Abstract Metal-organic framework (MOF) glasses have emerged as a promising class of materials owing to their unique combination of gas adsorption capabilities and superior moldability compared to conventional crystalline MOFs. However, their physical processing has remained largely constrained to powders or bulk monolithic solids. Inspired by the fiberization of conventional silica glasses that unlocked advanced functional architectures, developing a reliable processing strategy to draw MOF glasses into continuous fibers represents a critical frontier. Herein, we report a rational strategy to impart high spinnability to ZIF-62 (Zn(imidazole)1.75(benzimidazole)0.25) glasses through the in situ structural incorporation of one-dimensional (1D) γ-AlOOH nanobelts during the framework assembly. The composite glass containing an optimized 1 wt % fraction of γ-AlOOH exhibits enhanced fiber-drawing capability under tensile stress at elevated temperatures. This behavior is driven by the shear-induced alignment of the embedded nanobelts parallel to the stretching direction, mediated by interfacial interactions between the surface hydroxyl groups of γ-AlOOH and the imidazolate linkers, which successfully stabilizes the viscous MOF liquid matrix during elongation. The resulting composite glass fibers display mechanical resilience, enduring a bending curvature of 1.89 mm-1 at a diameter of 70 μm while fully preserving the intrinsic CO2 adsorption properties of the framework. This structural engineering of spinnable MOF glasses provides a versatile toolkit for fabricating advanced fibrous MOF architectures, opening up a wide horizon for mechanically resilient membrane filters, porous glass wool insulation, and intricate 3D structures.
Abstract Electrocatalytic urea synthesis offers a sustainable, carbon- and energy-efficient alternative to the Haber-Bosch process under ambient conditions. It is a sustainable strategy in which simultaneous reduction of carbon dioxide (CO2) and nitrogen molecules (nitrogen, nitrate, nitrite, nitric oxide, etc.) lead to form urea. However, electrochemical urea synthesis faces multiple challenges including activation of CO2 and nitrogen molecules (nitrogen, nitrate, nitrite, nitric oxide, etc.), low production and selectivity toward urea production. The C–N coupling reaction is considered the most challenging part for urea synthesis. With respect to all this, this review focuses on fundamental reaction mechanisms followed by recent progress for electrochemical urea production. Recent advances highlight the rational design of heterogeneous catalysts─ranging from transition-metal-based systems (Cu, Ni, Fe, Co) to single-atom catalysts─that enable simultaneous activation of CO2 and nitrogen molecules. This review summarizes proposed reaction pathways by correlating catalyst active centers with mechanistic insights into CO2/N-containing species activation and coupling. The critical challenges related to low yield and Faradaic efficiency are outlined, providing perspectives for translating laboratory breakthroughs into practical urea electrosynthesis technologies. Collectively, these advances establish electrocatalytic urea synthesis as a frontier in sustainable chemistry, bridging carbon capture with nitrogen cycle management, and paving the way toward scalable green urea production.
Abstract Developing polyethylene-like (PE-like) materials with built-in chemical recyclability provides a promising strategy for addressing the end-of-life challenges of persistent polyolefins. Entropy-driven ring-opening polymerization (ROP) of macrolactones offers an attractive route to floor-temperature (Tf)-regulated long-chain polyesters that combine PE-like performance, thermal stability, processability, and chemical recyclability. However, achieving functional PE-like polyesters remains challenging, as it requires balancing efficient polymerization, retention of reactive functional groups, tunable material properties, and selective chemical recycling. Here, we designed and synthesized ambrettolide-derived 17-membered macrolactones bearing an internal double bond, epoxide, or five-membered cyclic carbonate group and achieved their selective ROP using a Lewis pair catalytic system. The resulting long-chain polyesters exhibited well-defined structures, high molecular weights, and preserved functional groups. These polyesters exhibited PE-like tensile behavior, melt reprocessability, tunable surface wettability, excellent gas barrier properties, and stable melt processability. Moreover, bulk melt depolymerization enabled recovery of the corresponding macrocyclic monomers, and the recovery yields were governed by the stability of the fused functional moieties. The purified recovered monomers retained their repolymerizability. This work establishes functional Tf-regulated long-chain polyesters as versatile platforms with tunable performance, processability, and recyclability.
Abstract Pt-based catalysts are widely used for propane dehydrogenation (PDH), yet high-temperature operation causes severe deactivation through sintering and coking. Strong metal–support interaction (SMSI) offers a potential solution by improving durability via oxide encapsulation, although excessive or uncontrolled encapsulation often reduces activity by blocking accessible metal sites. These limitations make it a key outstanding challenge to achieve precisely controlled SMSI overlayer thickness and to clarify its role in balancing activity and stability. Here, we addressed this issue by regulating Ga loading on SiO2 through atomic layer deposition and leveraging the high mobility of GaOx during reduction together with strong Pt–Ga interactions. This strategy enabled atomic-scale control of GaOx encapsulation and revealed a clear thickness–performance relationship, with near-monolayer Pt@GaOx outperforming bilayer and 3–4-layer structures for PDH. The optimized catalyst delivered a propylene formation rate of 160 molC3H6·gPt–1·h–1 with >97% selectivity and stable operation for 260 h. Spectroscopic and kinetic studies showed that Pt-induced interfacial charge redistribution tuned defect-rich, coordinatively unsaturated Ga sites, enabling C–H activation and propylene desorption, thereby limiting deep dehydrogenation and coke formation. In parallel, geometric confinement by the GaOx overlayer inhibited sintering. These findings establish controlled SMSI as an effective strategy for engineering oxide–metal interfaces toward active and durable catalysis.
Abstract Vat photopolymerization exemplifies one of the most attractive and prospective processing approaches, producing unique prototypes, specifically functional systems, or biocompatible products in the next generation of biobased materials. This work summarizes and presents specific strategies for developing chemical solutions for three-dimensional (3D)-printable resins derived exclusively from biobased compounds. The photocurable systems used in additive manufacturing require a primary reactive resin precursor. Usually, rheological modifications that regulate the flow characteristics of the polymerizable main system require the use of reactive diluents, which are low-molecular-weight, low-viscosity, and polymerizable. Such systems often exhibit excessive volatility, resulting in environmental issues such as increased VOCs or hazardous chemical character. This overview presents and describes the main reactive resin precursors, based on bioderived polyesters and terpene-based systems, along with fully biobased reactive diluents synthesized from biotechnological products (itaconic acid) and other sources (biophenols). Lastly, the partly and fully biobased photoinitiators, produced from sources, such as riboflavin, coumarin, or curcumin, are introduced as an alternative to the highly hazardous and toxic commercial photoinitiators, such as BAPO and TPO, which pose serious health hazards. Fully biobased precursors stand in this perspective as substances obtainable from alternative feedstocks to petroleum-based ones (e.g., biotechnological production, extraction from biomass, and reformulation of complex substances). This work reviews the reported options and experimental findings and suggests the most promising pathways to environmentally friendly vat photopolymerization resins.
Immune cell membrane engineering strategies, such as chimeric antigen receptors and multispecific antibodies, hold great promise for cancer therapy but are often limited by immune-related adverse effects caused by nonspecific antigen recognition and excessive activation. Here, we present a multifunctional DNA nanotoolbox (MDNT) for stable engineering of T/NK cell membranes, enabling dual-parameter-guided tumor targeting and light-controllable regulation of cellular activity. The MDNT, based on an amphiphilic DNA triangular prism with tetravalent cholesterol anchors, ensures robust membrane insertion. An ATP-activated Sgc8 aptamer module confers selective recognition of PTK7-positive tumor cells, while the photosensitizer chlorin e6 enables light-triggered reactive oxygen species generation for spatiotemporal control of immune cell activity, eliminating overactivated cells and reducing toxicity. By integrating immune cytotoxicity with photodynamic effects, MDNT significantly enhances antitumor efficacy. This work provides a modular, programmable, and controllable functional interface between DNA nanodevices and immune cells, offering a strategy to improve both safety and therapeutic performance in cancer immunotherapy.
Late-transition-metal catalysts have demonstrated exceptional capability in synthesizing in-chain keto-functionalized polyethylenes (keto-PEs); however, their homogeneous catalytic systems are highly prone to reactor fouling, which disrupts continuous slurry-phase production processes. In this contribution, MgO-supported phosphinophenolate nickel catalysts were developed for the nonalternating copolymerization of ethylene and carbon monoxide (CO). The heterogeneous catalyst demonstrated a high activity of similar to 105 g mol-1 h-1 and exhibited superior thermal stability compared to its homogeneous counterpart, particularly at elevated polymerization temperatures. Notably, the supported catalyst produced free-flowing keto-PEs with improved molecular weight and controlled spherical morphology, effectively preventing reactor fouling through robust catalyst immobilization. The resulting copolymer displayed thermal, crystalline, and tensile properties comparable to those of commercial high-density polyethylene.
Materials databases are increasingly the backbone of data-driven discovery for energy materials. In this Perspective, we map the ecosystem of computational and experimental databases, and argue that database architecture, which covers ingestion, curation, metadata, provenance, and access interfaces, strongly influences the performance and trustworthiness of modern AI models. We classify computational repositories into bulk-property and surface/interface resources, and summarize representative experimental databases spanning crystal structures, catalysis, energy storage, and characterization. Beyond single-modality repositories, we highlight integrated platforms that connect computed descriptors with context-rich experimental evidence and tool interfaces, enabling iterative hypothesis testing and closed-loop validation. Building on these examples, we propose a database-model-experiment roadmap for training and deploying graph neural networks, machine learning interatomic potentials, and large language model-based AI Agents. Finally, we outline key bottlenecks that must be addressed for reliable autonomous discovery, including FAIR (Findable, Accessible, Interoperable, Reusable)-aligned standardization, bias and missing negative results, and cross-code reproducibility.
The increasing lithium (Li) demand, attributable to its essential function in energy storage applications, has necessitated the advancement in Li extraction and recovery methods. Brine-based Li extraction presents a cost-effective and scalable solution; however, challenges such as high magnesium-to-Li (Mg/Li) ratios and environmental concerns necessitate innovative approaches. This review comprehensively examines various Li recovery techniques from brine, focusing on precipitation, adsorption and ion exchange, membrane separation, electrochemical separation, solvent extraction, and hybrid technologies. Precipitation methods, including carbonate and aluminate precipitation, offer straightforward processing but face selectivity challenges in high Mg/Li ratio brines. Adsorption and ion exchange techniques, particularly Li-ion sieves and layered double hydroxides, have demonstrated high selectivity and efficiency. Electrochemical methods present promising low-energy alternatives for Li separation. Furthermore, solvent extraction and advanced membrane-based techniques provide additional pathways for Li recovery, enhancing the yield and purity. This Perspective highlights recent advancements, process optimizations, and emerging strategies aimed at improving Li recovery while reducing environmental impact. Comparative assessment of these techniques is provided, considering factors such as the Mg/Li ratio, operational feasibility, energy consumption, and scalability. Special emphasis is placed on emerging strategies such as engineered sorbents, electrochemical separation, and advanced membrane filtration, which offer sustainable alternatives to traditional methods. Additionally, this review bridges the gap between laboratory-scale research and industrial applications, outlining key challenges and potential solutions for Li extraction. This Review provides a roadmap for developing more efficient, sustainable, and scalable Li extraction processes. The insights presented here aid researchers, industry professionals, and policymakers in advancing Li recovery technologies to meet growing global demand.
Abstract Dynamic covalent bonds (DCBs), known for their reversible cleavage and reformation under stimuli, have become a key focus in polymer science for designing adaptive materials. Among various dynamic motifs, sulfur is particularly notable for its abundance and versatile chemistry. Incorporating sulfur-based DCBs into polymer networks enables the creation of covalent adaptable networks (CANs) that combine the robustness of thermosets with the reprocessability of thermoplastics. This synergy imparts transformative functions such as self-healing, shape memory, and controllable degradation, addressing environmental challenges in material lifecycle. This minireview centers on sulfur chemistry, systematically elucidating the exchange mechanisms, characteristics, and applications of key sulfur-containing DCBs, including dynamic sulfur–sulfur or sulfur–selenium exchange, dynamic thioester exchange, reversible thiol-Michael addition, dynamic thioacetal exchange, dynamic thiocarbamate exchange, dynamic thiourea exchange, dynamic trithiocarbonate exchange, dynamic benzyl sulfide exchange, dynamic disulfenamide-amine exchange, dynamic NOS exchange, and dynamic sulfur-phenolate exchange. We compare the factors governing their dynamic behavior and illustrate how rational bond design enables precise control over material properties. Finally, current challenges and future perspectives are discussed, aiming to guide the development of next-generation sustainable, adaptive, and intelligent polymeric materials.
Abstract π-conjugated two-dimensional (2D) organic single-crystalline films (OSCFs) hold great promise for next-generation organic electronics, thanks to their ultrathin morphology, absence of grain boundaries, long-range molecular order, and excellent charge transport properties. Among various fabrication strategies, solution-processed approaches have garnered significant attention due to their ability to regulate nucleation and growth dynamics, thereby enabling the scalable fabrication of large-area, high-quality, 2D OSCFs. This review systematically examines the key parameters governing the large-area growth of 2D OSCFs, with a focused discussion on the advantages and limitations of representative solution-processed approaches. Recent breakthroughs in 2D OSCF-based field-effect transistors are highlighted along with their emerging applications in integrated organic circuits. Finally, the key challenges and further perspectives are outlined in order to promote the future development of the 2D OSCFs in next-generation high-performance organic electronic devices.
Abstract The global production and consumption of plastics generate vast amounts of waste, creating a pressing challenge for sustainable management. Varieties of solutions have been developed to convert discarded plastics into valuable resources, which can be primarily categorized into mechanical and chemical approaches. This review focuses on chemically recyclable polymers, with a particular emphasis on recent progress in precise chemical structural design, aiming at enabling or enhancing the recyclability of polymers. We first examine strategies for endowing linear polymers with recyclability, including the incorporation of renewable linkages, the redesign of monomers with tailored recyclability, and the chemical transformation of otherwise unrecyclable polymers. Precision chemistry provides a versatile toolkit to balance the often-conflicting requirements of material stability and recyclability. At last, we discuss recycling strategies for traditionally nonrecyclable polymer networks, with particular attention to covalent adaptable networks (CANs) that exploit dynamic covalent bonds.
Atomic-level control of metal-support interfaces is a key lever for electrocatalysis with low energy input, high selectivity, and long-term durability. While single-atom catalysts maximize atom utilization and provide well-defined coordination motifs, their isolated sites can limit cooperativity and compromise stability under the operating conditions. Single-atom support (SAS) overcomes these constraints by embedding atomically dispersed metal centers into the support framework as electronically active modulation units, enabling strong metal-support interactions (SMSI), directional charge migration, and programmable coupling with clusters or nanoparticles. This review summarizes atomic-level regulation strategies for SAS-enabled composite catalysts and extracts structure-function principles across the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), CO2 reduction reaction (CO2RR), and electrocatalytic nitrate reduction reaction (NO3RR). We highlight four regulation modes: coordination engineering (coordination number, heteroatom, and axial ligation), spin-state control, defect engineering (vacancies and edges), and geometric tailoring (confinement and curvature/strain), which jointly tune ligand fields, d-band descriptors, intermediate binding, and interfacial transport. Remaining challenges include predictive design, operando tracking of dynamic active structures, unified descriptor frameworks, and scalable synthesis under industrial conditions. We finally outline a closed-loop roadmap integrating data-driven prediction, stimuli-responsive modulation, multimodal operando characterization, and feedback learning.
