Supercritical Solvothermal Synthesis of Single-Crystalline Covalent Organic Frameworks and Their Applications

IF 14.7 Q1 CHEMISTRY, MULTIDISCIPLINARY
Lan Peng*, Yunqi Liu and Dacheng Wei*, 
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引用次数: 0

Abstract

Covalent organic frameworks (COFs) are a rapidly evolving class of crystalline porous materials with customizable topologies, tunable functionalities, and a broad scope of applications ranging from catalysis to optoelectronics. Despite substantial progress in framework design, the controlled growth of single-crystalline COFs remains a formidable challenge due to the relatively poor reversibility of covalent bond formation and the difficulty in modulating nucleation and growth kinetics. Traditional solvothermal strategies often yield polycrystalline powders and require prolonged reaction times, limiting access to defect-free structures essential for in-depth structural characterization and advanced functional applications.

In this Account, we present the supercritical solvothermal method as a transformative strategy that simultaneously achieves ultrarapid synthesis and high crystallinity of COFs. By leveraging the unique physicochemical properties of supercritical carbon dioxide (sc-CO2), notably its low viscosity, high diffusivity, and tunable solvent density, this method overcomes the trade-off between synthesis duration and crystal quality. This approach enables the synthesis of single-crystalline COFs in a few minutes, compared to hours or days in conventional systems. Mechanistically, sc-CO2 facilitates dynamic mass transport and enhanced molecular mobility, which accelerate nucleation while promoting defect self-healing during framework propagation. Time-resolved characterization combined with template infiltration experiments reveals that the exceptional penetrability of sc-CO2 enables framework formation even within confined micropores and allows for precise morphological tuning of COFs. Furthermore, we demonstrate that weak intermolecular forces such as interlayer electrostatic repulsions and hydrogen bonding can be amplified under supercritical fluid conditions to modulate crystal morphology, leading to the formation of rare helical COF crystals and enabling structure manipulation via rational side-group engineering.

Single-crystalline COFs exhibit specific properties and potential applications, particularly in nonlinear optics, optoelectronics, and chemical sensing. These crystals display high second harmonic generation efficiencies due to their noncentrosymmetric packing, as well as robust third-order nonlinear responses enabled by chromophore alignment and π-electron delocalization. In optoelectronic applications, dual-state COF phototransistors demonstrate room-temperature responsivity of ∼4.6 × 1010 A·W–1 and detectivity of 1.62 × 1016 Jones, enabling high-contrast neuromorphic imaging under low-light and aqueous conditions. In chemical sensing applications, COF/graphene heterostructures synthesized via this method deliver unprecedented detection limits, down to 10–19 M for methylglyoxal and 10–10 M for mercury ions in biofluids, by integrating photochemical gating effects and exploiting ordered charge-transfer interfaces.

Overall, this Account establishes the supercritical solvothermal method as a general and scalable platform for single-crystal COF synthesis. It not only broadens the synthetic scope to previously inaccessible topologies and linkage chemistries but also paves the way for the integration of COFs into high-performance photonic, electronic, and biomedical devices. Future opportunities lie in tuning fluid dynamics for dimensionality control, coupling with nucleation or competitive reaction strategies to access new architectures, and extending the kinetic framework to guide crystallization in other polymeric and supramolecular materials.

Abstract Image

单晶共价有机骨架的超临界溶剂热合成及其应用
共价有机框架(COFs)是一种快速发展的晶体多孔材料,具有可定制的拓扑结构,可调节的功能,以及从催化到光电子的广泛应用范围。尽管在框架设计方面取得了实质性进展,但由于共价键形成的可逆性相对较差,并且难以调节成核和生长动力学,单晶COFs的受控生长仍然是一个巨大的挑战。传统的溶剂热策略通常会产生多晶粉末,并且需要较长的反应时间,限制了深入结构表征和高级功能应用所必需的无缺陷结构的获取。在本报告中,我们提出超临界溶剂热法作为一种变革策略,同时实现超快速合成和高结晶度的COFs。通过利用超临界二氧化碳(sc-CO2)独特的物理化学性质,特别是其低粘度,高扩散率和可调节的溶剂密度,该方法克服了合成时间和晶体质量之间的权衡。这种方法可以在几分钟内合成单晶COFs,而传统系统需要数小时或数天。从机制上说,sc-CO2促进了动态质量传递和分子迁移率的增强,从而加速了核的形成,同时促进了框架传播过程中缺陷的自愈。时间分辨特性与模板渗透实验相结合表明,sc-CO2的卓越渗透性即使在受限的微孔内也能形成框架,并允许COFs的精确形态调整。此外,我们证明了在超临界流体条件下,层间静电斥力和氢键等弱分子间力可以被放大来调节晶体形态,从而形成罕见的螺旋COF晶体,并通过合理的侧基工程实现结构操纵。单晶COFs具有特殊的性能和潜在的应用,特别是在非线性光学,光电子学和化学传感方面。这些晶体由于其非中心对称填充而具有较高的二次谐波产生效率,并且由于发色团排列和π电子离域而具有鲁棒的三阶非线性响应。在光电应用中,双态COF光电晶体管的室温响应率为~ 4.6 × 1010 A·W-1,探测率为1.62 × 1016 Jones,可在弱光和水环境下实现高对比度的神经形态成像。在化学传感应用中,通过这种方法合成的COF/石墨烯异质结构提供了前所未有的检测限,通过整合光化学门控效应和利用有序电荷转移界面,甲基乙二醛的检测限低至10-19 M,生物流体中汞离子的检测限低至10-10 M。总的来说,本论文建立了超临界溶剂热法作为单晶COF合成的通用和可扩展的平台。它不仅将合成范围扩大到以前无法进入的拓扑结构和链接化学,而且为将COFs集成到高性能光子,电子和生物医学设备中铺平了道路。未来的机会在于调整流体动力学以进行维度控制,与成核或竞争反应策略耦合以获得新的结构,并扩展动力学框架以指导其他聚合物和超分子材料的结晶。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
17.70
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