Qiaowei Li

The photocatalytic cycloaddition of CO ₂ with epoxides offers a sustainable approach for CO ₂ fixation and value‐added carbonate synthesis, yet developing well‐defined photocatalysts that integrate narrow bandgap, abundant active sites, and strong CO ₂ enrichment ability remains challenging. Herein, a new conjugated metal−organic framework (MOF) using hexahydroxytriphenylene as linkers and hexanuclear [Nd ₆ ( μ ₆ ‐CO ₃ )O ₁₂ ] ⁸⁻ as inorganic nodes is constructed. The obtained FDM‐154 possesses interconnected 13.6 Å pores and a surface area of 532 m ² g ⁻¹ , enabling efficient CO ₂ enrichment (28.5 cm ³ g ⁻¹ ). Furthermore, FDM‐154 features a narrow optical bandgap of 1.12 eV, which facilitates photogenerated charge separation under visible light. Additionally, the MOF backbone is decorated with dense photoactive organic linkers and Nd ³⁺ Lewis acid sites that serve as active centers to efficiently activate both CO ₂ and epoxide substrates during the photocatalytic process. FDM‐154 photocatalyst achieves high yield for CO ₂ cycloaddition with epichlorohydrin under mild conditions, resulting from the combined effect of its suitable band structure, accessible active sites, and pore confinement effect.

Direct air capture (DAC) is a promising strategy for mitigating atmospheric CO2 accumulation, yet sorbent evaluation remains dominated by equilibrium uptake under static conditions that fail to capture kinetic, humid, and process-level constraints relevant to real operation. Here we establish a dynamic evaluation framework that replaces equilibrium-centric metrics with a unified platform integrating high-precision gravimetric measurements, ppm-level CO2 nondispersion infrared detection, and capacitive humidity sensing, enabling direct quantification of adsorption kinetics, H2O/CO2 coadsorption, breakthrough behavior, and regeneration energy under low CO2 concentration and dry/humid conditions. Using TAEA@MIL-101(Cr) as a benchmark system, we introduce a sonication-assisted impregnation strategy that enables coordinated amine anchoring with preserved porosity and strong CO2 chemisorption. The optimized material exhibits a high equilibrium CO2 of 3.12 mmol g–1 (13.8 wt %) at 298 K, a dynamic breakthrough capacity of 12.4 wt % under dry conditions, and a retained capacity of 9.7 wt % at 50% relative humidity. Complete regeneration is achieved at 50 °C, enabling low-energy temperature-swing operation. This work establishes a generalizable dynamic benchmarking framework for DAC sorbents and positions TAEA@MIL-101(Cr) as a reference platform bridging molecular design, kinetic performance, and process-level energy requirements to complement conventional equilibrium evaluation.

Precise control of interfacial reactive hydrogen is crucial for improving the selectivity of proton-coupled electron transfer reactions in electrocatalysis. In the nitrate electroreduction to ammonia reaction, a fundamental trade-off is identified for copper (Cu)-based catalysts, where slow water dissociation at low potentials causes reactive hydrogen scarcity, whereas at high potentials, elevated reactive hydrogen flux is diverted into hydrogen evolution. To overcome this mismatch, we coated a poly(sodium acrylate) hydrogel on a Cu foam-supported Cu nanoarray, empowering the Cu catalyst surface with a hydrophilic, hydrogen-bonded network. The resulting Cu@PANa/CF catalyst achieved a Faradaic efficiency for NH3 exceeding 90% over a wide potential window and reached a peak of 98% at −0.3 V vs RHE, while delivering a 2-fold higher NH3 yield rate at low overpotentials compared to bare Cu/CF. In situ characterizations and mechanistic analyses corroborated that the PANa hydrogel enriched water on the interface and facilitated the generation and stabilization of reactive hydrogen, thereby sustaining an effective hydrogen supply. In parallel, hydrogen-bonding interactions between the PANa hydrogel network and the nitrogenous intermediates stabilized key reaction species (*NO2H, *NH2O, and *NH2OH) and lowered the free energy difference of the rate-determining step (*NO2 to *NO2H). Together, these effects suppressed competing reactions and directed reactive hydrogen toward sequential hydrogenation, enabling efficient NO3–-to-NH3 conversion. This work demonstrates that designing microenvironments of Cu catalyst surface through a hydrogen-bonded network can effectively complement electronic tuning and provides a broadly applicable framework for selectivity control in electrocatalysis.

Precise control over the presence and position of knots in polymers remains a long-standing synthetic challenge, with theory indicating broad implications for properties and function. Here we report on a topological synthon approach—extension and macrocyclization of an overhand knot—that enables the high yielding synthesis of closed-loop trefoiled polymers with narrow polydispersity and tunable topological parameters. From the same set of building blocks we prepared linear, cyclic and trefoiled topoisomers of matched chemical composition, allowing topology–property relationships to be examined directly. Low-temperature ultrahigh-vacuum scanning tunnelling microscopy resolved three conformers of trefoiled polystyrene, with high-, medium- and low-symmetry forms whose populations depend on chain length, local flexibility and solvation. Coarse‑grained Langevin dynamics reproduce these distributions and indicate that bending energy and conformational entropy govern conformer stability. Metal binding localizes the knotted region, reminiscent of protein/DNA knot translocation. The synthon also affords trefoiled poly(ethylene glycol) and trefoiled polystyrene–poly(ethylene glycol) diblock copolymers, demonstrating the generality of the approach across polymer backbones.

Lithium-sulfur (Li-S) batteries are promising next-generation energy storage systems, yet critical challenges including severe sulfur volume expansion, uncontrolled lithium polysulfide (LiPS) shuttling, and sluggish sulfur redox kinetics impede their practical application. Herein, we develop a metal-organic framework (MOF) functionalization strategy across three distinct structural modules (MOF backbone, grafted modulators, and engineered pore space) to tackle these issues. Specifically, in the newly synthesized Zr-based spn topology FDM-221, its high surface area (1956 m² g^-1) and large pore volume (1.35 cm³ g^-1) provide ample pore space to accommodate sulfur volume expansion even after high sulfur encapsulation. Furthermore, sulfiphilic sites (coordinatively unsaturated Zr(IV) in the framework backbone) and lithiophilic moieties (S atoms from the benzotrithiophene-based linker and F atoms from the dangling modulators) work in tandem to furnish robust binding sites for LiPS adsorption while concurrently accelerating the redox catalysis of sulfur species. Li-S batteries based on this trinity structure deliver a high capacity of 1164 mAh g^-1 at 0.1C and excellent cycling stability over 1000 cycles at 2C, demonstrating the great potential of this MOF design strategy for next-generation batteries.

Foundation models require massive amounts of training data, which are often costly to obtain in materials science. Meanwhile, long-established physical knowledge such as molecular force fields and geometric analysis provides direct guidance for material behavior, but remains insufficiently leveraged. Here we demonstrate that expert knowledge can directly supervise pre-training and substantially reduce data requirements. A set of potential energy surface (PES) basis functions, which encode guest-host interaction energetics, is developed as unified descriptors for different guest molecules. A multi-modal architecture is designed to fuse information from both material structure and PES. Pre-training is achieved by learning comprehensive geometric features spanning different spatial scales. Consequently, a foundation model for porous materials is developed under limited data regimes, named SpbNet. SpbNet is evaluated on over 50 downstream tasks, including adsorption, separation, and intrinsic properties, etc. SpbNet consistently outperforms models pre-trained on datasets nearly 20 times larger, reducing the relative errors by over 20%. In addition, SpbNet demonstrates strong generalization capabilities across both in-distribution and out-of-distribution materials, such as Metal Organic Frameworks, Covalent Organic Frameworks, and zeolites.

As a broad-spectrum antimicrobial agent, furaltadone is widely used in various sterilization fields. They are easily excreted into wastewater, resulting in bioaccumulation and posing risks to the local environment. In this work, a new metal-organic framework (MOF) with a previously unreported self-catenated net feature was synthesized using an asymmetric linker to remove the furaltadone antibiotic from aqueous media. The distinctive ring arrangement within the network is guided by the highly unsymmetrical organic linker, while strong hydrogen bonds between neighboring building units provide additional stabilization to this structure. Boasting high surface area and large pore volume, the MOF with self-entanglement strongly interacts with furaltadone molecules via prominent interaction sites. Highly efficient removal of furaltadone under neutral conditions with rapid uptake, high capacity (95.1% adsorption rate and up to 278.6 mg g^-1 maximum monolayer capacity) and cyclability was achieved. These attributes establish the presented MOF as a promising adsorbent for mitigating antibiotic contamination in environmental remediation.

Metal–organic frameworks typically rely on discrete molecules as building units, and creating frameworks featuring continuous organic or inorganic subnet moieties, such as chains and layers, is challenging. While all-inorganic subnets have been used as units with infinite connectivity, the intrinsic disorder in organic chains and layers hinders their role as well-defined building blocks for reticular materials. Here we report the one-pot synthesis of a series of Zr₆O₈-based or Hf₆O₈-based metal–organic frameworks that feature boroxine-based one-dimensional and two-dimensional covalent organic frameworks—chains with diverse conformations and layers with specific topology, respectively—as the organic components. The spatial compatibility between the constituents locks the infinite organic units into patterned arrangements and thus generates metal–organic frameworks with distinct structural entities and pore environments in separate sections along specific directions. The coexistence of extended covalent organic frameworks and discrete inorganic units, side by side and yet independent of each other, leads to high structural compartmentalization in space.

Although the superiority of hierarchical structure has driven extensive demand for applications, establishing hierarchy in a long-range-ordered single crystal remains a formidable challenge due to the inherent competition and contradiction between single crystallinity and controllable hierarchical structure. Herein, we demonstrate a growth and dissociation kinetics cooperative strategy for synthesizing a family of hollow single-crystalline mesoporous metal-organic frameworks (meso-MOFs) with hierarchical structures. The approach employs a dual-template method, integrating both hard and soft templates. By adjusting the HCl/CH₃COOH ratio, the reaction system's pH can be tuned to regulate the dissociation kinetics of the acid-sensitive seeds serving as hard templates for the formation of hollow structure, while simultaneously modifying the concentration of the dual acids to control the growth kinetics of meso-MOF shells. The competition between maintaining a single crystallinity and achieving a well-defined hierarchical structure can be effectively balanced. Driven by the two interfacial kinetics, we successfully obtained the octahedral meso-MOF nanoparticles that not only exhibit a well-defined hollow structure with precisely controllable hollow size (∼81-1120 nm) and tunable wall thickness (∼28.6-61.3 nm) but also retain their single-crystal integrity. Specifically, the dissociation kinetics of seeds governed the formation of hollow structures, while the growth kinetics of single-crystalline meso-MOF shells ensured uniform coverage and structural integrity. Based on this strategy, we further developed a series of novel hollow meso-MOFs with hierarchical nanostructures, including hollow open-capsule meso-MOFs, 2D hollow meso-MOFs, hollow interlayer-structured meso-MOFs, macro-meso-micro trimodal porous MOFs, and so on.