Materials Chemistry Frontiers最新文献

Chiral covalent organic frameworks (COFs) have emerged as a promising class of circularly polarized luminescent (CPL) materials. This review systematically summarizes the synthesis and CPL activity of chiral COFs, including synthetic strategies, chirality–luminophore integration approaches, and film fabrication techniques for potential applications as well as mechanistic insights for chiroptical properties. Moreover, this review provides perspectives on future efforts for optimizing CPL performance, exploring diversified frameworks, and elucidating chirality transfer kinetics to unlock applications in optical encryption and biomedicine.

Porous materials (PMs) are a class of special materials characterized by their internal pore network structures, which afford them a larger specific surface area and a greater number of accessible active sites. Consequently, they find widespread applications in catalysis, energy storage and conversion, etc. Carbon dots (CDs), an emerging class of zero-dimensional carbon nanomaterials, possess highly cross-linked or carbonized cores along with abundant surface functional groups. The precursors of CDs are diverse and cost-effective, allowing for the tailoring of specific structures through controlled reaction conditions. Initially, CDs were extensively utilized in bioimaging and fluorescence detection due to their characteristic photoluminescence properties. However, in recent years, a substantial body of research has focused on employing CDs as fundamental building blocks or modifying species to fabricate various PMs, with experimental evidence underscoring their significant role. In this review, PMs are categorized into porous carbons, porous inorganic materials, and porous gel materials based on their fundamental constituents. We summarize recent advances in PMs constructed using CDs, with a particular emphasis on the influence of CDs regarding the morphology and pore structure of these materials, as well as the underlying mechanisms. This systematic overview aims to provide new insights into the design of porous materials and the multifunctional applications of CDs.

The development of composite polymer electrolytes (CPEs) that simultaneously achieve high ionic conductivity, mechanical flexibility, and interfacial compatibility is crucial for advancing solid-state lithium–sulfur (Li–S) batteries. Herein, we report a dual-phase electrolyte system based on a poly(vinylidene fluoride) (PVDF) matrix embedded with a cerium-doped sulfide glass–ceramic filler, Li₇P_2.9Ce_0.1S₁₁. Cerium incorporation facilitates lithium-ion transport by inducing lattice distortion and increasing vacancy concentrations, while strong interfacial bonding with PVDF ensures uniform filler dispersion and mechanical robustness. The resulting CPE exhibits a high ionic conductivity of 9.00 × 10⁻⁴ S cm⁻¹ at 25 °C and a lithium-ion transference number of 0.623, with an apparent oxidative stability limit of 4.56 V vs. Li⁺/Li as determined by linear sweep voltammetry. The galvanostatic intermittent titration technique (GITT) confirms a lithium diffusion coefficient of 4.8 × 10⁻⁷ cm² s⁻¹, highlighting fast transport kinetics. When applied in a Li–S cell with high sulfur loading (5 mg cm⁻²) and lean electrolyte (5 μL mg⁻¹), the CPE enables a stable discharge capacity of 642 mAh g⁻¹ over 1000 cycles at 1C with 39% capacity retention. A symmetric Li|CPE|Li cell further demonstrates dendrite-free cycling over 330 hours at 1 mA cm⁻². This work demonstrates that Ce-doped Li₇P₃S₁₁-based CPEs offer a viable pathway toward stable, high-performance, solid-state Li–S batteries operating under practical conditions.

Nature's fundamental processes have inspired the development of robotic systems. Living organisms generate movements through complex molecular mechanisms, particularly evident in muscle tissue, where natural protein motors generate motion across multiple length scales. While traditional rigid robots have achieved significant technological advances, the emergence of supramolecular soft robotics presents promising opportunities for functional applications in biomimetic and stimuli-responsive materials. However, the high structural requirements of supramolecular nanoassemblies in supramolecular soft robotic systems greatly hamper their rapid development. Herein, we demonstrate macroscopic movements of supramolecular visible-light driven soft robotic materials in aqueous media without high orientational order, high aspect ratio, and highly charged nature. Through delicate molecular design of indigo amphiphiles (IAs), the supramolecular assembly behavior of IAs was significantly influenced by altering the alkyl-linker chain lengths, resulting in nanostructures ranging from rod-like micelles to vesicles. Upon red-light laser irradiation to IA supramolecular soft robotic materials, the IA soft robotics bent towards the light source, enabled by transformation of IA nanoassemblies and water ejection from the soft robotics, achieving macroscopic photoactuation function with speed up to 25.4 ± 2.8° min⁻¹. The result paves the way for the design of next generation visible-light controlled biomimetic supramolecular soft robotic systems.

Aqueous proton batteries have garnered significant interest owing to their cost-effectiveness and enhanced safety. However, achieving all-organic rocking-chair proton batteries remains a challenge due to the lack of suitable organic electrode materials in acid electrolytes. This study presents an all-organic rocking-chair proton battery employing a diquinoxalino [2,3-a:2′,3′-c] phenazine (HATN) anode paired with a 2,6-dihydroxynaphthalene (2,6-DHN)@CMK-3 cathode, operating in 9.5 m H₃PO₄ electrolyte. Its working mechanism includes reversible –C–O–H/–CO conversion at the cathode coupled with –CN/–C–N–H conversion at the anode. Thanks to its rapid reaction kinetics, this proton battery exhibits a reversible discharge capacity of 101 mAh g⁻¹ at 1 A g⁻¹, a satisfactory energy density of 61 Wh kg⁻¹, and an exceptional cycling stability beyond 6000 cycles. Notably, benefiting from the low freezing point of the 9.5 m H₃PO₄ electrolyte, this proton battery sustains robust rate capability and stable cycling down to −50 °C, highlighting its suitability for operation under cold conditions.

Covalent organic frameworks (COFs) have demonstrated significant potential in visible-light-driven photocatalysis due to their tunable structures and adjustable bandgaps. However, most COFs exhibit a limited light absorption range and poor solar energy utilization, leading to low catalytic efficiency. Developing COFs with a broad absorption range is therefore crucial for enhancing solar utilization and photocatalytic reaction rates. This study constructed three benzothiadiazole-based donor–acceptor (D–A) COFs (HIAM-0032 to HIAM-0034) with fes topology, extending the light-absorption range into the near-infrared region. Among the three COFs, HIAM-0033 exhibited a remarkable photocatalytic hydrogen production rate of 7.8 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 4.1 and 11.4 times higher than those of HIAM-0034 (1.9 mmol g⁻¹ h⁻¹) and HIAM-0032 (0.7 mmol g⁻¹ h⁻¹). Photoelectrochemical analyses revealed that the superior performance of HIAM-0033 originates from enhanced donor–acceptor interactions, which reduce the exciton binding energy, accelerate charge separation and migration, and increase carrier concentration. This work sheds light on the design and synthesis of COFs with broad light-harvesting capability to realize efficient photocatalysis.

The introduction of “heterogeneity within order” to metal–organic frameworks (MOFs) commonly leads to an increase in structural complexity, posing the question of whether it is possible to spatially arrange multiple components in a simple network. Here, we focus on the integration of quaternary components into a simple pcu-b (primitive cubic unit-biparticle) network using a [Zn₄O]-core cluster and paddle-wheel secondary building units (SBUs) alongside organic linkers. We systematically explore a design space of over 180 candidate configurations, identifying an optimal structure that balances synthetic feasibility and functional potential. Experimental validation confirmed the successful synthesis of the predicted framework, named MAC-5, which exhibits unique anisotropic modulation enabled by the controlled spatial arrangement of distinct Zn₄O(COO)₄(NN)₂ and paddle-wheel SBUs. Extending this approach, we synthesized a series of iso-reticular analogues, presenting the tailored multiple functions from different multicomponent frameworks. The hetero-SBU arrangement of MAC-5 enhanced the thermal and chemical stabilities and enabled programmable metal doping that defies expectations in pcu-based systems. This work establishes a reticular chemistry approach to engineering functional complexity within simple network topologies, providing a blueprint for the rational design of multicomponent MOFs with tailored properties.

The limited efficacy and potential off-target toxicity of nanotherapeutic drugs remain significant challenges in liver cancer treatment. To address these issues, a novel targeted therapy approach utilizing a multifunctional nanocomposite, DOX/Ti₃C₂/PDA/PEG–FA, was developed for combined photothermal/chemotherapy (PTT/CHT) tumor treatment. The folic acid (FA)-modified nanomaterial facilitated specific targeting of folate receptor-overexpressing liver tumor cells, ensuring enhanced accumulation of the drug within the tumor site. Upon near-infrared (NIR) laser irradiation, the Ti₃C₂/PDA core exhibited efficient photothermal conversion, leading to a rapid temperature elevation in the tumor region while simultaneously triggering controlled DOX release due to the photothermal and acidic stimulation, thereby promoting chemotherapy. In vitro results demonstrated that the DOX/Ti₃C₂/PDA/PEG–FA nanocomposites effectively inhibited the proliferation of HepG2 cells. Moreover, in vivo studies in the HepG2 xenograft mouse model showed a significant reduction in the tumor volume and complete tumor ablation with minimal side effects, indicating the high efficiency and low toxicity of the targeted PTT/CHT combination therapy. This study introduces a novel DOX/Ti₃C₂/PDA/PEG–FA nanoplatform, which paves the way for targeted cancer therapy through a synergistic mechanism, significantly improving therapeutic efficacy against liver cancer while concurrently reducing systemic adverse effects.

Biomass-derived hard carbon materials are considered promising anodes for sodium ion batteries (SIBs). Herein, we present a simple pre-oxidation strategy to prepare bamboo-derived hard carbon featuring a closed pore structure and pseudo-graphitic domains, with an expanded interlayer spacing of 0.39 nm. It exhibits outstanding performance and strong potential for SIB applications.

We report a combination strategy using small-molecule matrix and polymer matrix to tailor ultralong organic room temperature phosphorescence (UORTP). 5H-BTCz can be regarded as an excellent phosphorescence unit due to its characteristics of “large size + hetero atom + high rigidity”. When doped into small-molecule matrix, such as DBT and DMAP, 5H-BTCz displays observable green/yellowish-green UORTP with controllable intensity and lifetime as charge separation and charge recombination occur between 5H-BTCz and matrix molecules. In particular, the structural similarity between 5H-BTCz and DBT and the formation of strong π–π interactions significantly facilitate charge transfer between host and guest, leading to higher phosphorescence intensity but shorter phosphorescence lifetime of 5H-BTCz@DBT. Moreover, when 5H-BTCz is copolymerized into an MA/PETA crosslinked network, a self-standing UORTP film could be obtained owing to the moldability and oxygen isolation capacity of the polymer films. Furthermore, we couple the small-molecule matrix with the polymer matrix, and the advantages of both are realized in the newly doped UORTP system. The phosphorescence lifetime can be tuned in a wide range, and the phosphorescence quantum yield can be maximized to 22.18%. We believe that this work can provide a new strategy to efficiently regulate UORTP and lay the foundation for intelligent organic phosphorescence materials.