Materials Chemistry Frontiers最新文献

Efficient capture of sulfur hexafluoride (SF₆) is challenged by the molecule's chemical inertness and the persistent trade-off between adsorption capacity and selectivity in porous materials. Herein, we report a series of semi-cycloaliphatic microporous polyimides (MCPIs) via a “conjugation interruption” strategy that synergizes steric confinement with electrostatic modulation. By incorporating bicyclo[2.2.2]oct-7-ene (BCO) units into the polymer backbone, we effectively disrupt global π-electron delocalization. Density functional theory calculations show this interruption localizes electron density onto the imide carbonyls, thereby amplifying the local electric field (LEF). This intensified LEF, acting in concert with BCO-directed ultramicropores (∼6.1 Å), creates high-affinity “electro-inductive traps” for SF₆. Consequently, MCPI-1 exhibits a high SF₆/N₂ selectivity of 140 and an SF₆ uptake of 1.69 mmol g⁻¹ at 273 K and 100 kPa. These findings highlight that modulating electron localization via backbone conjugation breaking provides a precise molecular engineering dimension to transcend the limitations of conventional aromatic frameworks.

When interacting with the dynamic world, creatures always outdo their electronic counterparts because of their sophisticated sensory systems. From direct perception of the world via soft tissue to intelligent information processing, immensely varied biological movements of organisms mostly rely on accurate ion transport. Imitating the flexible structure of biological systems and the functional mechanism based on ion transport would essentially solve the unmet needs of modern sensing technology. Simultaneously, the establishment of ionic sensor systems would effectively narrow the gap between the biological systems and the artificial equipment to promote seamless interaction of both sides, which could bring a revolution in advanced operations and medical rehabilitation. The outstanding properties of hydrogels enable them to be used as ion conductors like biological tissues for the development of ionic sensory systems. In this review, we introduce the basic principles of ion transport in hydrogels, and discuss the five key elements of hydrogel ionic sensory systems: ionic sensors, ionic transporters, ionic processors, ionic effectors, and ionic power sources, in terms of their structures, working mechanisms and applications. Finally, we suggest future directions and potential challenges of hydrogel-based ionic sensory systems.

Transition metal-based layered chalcogenides show intriguing magnetic properties, high tunability, and cleavability that allow the fabrication of heterostructures with peculiar functional properties for designing spintronic devices, such as new types of low-power memory. TaFeTe₂ layered van der Waals telluride can be synthesized by chemical vapor transport reactions. The optimized synthesis conditions yield bulk single crystals of the new monoclinic polymorph with unit cell parameters of a ∼ 7.3 Å, b ∼ 6.1 Å, c ∼ 8.2 Å, and β ∼ 93° according to the indexing of the electron diffraction patterns. Study of its crystal structure using high-resolution transmission electron microscopy confirms the monoclinic distortion and indicates the presence of hexagonal Ta honeycombs and Fe–Fe dumbbells. Band structure calculations show a ferromagnetic ground state with magnetic moments of 1.5µ_B on Fe atoms oriented perpendicular to the structural layers. Magnetic susceptibility and magnetization measurements confirm the spin-glass state with T_f = 23 K and strong perpendicular magnetic anisotropy.

Birefringent materials are essential for polarized light modulation in optical communications and laser technologies, yet synthesizing high-performance UV/DUV variants remains challenging. This study proposes a multiscale microstructural modulation strategy. First, introducing substituents, such as [CH₃], [NH₂], and [CH₃CO], into guanidinium cations enhances their polarizability anisotropy. Second, by leveraging the differences in basicity among guanidine derivatives, their pH control enables the precise regulation of B–O polymerization, achieving interconversion among the [B(OH)₃], [B₃O₃(OH)₄]⁻, [B₄O₅(OH)₄]²⁻, and [B₅O₆(OH)₄]⁻ groups. Third, hydrogen bond-directed self-assembly facilitates the coplanar arrangements and ordered stacking of π-conjugated cations and borate anionic clusters, further enhancing the optical anisotropy. Among the synthesized compounds, four exhibit DUV cutoff edges <200 nm and large birefringence (0.077–0.143 at 546 nm). Notably, DGBH combines a wide bandgap (HSE06 = 6.18 eV) with cm-scale crystal growth, showing strong DUV birefringent potential. GBH-2 achieves a birefringence (Δn_exp. = 0.311 at 546 nm) that is 14.80 times that of its structural analog Ba₂B₁₀O₁₆(OH)₂·(H₃BO₃)·H₂O. Validated experimentally and theoretically, this exceptional performance originates from the synergy among cation modification, precise control of B–O polymerization, and optimized functional motif arrangement, breaking conventional paradigms. This pioneering strategy provides a valuable framework for accelerating the discovery of high-performance birefringent materials.

The synergistic effects of bacterial infection and oxidative stress remain critical barriers to tissue repair in chronic wounds. Although cerium oxide (CeO₂)-based nanozymes show promise, achieving a precise balance between their pro-oxidant and antioxidant activities is essential for therapeutic safety and efficacy. Herein, we report a multifunctional nanotherapy platform based on silver nanoparticle (AgNP)-decorated CeO₂ hollow multishelled structures (Ce HoMS/Ag). The hollow multishelled structure facilitates uniform AgNP dispersion and high active-site exposure. The Ag loading nonlinearly modulates the surface oxygen vacancies on CeO₂ HoMS, with the oxygen vacancy concentration decreasing initially and then increasing. This site-specific modification suppresses peroxidase-like activity, while the sustained release of Ag⁺ from Ce HoMS/Ag endows it with potent bactericidal activity against MRSA and E. coli. Moreover, the catalase- and superoxide dismutase-like activities of Ce HoMS/Ag enable effective scavenging of reactive oxygen species, thereby significantly accelerating wound closure and enhancing tissue regeneration in diabetic mouse wound models. This combination of defect engineering and hierarchical structure design provides an antibiotic-free strategy for simultaneous infection control and oxidative stress modulation in chronic wounds.

The selective and sensitive detection of heavy metal ions remains a grand challenge at the interface of materials chemistry, environmental monitoring, and public health. This review adopts a mechanism-centric perspective to deconstruct how molecular recognition principles—rooted in coordination chemistry, supramolecular interactions, and confinement effects—govern sensor performance. Rather than compiling materials by category, we critically examine structure–mechanism–performance relationships across emerging platforms including metal–organic frameworks, covalent organic frameworks, quantum dots, MXenes, molecularly imprinted polymers, biomolecular scaffolds, and functionalized mesoporous materials over the past five years. We further compare how these platforms balance sensitivity, selectivity, reversibility, interfacial transport, and practical deployability under chemically complex conditions. Special emphasis is placed on the interplay between thermodynamic affinity, kinetic reversibility, and transduction efficiency in realistic sample matrices. Beyond analytical performance, this review also discusses how interfacial design influences anti-interference capability, regenerability, and the integration of sensing with adsorptive capture in environmentally relevant systems. We highlight conceptual innovations such as multi-modal sensing, self-healing and regenerable interfaces, wearable and microfluidic integration, and machine learning-assisted selectivity enhancement. Persistent challenges—matrix effects, reproducibility gaps, and operational stability—are examined alongside strategies to bridge lab-scale sensing and field deployment. By consolidating these insights, this review provides not only a critical assessment of recent advances, but also a practical framework for identifying the key materials and mechanistic descriptors that govern translation from proof-of-concept sensing to robust real-world monitoring. This review concludes with a forward-looking framework for the rational design of intelligent sensing architectures capable of adapting to evolving environmental complexities.

Passivation of external surface acid sites in zeolites is a widely used strategy to enhance catalytic stability and to mitigate undesired non-shape-selective reactions. However, the synthesis of zeolites with a uniform and thickness-controllable Si-zoned shell in a true one-pot process remains a significant challenge. Here, we develop an ethanol-mediated one-pot route to synthesize surface Si-zoned ZSM-5 zeolites. Ethanol creates a favorable synthesis environment that promotes a classical, layer-by-layer crystallization pathway, enabling the near-quantitative utilization of aluminosilicate species during the initial crystallization stage. This complete consumption of framework-forming species allows soluble silicate species to be subsequently added directly into the mother liquor, where they are selectively incorporated onto the preformed ZSM-5 crystals to build a thickness-tunable silica-rich shell. Notably, bulk and surface analyses together with probe reactions using bulky molecules confirm that the silica-rich shell is structurally continuous and effectively inert toward bulky reactants. This ethanol-mediated strategy offers a facile, high-yield, and scalable one-pot platform for engineering surface compositions in zeolites. The resulting surface Si-zoned ZSM-5 offers a versatile basis for the design of catalysts with improved stability and shape-selectivity.

We present a theoretical framework to predict the open-circuit voltage and short-circuit current density of small-molecule bulk heterojunction solar cells. The method is based on the reciprocity relation and on a quantum mechanical description of the elementary processes. Radiative and non-radiative decay rates are evaluated through Fermi's golden rule. The Franck–Condon weighted density of states, computed via the generating function formalism, is employed as a genuine predictive tool, in that it enters the expression for both radiative and non-radiative decay rates and determines the absorption profile governing photogeneration. The method requires only a limited set of experimentally accessible inputs, namely the redox potentials and absorption spectra of the donor and acceptor materials, and involves a small number of adjustable parameters with negligible impact on the results. This makes the framework suitable for studying different donor–acceptor combinations in small-molecule organic solar cells based on either fullerene or non-fullerene acceptors. The model provides a direct interpretation of open-circuit voltage by linking voltage losses and photocurrent generation to specific processes, such as non-radiative recombination, subgap effects, and absorption-edge broadening. It also captures the temperature dependence of open-circuit voltage and short-circuit current density, which is essential for evaluating device performance under realistic operating conditions. Overall, the proposed approach provides a unified and computationally efficient framework for predicting open-circuit voltage and short-circuit current density and for relating them to the underlying physical processes in small-molecule organic solar cells.

The pursuit of artificial systems that emulate the precision and adaptability of biological nanochannels has culminated in the development of photoresponsive ionic nanofluidics. Incorporating photoisomerizable molecular switches (e.g., azobenzene, spiropyran, diarylethene) enables precise molecular-level control, enabling multi-dimensional regulation of pore size, surface charge, and wettability, offering unique advantages for smart ion-transport regulation. Despite substantial progress, the field still lacks a systematic framework connecting molecular modification strategies, transport regulatory mechanisms, and applications, which restricts the rational design of high-performance nanofluidic systems. This review addresses this critical gap by establishing a comprehensive, hierarchical molecule-strategy-mechanism-application framework based on recent developments. We systematically categorize and critically analyze three core modification approaches (i.e., direct grafting, mediator-assisted tethering, and host–guest embedding), elucidate the hierarchical regulatory mechanism from single-property modulation to multi-dimensional synergistic control, and map these fundamental principles to advanced applications in energy conversion, ionic gating, and biomimetic devices. By integrating these principles and outlining a forward-looking research roadmap, this review provides a foundational blueprint for the rational design of next-generation, high-performance photonic nanofluidic channel devices with great potential across energy, environmental, and biomedical sectors.

Pervaporation (PV) desalination using thin-film nanocomposite (TFN) membranes has emerged as a promising solution to global water scarcity, offering exceptional salt rejection, broad salinity tolerance, and high water recovery efficiency. Membrane performance is governed by the structural architecture and chemical composition of the selective, gutter, and support layers, which collectively regulate water transport through nanoengineered channels. In this review, we critically discuss the fundamental mechanisms underpinning PV desalination, operational parameters, process configurations, and recent advances in TFN membranes. Special emphasis is placed on material–structure–property relationships, particularly the role of nanomaterials in selective layers, as they demonstrate potential to address the trade-off between water flux and salt rejection. Furthermore, we summarize the current status and challenges of TFN membranes in PV desalination, including fouling and scalable fabrication. Future directions should focus on rational membrane design, scalable fabrication, and practical evaluation of desalination performance. Consequently, high-performance TFN membranes are expected to emerge as a critical pathway toward sustainable, high-efficiency PV desalination systems.