Materials Chemistry Frontiers最新文献

The development of high-capacity anode materials with stable long-term cycling performance remains a critical challenge for next-generation lithium-ion batteries (LIBs). In this work, a CuMn₂O₄/VS₂ heterostructure composite was successfully synthesized via a facile hydrothermal method to overcome the intrinsic limitations of pristine CuMn₂O₄, including poor electronic conductivity and severe volume expansion during cycling. The engineered heterostructure, consisting of CuMn₂O₄ spinel nanoparticles anchored on conductive VS₂ nanosheets, provides strong interfacial coupling that facilitates rapid electron transport, lower Li⁺ diffusion pathways, and enhanced structural stability. Comprehensive characterization using XRD, FTIR, Raman, XPS, BET, FESEM, and TEM confirms the formation of a well-integrated and porous architecture with high surface area. As a result, the composite electrode exhibits an initial discharge capacity of 752 mAh g⁻¹ and retains 485 mAh g⁻¹ after 500 cycles at 0.1 A g⁻¹ current density, corresponding to a capacity retention of 64.26%, significantly outperforming pristine CuMn₂O₄ (190 mAh g⁻¹). Additionally, the electrode demonstrates excellent rate capability and enhanced cycling stability, despite an initial irreversible capacity loss of 33.5%. The improved electrochemical performance is attributed to enhanced charge-transfer kinetics, improved electrical conductivity provided by VS₂, and efficient utilization of active sites due to the heterostructure design. These findings highlight the significance of rational heterostructure design in developing durable, high-performance anode materials for next-generation LIB applications.

Phosphates and phosphonates have attracted extensive research owing to their diverse functional capabilities. In this work, two new hydrated ionic cocrystals, [C(NH₂)₃]₂(PhPO₃)·2H₂O (1) and (C₅H₇N₂)₂(PhPO₃)·5H₂O (2), were synthesised using a simple solution evaporation method. Single-crystal structural analyses revealed that both compounds crystallise in polar space groups and feature phenylphosphonate anions, guanidinium or 4-aminopyridinium cations, and lattice water molecules. Compounds 1 and 2 exhibit pronounced second-harmonic generation (SHG) responses of approximately 0.74 × KH₂PO₄ (KDP) and 2.0 × KDP, respectively, together with high laser damage thresholds of 1.44 GW cm⁻² (1.82 × KDP) and 1.23 GW cm⁻² (1.56 × KDP). The two compounds exhibit UV absorption edges at short wavelengths of 285 nm and 330 nm, respectively. Notably, substantial proton conductivities of 1.25 × 10⁻³ S cm⁻¹ and 3.94 × 10⁻³ S cm⁻¹ were measured for compounds 1 and 2, respectively. Overall, compound 2 outperforms compound 1 and many reported phosphonate-based materials in terms of SHG and proton conductivity. Theoretical calculations attribute these exceptional properties to the synergistic interaction between the phosphonate anion with a large hyperpolarizability, the push–pull π-conjugated cation, and the extended hydrogen-bond network. This study establishes a new structural paradigm for the design of advanced multifunctional materials.

Silicon tetrachloride (SiCl₄), the major byproduct of the Siemens process for polysilicon production, is essential for the modern electronics and semiconductor industries but has limited value and poses significant environmental challenges if not upcycled properly. Beyond converting it into common silicon products, recent research has shown its promise in advanced energy and catalysis fields. Herein, we report that the modification of a leading catalyst material—layered double hydroxides (LDHs)—with SiCl₄ can significantly alter the product selectivity of heterogeneous CO₂ hydrogenation. Specifically, SiCl₄ exfoliates and covers CoZnAl–LDH, disrupting the layered structure, altering the electronic structure, and shifting the pathway from deep hydrogenation towards CH₄ to directly produce CO. This work provides new insights into the potential of SiCl₄ as a reagent for the synthesis of efficient catalysts for advanced energy catalysis.

Severe recombination of photogenerated carriers and inefficient transfer rate have become the key factors limiting photocatalytic hydrogen production. Herein, we constructed a delicately structured and highly efficient photosystem by decorating TiO₂ nanofibers with Pt/CdS nanoparticles via a green synthesis method. Benefiting from the dual-facilitated all-solid-state Z-scheme heterojunction and internal Pt nanoparticles, such a ternary composite achieves effective spatial separation of photoinduced electrons and holes. As expected, the optimized TiO₂–Pt–CdS photocatalyst exhibits superior activity in photocatalytic hydrogen evolution (4.02 mmol g⁻¹ h⁻¹), representing 279% and 1335% improvement compared with TiO₂–CdS (1.06 mmol g⁻¹ h⁻¹) and TiO₂ (0.28 mmol g⁻¹ h⁻¹), respectively. The rational structural design of the nanofiber composite, strong interfacial interaction, and Pt nanoparticles at the TiO₂–CdS interface promote the formation of a built-in electric field and enhanced charge transport, which can drive the directional migration of charges with high redox ability and high speed. This work provides a promising design strategy for photocatalysts with improved solar conversion efficiency.

Na–air batteries offer advantages such as high theoretical energy density and abundant precursor resources. Owing to the low first ionization energy of sodium ions, Na–air batteries have more competitive low-temperature performance compared to similar batteries. However, at low temperatures, Na–air batteries continue to encounter critical challenges, including safety risks associated with dendrite growth during cycling and increased interfacial impedance induced by the elevated viscosity of the electrolyte. Herein, a strategy is proposed to improve battery safety and ensure stable operation of the battery at low temperature, preparing a liquid anode with low voltage gap and high safety by dissolving metallic sodium and biphenyl in ethylene glycol dimethyl ether solvent, and adding antifreeze additives to the liquid system to improve the low-temperature cycle performance of the battery. The prepared liquid anode reacts mildly with water, while leveraging the low viscosity and weak solvation properties of 1,3-dioxolane, enabling the assembled hybrid Na–air battery to maintain a low voltage gap of 0.54 V at −30 °C and to cycle stably for over 750 cycles. This work offers a viable strategy for developing batteries with high safety and stability at low temperatures, and provides a valuable reference for the design of batteries operating under extreme conditions.

For the first time, an amino acid-derived polymeric supramolecular hydrogel, poly(Cu(lysine methacrylamide)₂-random-acrylamide) [poly(Cu(LysMAM)₂-r-AM)], is synthesized via radical polymerization of Cu(lysine methacrylamide)₂ (Cu(LysMAM)₂) and acrylamide (AM) at room temperature. The hydrogel exhibits remarkable multifunctionality by demonstrating rapid self-healing within 5 seconds at 25 °C for a 3 mm cut, along with excellent load-bearing capability with a tensile strength of 0.14 MPa and an ultimate strain exceeding 35%. It further shows responsiveness to Cu²⁺ ions, possesses inherent electrical conductivity, and displays strong underwater adhesion driven by hydrophobic aggregation, highlighting its advanced and versatile performance characteristics. Upon treatment with 8-hydroxyquinoline, the hydrogel disassembles into poly(LysMAM-r-AM), which further forms a nanogel in the presence of Cu²⁺ at pH 9.5. The polymer selectively senses different heavy metals such as cadmium, lead, zinc, mercury, and nickel, but forms a nanogel exclusively with copper. Notably, the incorporation of Cu²⁺ imparts conductivity to the hydrogel, allowing it to function as a pressure-sensitive material. The conductivity variation with applied pressure makes this hydrogel a promising candidate for flat-foot detection via shoe sensors. This innovative hydrogel platform, combining metal selectivity, self-healing, underwater adhesion, and conductivity, opens avenues for applications in healthcare, wearable sensors, and adhesives.

The prospects for oncological therapeutics are greatly expanded by the development of engineered nanodrugs that seamlessly integrate diagnostic and therapeutic functions into a single platform. Herein, we introduce an intelligent probe constructed by engineering a Mn₃O₄ shell onto two-dimensional PdAu nanosheets, designed to enable magnetic resonance imaging-based diagnosis while simultaneously delivering synergistic chemodynamic and photothermal therapy. The Mn₃O₄ shell is specifically engineered to degrade under mildly acidic and reductive intracellular conditions, releasing Mn²⁺ ions that bind to surrounding proteins, thereby markedly enhancing longitudinal relaxivity and facilitating specific tumor diagnosis, including the detection of early pulmonary metastases as small as 0.6 mm. In parallel, Mn²⁺ ions initiate chemodynamic therapy via Fenton-like reactions, catalyzing the conversion of H₂O₂ into cytotoxic ˙OH radicals. Moreover, the diagnostic imaging provides anatomical guidance for near-infrared irradiation, enabling targeted photothermal therapy and achieving synergistic therapeutic effects against both subcutaneous tumors and pulmonary metastases. Overall, this study presents an integrated nanoplatform that combines responsive imaging and multimodal therapy, representing a meaningful step forward in the design of functional nanomedicines for cancer diagnosis and treatment.

Large-area superspreading enables efficient cooling, cleaning, and liquid redistribution, yet the physical mechanisms that coordinate multi-scale surface structures with hydration conditions remain poorly defined. Here, we identify Racomitrium canescens moss leaves as a natural model that exhibits exceptional spreading performance, with fresh leaves driving water droplets to fully wet the surface in only 0.1 s, an order of magnitude faster than their dehydrated counterparts. Morphological analysis reveals a hierarchical arrangement of micrometer papillae and submicron wrinkles that suggests a multi-level wetting strategy. To elucidate this behavior, we fabricated wrinkled micropillar-arrayed surfaces (WMPS) that reproduce the essential architectural features of the moss leaves. The synthetic surfaces replicate the superspreading phenomenon, enabling a 2 µL droplet to spread completely within 0.9 s and cover an area of 160 mm². Systematic structural decoupling demonstrates that rapid spreading arises from the synergistic action of capillary transport within the micropillar network, enhanced contact-line mobility provided by nanoscale wrinkles, and hydration-induced reduction of the surface-energy barrier. In addition, the bioinspired WMPS provides effective evaporative cooling and maintains contamination resistance, reducing steady-state temperature by 6.3 °C under one-sun irradiation. This work establishes a mechanistic framework for understanding hierarchical wetting and offers a scalable approach to engineering high-performance thermal-management surfaces.

Achieving strong yet reversible underwater adhesion while maintaining low mechanical stiffness remains a key challenge for hydrogel adhesives, especially for temporary stabilization of fragile submerged objects. Here, we report a bioinspired ternary hydrogel in which hydrophobicity is functionally balanced to reconcile adhesion, compliance, and salt tolerance. By systematically tuning hydrophobic content within a cationic polymer network, we construct a hydrogel framework that suppresses salt-induced swelling and restructures hydrogen-bonded water populations, facilitating interfacial dehydration and reversible physical interactions. The resulting hydrogel adopts a tough yet compliant architecture (elastic modulus on the order of 100 kPa) that sustains large stresses while remaining mechanically conformable, enabling stable underwater adhesion (∼0.3 MPa) without chemical curing. Importantly, the adhesion is residue-free, reversible, and repeatable across cycles, demonstrating that high interfacial strength can be achieved without sacrificing detachability. Demonstrated under the stringent conditions of in situ stabilization of submerged cultural heritage, this work establishes a composition-balancing strategy for designing tough yet compliant hydrogel adhesives for reversible underwater applications.

Postsynthetic modification (PSM) of the linkages in covalent organic frameworks (COFs) is usually performed on isolated samples due to their incompatibility with the crystallization conditions. In this work, we report a one-pot PSM strategy that reduces imine-linked to amine-linked COFs via an iminium-activated process under acidic conditions. Using Hantzsch ester as a mild, chemoselective reductant, this method eliminates the need for isolating pristine COFs prior to transformation and shows better functional group tolerance compared to previous methods (NaBH₄ and HCOOH). The resulting amine-linked COFs retain high porosity and crystallinity. As a demonstration, a H₃PO₄-loaded amine-linked pyrene COF achieves a proton conductivity of 4.9 × 10⁻² S cm⁻¹ at 95 °C and 80% relative humidity with a low activation energy of 0.16 eV. This one-pot strategy offers a streamlined and general approach to accessing functionalized COFs.