming micelles and gels with tunable viscoelastic properties that have been utilized in drug delivery and personal care formulations. Formulations that combine multiple PEO-PPO-PEO copolymers with differing molecular weights and block lengths may provide a route to access systems with new properties that are optimized for specific delivery applications. This study investigates the rheology and microstructure of F127/P123 blends in water across a range of concentrations and temperatures by integrating bulk rheology, dynamic light scattering (DLS) microrheology, and small-angle X-ray scattering (SAXS). Our results demonstrate that increasing the F127 content enhances elasticity of gel samples at higher concentrations and temperatures, attributed to stronger intermicellar interactions from the longer PEO chains, whereas P123-rich blends exhibit more fluid-like behavior. Intriguingly, discrepancies between bulk rheology and microrheology measurements reveal that microstructural mechanisms governing gelation are not fully captured at the macroscopic scale. Specifically, microrheology uncovered an unexpected trend: decreasing the F127 ratio led to reduced probe particle mobility, contradicting bulk modulus trends and suggesting localized structural constraints. SAXS analysis further elucidates the relationship between micellar packing and phase transitions, providing nanoscale insights into the system's structural evolution. These findings underscore the importance of multiscale characterization in bridging the gap between micro-and bulk rheology, offering critical insights for the design and optimization of Pluronic (R)-based formulations in biomedical and industrial applications.

Chiral metal halide perovskite semiconductors (CMHS) are fascinating semiconductors with unique chiroptical properties and spin-polarized charge transport. Achieving long spin lifetimes and high carrier mobility concurrently is essential to realize the true potential of CMHS in manipulating charge, spin, and light. While conventional monolayer n = 1 CMHS possess appreciable anisotropy factors of circular dichroism (gCD) and photoluminescence (glum), imparting chirality to quasi-2D CMHS (n > 1) with enhanced carrier mobilities is underexplored. Herein, we systematically investigate the layer number (n-value) dependence and emergent trade-offs in chiroptical properties, spin-relaxation times, and carrier mobilities in chiral quasi-2D (R/S-MPEA)2MAn-1PbnI3n+1 single crystals and thin films (R/S-MPEA: R/S-β-methylphenylethylammonium; MA: methylammonium; n = 1-3). Films with n = 2 exhibited the highest gCD of 8 × 10-3, an order of magnitude larger than their n = 1 and n = 3 counterparts. On the other hand, n = 3 films demonstrated enhanced spin lifetimes up to 15 ps along with increased carrier mobility up to 11.6 cm2 V-1 s-1. As a result, photodiode-type photodetectors based on n = 3 CMHS reveal high specific detectivity and superior discrimination of circularly polarized light, outperforming n = 1 and 2. These findings highlight the potential of quasi-2D CMHS as tunable, high-performance platforms with longer spin lifetime and diffusion length, enabling new functionalities.

Autonomous synthesis platforms promise rapid exploration of vast parameter spaces; yet, integrating in situ structural characterization in closed-loop synthesis optimization remains challenging. We demonstrate a realization of such a closed-loop platform coupled with a droplet-flow microreactor, in situ X-ray scattering methods (SAXS/WAXS), and Gaussian process optimization to synthesize citrate-reduced Au nanoparticles with targeted characteristics. The system efficiently explored ∼19,000 synthesis recipes through 365 experiments, achieving precise control over size (4-60 nm) and polydispersity (σ < 0.11) across large citrate/gold ratios, exceeding traditional synthesis boundaries (1-10). Beyond confirming classical Turkevich-Frens trends, partial-dependence analysis revealed strong nonlinear coupling among precursor, citrate, and pH effects. Combining quantitative SAXS/WAXS analysis with electron microscopy characterization, we uncovered that crystallite size (dc) and particle size (d) follow dc = 0.18d + β, where synthesis chemistry controls the intercept β while maintaining a universal slope. This parallel-band structure enables independent tuning of crystallite domain size at fixed particle diameter through a combination of chloride, gold precursor, citrate, and pH contributions (cross-validated Spearman ρ = 0.7 ± 0.1). High-resolution electron microscopy shows multiple lattice-fringe orientations within single particles, directly confirming polycrystalline domains and the ability to tune dc at the fixed d. The platform's validation includes indistinguishable static versus flowing measurements, stable droplet transport at 100 °C, and <5% run-to-run variation, establishing a robust framework for mapping and controlling multiscale nanoparticle structure across expansive chemical spaces. The developed closed-loop platform can be applied to a borad range of nanosyntheis processes.

Physically gelled soft materials, driven by the self-assembly of low-molecular-mass gelators (LMGs), have emerged as a platform for designing advanced gels that exhibit reversible gelation and property tunability. Liquid crystal (LC) gels are of great interest due to their supramolecular orderings as gel hosts and their enhanced electro-optical properties. In this study, we demonstrate the physical gelation of a nematic LC driven by nanoplate self-assembly, expanding the concept of gelators from small molecules to nanoparticles. These nanoplates are functionalized with promesogenic ligands and form a fibrillar network in LCs with face-to-face interplate stacking, resembling LMGs. The critical gelation volume fraction in the tilt test is only 0.14 v %, comparable to values reported for LMGs. Rheological analyses confirm viscoelastic properties characteristic of gelation. In situ small-angle X-ray scattering (SAXS) characterizes the formation of nanoplate networks in the LC with decreasing temperature, wherein LC mesogens become trapped in pores. Molecular dynamics (MD) simulations reveal that the interaction between ligand-coated nanoplates and LC-forming mesogens induces a multidomain LC structure, increasing friction between LC domains and stabilizing the gel. This study establishes direct relationships among molecular interactions, nanostructures, and mechanical properties in physically gelled LCs. The findings inspire the future gelator design of both LMGs and nanoplates, with potential applicability in bioscaffold engineering and liquid crystalline nanocomposites.

Two-dimensional (2D) magnetic materials have attracted considerable interest owing to their potential applications in spintronics and fundamental investigations into low-dimensional magnetism. Cr2Te3, a quasi 2D non van der Waals magnet, exhibits a complex magnetic phase diagram due to competing magnetic interactions within and between layers. However, the precise nature and evolution of these magnetic phases remain unclear. Here, we utilize an ultrahigh-sensitive composite magnetoelectric technique, which probes the ac magnetostrictive coefficient, to systematically explore the temperature magnetic field phase diagram of Cr2Te3 single crystals. Our results reveal the coexistence of multiple magnetic phases, including canted ferromagnetic, antiferromagnetic, and paramagnetic states. Another canted ferromagnetic phase and a possible triple point have been proposed. The updated phase diagram provides deeper insights into the specific spin configurations associated with each phase. These findings also highlight the decoupled magnetic ordering between the Cr1/Cr3 layers and the Cr2 layer near the magnetic ordering temperature.

Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm (refs. 1,2), enabling ever smaller microdevices as today's fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces3,4. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as 'paint'. We use this approach to synthesize more than 20 different types of NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering5-11.

Designing superlattices of nanocrystals to mimic and extend the properties of atomic crystals has been a long-standing motivation in materials chemistry. Interstitial solid solutions, such as steel, are well-studied atomic lattices in which mobile components move among the interstices. These materials exhibit unique properties, including reversible structural changes and phase transitions. Interstitial solid solutions possess unique dynamic structures and reversible responses, which motivate the creation of their colloidal equivalents. Here we report a fully thermo-reversible colloidal interstitial solid solution by combining liquid crystals and nanocrystals functionalized with promesogenic ligands. Mesogen molecules fill and diffuse among the interstices of a superlattice, resulting in a super-large thermal expansivity. The approach uses a modular design of interparticle interactions, allowing control of interparticle distance, microstructure and transition between crystallographic forms.

Thermotropic liquid crystals (LCs) present opportunities for synergistic interactions with ligand-functionalized nanoparticles (NPs). Understanding the dynamics and structures of ligand-coated NPs in an anisotropic LC environment allows for better design and control of versatile LC-NP hybrid materials. Here, simulations and experiments yield direct evidence that cyanobiphenyl LCs induce anisotropy in the biphenylalkyl ligand shells of spherical NPs. The ellipsoidal NP aligns with the LC director. Magnetic fields can dictate the directional ordering of mesogens and consequently allow control of the orientation of the nonmagnetic NPs. Controlling the alignment and deformation advances the design and engineering of these hybrid nanomaterials.

Cost‐effective redox‐active materials are essential for advancing redox flow batteries (RFBs). Iron, with its abundance and suitability as a redox couple, is a promising candidate; however, achieving stable and fast redox reactions in aqueous RFBs remains a challenge. This study presents an Fe‐based negolyte stabilized by a hexadentate ligand, where Fe–ligand bonds are enhanced through intermolecular interactions. The sulfonate‐substituted Fe complex exhibits a formal potential of −0.44 V versus Ag/AgCl and an exceptionally high rate constant of 0.69 cm s −1 . Near‐neutral RFBs incorporating 0.5 M Fe complex show excellent cycling stability, with no discernible capacity fading over 300 cycles. This performance is attributed to intermolecular hydrogen bonds that reinforce Fe–ligand coordination and promote the formation of stable trimeric clusters. Operando electrochemical Raman spectroscopy and density functional theory reveal that π‐backdonation from Fe(II) to the imino‐phenolate moiety further stabilizes the complex after reduction. In contrast, the hydroxyl‐substituted complex exhibits inferior stability due to weaker hydrogen bonding and less pronounced π‐backdonation. These findings underscore the importance of ligand design and intermolecular interactions in developing cost‐effective, high‐performance redox‐active materials for aqueous RFBs.

Coherent heterojunctions, quantum wells and multiple quantum wells are needed for high-performance devices; these are generally grown via a dedicated vapour phase epitaxy process. Here we demonstrate the growth of coherent perovskite heterojunctions and quantum wells made of mixed-dimensional perovskites using a solution process. By exploiting the solubility difference of methylammonium (MA+) and 4-(aminomethyl)piperidinium (4AMP2+), we assemble layered perovskites with different layer numbers. The resulting 4AMP-MAn-1PbnI3n+1 materials each with different layer numbers or bandgaps form quantum wells. Heterojunctions and quantum wells made of 4AMP-MA2Pb3I10 (n = 3) and 4AMP-MAPb2I7 (n = 2) with various barrier thickness are tailored by the solution temperature profile during crystal growth. Multiple quantum wells have been formed by cycling temperature profiles. The planar heterojunction and quantum wells have lattice matching without interfacial defects, and exhibit strong thermal stability. Type I band alignment at the n = 2/n = 3 heterojunction is confirmed by both computation and optical studies. This study opens a new direction for the development of sophisticated perovskite heterojunction and quantum well devices.

Despite their simplicity, tetrahedra can assemble into diverse high- and low-density structures. Here we report a low-density 'octo-diamond' structure formed by nanoscale solid tetrahedra with a 64-tetrahedron unit cell containing 8 cubic-diamond subcells. The formed crystal is achiral, but is composed of chiral bilayers with alternating handedness. The left- and right-handed chirality of the bilayers, combined with the plasmonic nature of the gold tetrahedra, produces chiroptical responses at the crystal surface. We uncover that the hydrophobic substrate facilitates the arrangement of tetrahedra into irregular ring-like patterns, creating a critical, uneven topography to stabilize the observed octo-diamond structure. This study reveals a potent way to affect colloidal crystallization through particle-substrate interactions, expanding the nanoparticle self-assembly toolbox.

In the fabrication of FAPbI3-based perovskite solar cells, Lewis bases play a crucial role in facilitating the formation of the desired photovoltaic α-phase. However, an inherent contradiction exists in their role: they must strongly bind to stabilize the intermediate δ-phase, yet weakly bind for rapid removal to enable phase transition and grain growth. To resolve this conflict, we introduced an on-demand Lewis base molecule formation strategy. This approach utilized Lewis-acid-containing organic salts as synthesis additives, which deprotonated to generate Lewis bases precisely when needed and could be reprotonated back to salts for rapid removal once their role is fulfilled. This method promoted the optimal crystallization of α-phase FAPbI3 perovskite films, ensuring the uniform vertical distribution of A-site cations, larger grain sizes and fewer voids at buried interfaces. Perovskite solar cells incorporating semicarbazide hydrochloride achieved an efficiency of 26.1%, with a National Renewable Energy Laboratory-certified quasi-steady-state efficiency of 25.33%. These cells retained 96% of their initial efficiency after 1,000 h of operation at 85 °C under maximum power point tracking. Additionally, mini-modules with an aperture area of 11.52 cm2 reached an efficiency of 21.47%. This strategy is broadly applicable to all Lewis-acid-containing organic salts with low acid dissociation constants and offers a universal approach to enhance the performance of perovskite solar cells and modules.