Chemistry of Materials最新文献

Eutectogels and DES-based elastomers offer eco-friendly, cost-effective solutions for wearable devices but face limitations in underwater applications due to their high hygroscopicity. In this study, we present a strategy for developing a core–shell elastomer (CSE) based on deep eutectic solvents (DESs) that remains stable and functions effectively underwater. The hydrophobic shell (HS) is composed of a natural DES of thymol and camphor, while the printable conductive core (CC) is based on a polymerizable DES of acrylic acid and choline chloride. By employing an interfacial polymerization approach, the core–shell interface is reinforced with strong covalent bonds rather than weak physical interactions, enhancing the structural integrity. The CSE demonstrates excellent mechanical properties, including a tensile strength of 548 kPa and a stretchability of up to 680% strain. Additionally, it exhibits hydrophobicity with a water contact angle of 91° and remains stable underwater and in harsh environments such as pH 1, pH 14, and saline water. As a result, the CSE serves as a reliable underwater strain sensor and enables Morse code communication. Furthermore, with the printability of CC, various structures can be fabricated, expanding its potential for developing advanced core–shell materials for underwater applications.

Organic cocrystals represent a cutting-edge strategy for fabricating high-performance organic functional materials, increasingly establishing their significance in materials science. This study investigates the influence of alkyl chain length modulation on the structure and vapochromic response properties by synthesizing two charge-transfer (CT) cocrystals composed of clamparene (CLP) and naphthalenediimide (NDI) derivative guests with varying alkyl chain lengths. Structural characterization reveals significant differences in the resulting materials, primarily due to variations in molecular packing arrangements induced by the alkyl chain lengths (C8 and C4), thus providing a unique platform for studying structure–property relationships. Solid-state characterization indicates that NDI8@CLPα exhibits a highly selective vapochromic response to para-xylene vapor, whereas NDI4@CLPα shows no discernible response. This result elucidates the regulatory role of alkyl chain length on intermolecular π–π stacking modes and, consequently, on the performance of the two CT cocrystals. This finding introduces a new dimension of structural control for the precise design of stimuli-responsive materials, particularly emphasizing the critical length requirement of alkyl chains in constructing such materials and offering significant guiding implications for the field of chemical sensors.

Molecular recognition-driven supramolecular assembly establishes a robust platform for topological morphological regulation and chiral signal transmission. Herein, we employ sugammadex (Sug) as a macrocyclic host that recognizes tetraphenylethylene pyridinium salt (TPE-Py) through synergistic hydrophobic and electrostatic interactions, forming a 2:1 TPE-Py⊂Sug complex exhibiting ratiometric fluorescence (emission redshift: from 555 to 600 nm). Crucially, competitive molecular recognition of neuromuscular blocking agents (NMBAs; e.g., rocuronium [Roc], vecuronium [Vec], pancuronium [Pan]) drives TPE-Py displacement due to Sug’s superior binding affinity for NMBAs, restoring TPE-Py’s intrinsic fluorescence (detection limits: 164.4 nM for Roc, 170.8 nM for Vec, 2187.7 nM for Pan). This recognition event orchestrates supramolecular topological reconfiguration: Electrostatically driven coassembly of displaced TPE-Py with NMBA⊂Sug yields a ternary NMBA⊂Sug@TPE-Py complex, inducing a morphological transition from nanoparticles to nanosheets─a signature of topological reconstruction. Chiral centers in NMBAs further modulate circular dichroism and chiroptical responses; notably for Vec, circularly polarized luminescence inverts from negative to positive (g_lum value changing from −2.4 × 10^–4 to 2.7 × 10^–4). Leveraging the fluorescence-concentration linearity with smartphone-based RGB analysis enables portable semiquantitative detection for NMBAs. This work establishes molecular recognition-driven topological reconfiguration as a paradigm for multichannel sensing and chiral regulation.

NASICON-type Na₃V₂(PO₄)₃ material features an open three-dimensional framework structure, which has garnered extensive attention due to its high ionic conductivity and structural stability. However, poor electronic conductivity, harmful phase transitions, and inadequate rate performance hinder their practical applications. Herein, a high-entropy Na_3.185V_1.725Mn_0.055Co_0.05Cu_0.045Cr_0.045Al_0.045Ni_0.035(PO₄)₃ (HE-NVTMP) cathode is elaborately crafted by multielement doping strategy. The cathode renders a high initial specific capacity of 197.7 mAh g^–1 and a large energy density of 552 Wh kg^–1 at 0.2 C. Additionally, the cathode maintains stable long-term cycling durability and minimal capacity fade under high 10 C-rate conditions (1100 cycles with 80.95% capacity retention). The synergistic high-entropy doping activates the V⁴⁺/V⁵⁺ redox couple, enhancing Na⁺ diffusion kinetics and achieving high reversibility. In situ XRD analysis reveals that the high-entropy effect optimizes the crystal structure and achieves a low volumetric strain (3.4%) by suppressing the two-phase reaction (Na₃V₂(PO₄)₃ → Na_3-xV₂(PO₄)₃ → NaV₂(PO₄)₃). The multielement synergy promotes the occurrence of single-phase reaction and inhibits phase separation. The full cell of HE-NVTMP//hard carbon delivers a high initial capacity of 107.7 mAh g^–1 at 0.5 C and an excellent rate performance (79.1 mAh g^–1 at 15 C).

Rechargeable lithium oxygen (Li–O₂) batteries are regarded as promising candidates for future energy storage systems due to their exceptionally high theoretical energy density. However, their practical implementation faces major obstacles, including high charge and discharge overpotentials and a semiopen battery structure that is highly sensitive to humidity. These factors lead to reduced efficiency and poor stability in moist air, significantly limiting real-world application. To address these challenges, a composite photoelectrode was developed by directly growing tungsten trioxide (WO₃) nanoribbons on carbon paper (CP), followed by the uniform deposition of platinum nanoparticles using atomic layer deposition. Compared to WO₃ photoelectrode, the resulting Pt–WO₃ photoelectrode enables stable operation of photoassisted Li–O₂ batteries under humid oxygen atmosphere. The batteries sustain stable operation for over 100 cycles without failure at current densities of 0.05 and 0.2 mA cm^–2. Advanced characterization and theoretical calculations confirm the formation of an ohmic contact between platinum and tungsten trioxide, which promotes the separation of photogenerated electrons and holes, improves charge transfer, and facilitates the reversible formation and decomposition of lithium hydroxide (LiOH). This strategy effectively overcomes critical barriers faced by conventional Li–O₂ batteries in real-world environments and provides a promising direction for the design of environmentally tolerant and photoelectrochemically efficient energy storage systems.

Self-sorting not only guides biological systems to generate specific products from multiple possibilities but also serves as a pivotal strategy for the higher-level assembly of supramolecular systems. Herein, we present the synthesis of a novel ternary macrocycle cocrystal (MCC), which is composed of phenanthrene[2]arene (P2), p-benzoquinone (BQ), and tetrachloro-1,4-benzoquinone (TCBQ), achieved through a self-sorting process. Ternary MCCs display superior photothermal conversion capability under 808 nm laser irradiation, rapidly attaining a temperature of 140 °C within a mere 18 s. Experimental and theoretical studies reveal that increasing the charge transfer effect in organic cocrystals can significantly improve their photothermal conversion capability and effectively reduce their HOMO–LUMO energy gap. Moreover, upon one sunlight illumination, a cotton cloth loaded with 50 mg of the ternary MCC demonstrates an impressive solar-driven interfacial water evaporation rate of 2.36 kg m^–2 h^–1, corresponding to an evaporation efficiency of 92.6%. Notably, the water evaporation rate of 10 wt % NaCl water is similar to that of pure water, suggesting that ternary MCCs have strong salt resistance.

The development of upconversion hydrogels that operate in water and under aerobic conditions remains a significant challenge, especially when postreaction separation and component recovery are needed. Here, we present the first supramolecular photocatalytic hydrogel based on a low-molecular-weight gelator (LMWG) that enables green-to-blue triplet–triplet annihilation upconversion (TTA-UC) in aerated water. The hydrogel forms through the coassembly of the LMWG, surfactant, and a sensitizer/emitter pair (PtOEP/DPAS), giving rise to nanostructured compartments that protect long-lived excited triplet states from oxygen quenching. Unlike previous systems based on biopolymers or covalent networks, this supramolecular gelation is fully reversible, allowing the photochemical reaction to be carried out in situ, followed by gel disassembly for the easy extraction of reaction products without the need for heat. Notably, up to 77% of the precious Pt-based sensitizer can be recovered from the gel matrix. This modular, recyclable platform offers an approach to performing photochemical transformations under mild and environmentally friendly conditions, with advantages over previous air-stable UC hydrogels in terms of reusability, extractability, and operational simplicity.

In lithium metal batteries (LMBs), the uncontrolled growth of lithium dendrites not only poses safety risks by potentially piercing the separator and causing short circuits, but also consumes active lithium, significantly reducing the Coulombic efficiency (CE). Moreover, the naturally fragile solid electrolyte interphase (SEI) tends to break and reform repeatedly, leading to sustained electrolyte consumption. In this study, trimethyloxonium tetrafluoroborate (TMOBF₄) is introduced as a dual-functional additive to promote uniform lithium deposition and stabilize the SEI. The TMO⁺ cation, possessing a lower reduction potential than Li⁺, preferentially adsorbs at dendrite protrusions, forming an electrostatic shielding layer that redistributes the Li⁺ flux. This adsorption suppresses localized Li⁺ accumulation and effectively mitigates dendritic growth. Simultaneously, the BF₄^– anion is involved in the Li⁺ solvation structure, significantly reducing the desolvation energy barrier and decomposing during cycling to form LiF, a critical component of a robust SEI. With the additive, the electrochemical performance of lithium cells is remarkably improved. Li||Li symmetric cell exhibits stable cycling stability for 2000 h at 0.5 mA cm^–2, and Li||LiFePO₄ cells retain 93.0% capacity retention after 300 cycles at 1 C. These results present a promising strategy for developing high-performance LMBs.

Crystalline organic–inorganic halometallate hybrids have emerged as promising materials for optoelectronic applications due to their structural diversity and tunable properties. We report a three-dimensional (3D) hybrid organic–inorganic crystal─[Fe(bpy)₃]₂Ag₆Br₁₁·NO₃ (bpy = 2,2′ bipyridine)─consisting of two-dimensional (2D) Ag(I)-based (Ag₆Br₁₁)_n^5n– anionic sheets, zero-dimensional (0D) [Fe(bpy)₃]³⁺ complexes (acting as the structure-directing agent), and interlayer disordered NO₃^– anions. Specifically, the thermodynamically unstable cation [Fe(bpy)₃]³⁺ is stabilized under ambient conditions by the two-dimensional (2D) inorganic anionic scaffold. The crystal exhibits strong ligand-supported argentophilic interactions (Ag···Ag bond distance of 2.98 Å), forming an extended (Ag₆Br₁₁)_n^5n– network, and displays broad UV–visible absorption with a band gap of 1.90 eV. Remarkably, this organic–inorganic hybrid shows a ∼10³-fold increase in photocurrent under 532 nm light illumination. Density functional theory calculations provided the mechanistic insights, and such a remarkable photoconductivity is attributed to an efficient charge delocalization and inorganic-to-organic charge transfer. Additionally, the crystal exhibits an ultralow thermal conductivity over a broad temperature range (≈0.3 W/m·K; 300–400 K), making it an excellent candidate for heat management applications.