Jiang Wen-Qian, Chen Yu-Mei, Bi Wen-Tao
School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Se Pu. 2023 Oct;41(10):901-910. doi: 10.3724/SP.J.1123.2023.08025.
This paper reviews the application of deep eutectic solvents (DESs) in the synthesis of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) as well as their prospects in the field of solid-phase extraction (SPE). Porous organic frameworks (POFs) have unique properties such as a large specific surface area, high porosity, and easy modification. Thus, these materials are widely applied in the fields of catalysis, adsorption, drug delivery, gas storage, and separation. POFs include MOFs, COFs, conjugated microporous polymers (CMPs), porous aromatic frameworks (PAFs), and covalent triazine frameworks (CTFs). MOFs are constructed from metal ions/clusters and organic ligands through coordination bonds and can be extended in two or three dimensions by repeated coordination with potential voids. COFs are formed from two monomers containing light elements (such as carbon, hydrogen, oxygen, nitrogen, boron, and other elements) via coordination bonds and have large two- or three-dimensional structures. However, conventional POF synthesis methods generally suffer from disadvantages such as long synthesis times, high temperature and pressure requirements, and the use of toxic and hazardous reaction solvents. DES consists of a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD) bound by hydrogen-bonding interactions. It is a promising green solvent for material synthesis owing to its low vapor pressure, high stability, and ease of preparation. DES can be used to prepare MOFs and COFs and, in specific cases, acts as a structure-directing agent, which has an important impact on the structure and properties of the resulting frameworks. Using appropriate DES formulations, researchers can modulate the crystal structures, pore sizes, and surface properties of MOFs and COFs, resulting in materials with excellent characteristics. SPE is an analytical technique in which a sample solution is added to an SPE column; the sample solution is forced through the stationary phase, and the target compounds are collected for analysis by elution with an organic solvent. Therefore, suitable stationary-phase materials are critical for SPE. Owing to their large specific surface areas and abundant active sites, MOFs and COFs exhibit outstanding adsorption capacity and selectivity in SPE and can effectively enrich target analytes from complex samples. DES-based MOFs and COFs have shown potential use in a wide range of applications, such as in environmental analysis, food testing, and biological sample analysis. Although DES-based MOFs and COFs for SPE are still in the early stages of development, their properties such as efficient enrichment and high selectivity offer good prospects for practical applications. Future research should continue to explore DES-based synthesis methods in depth to prepare other MOFs and COFs with the desired properties and investigate their potential applications in various fields. These efforts are expected to apply these novel materials in commercialized solid-phase extraction methods, bringing new development opportunities in the field of analytical chemistry.
本文综述了深共熔溶剂(DESs)在金属有机框架(MOFs)和共价有机框架(COFs)合成中的应用及其在固相萃取(SPE)领域的前景。多孔有机框架(POFs)具有独特的性质,如大比表面积、高孔隙率和易于修饰。因此,这些材料广泛应用于催化、吸附、药物递送、气体储存和分离等领域。POFs包括MOFs、COFs、共轭微孔聚合物(CMPs)、多孔芳香框架(PAFs)和共价三嗪框架(CTFs)。MOFs由金属离子/簇和有机配体通过配位键构建而成,并可通过与潜在空隙的重复配位在二维或三维空间中扩展。COFs由两种含轻元素(如碳、氢、氧、氮、硼等元素)的单体通过配位键形成,具有大的二维或三维结构。然而,传统的POF合成方法通常存在合成时间长、对温度和压力要求高以及使用有毒有害反应溶剂等缺点。DES由通过氢键相互作用结合的氢键受体(HBA)和氢键供体(HBD)组成。由于其低蒸气压、高稳定性和易于制备,它是一种有前途的用于材料合成的绿色溶剂。DES可用于制备MOFs和COFs,在特定情况下还可作为结构导向剂,这对所得框架的结构和性质有重要影响。通过使用合适的DES配方,研究人员可以调节MOFs和COFs的晶体结构、孔径和表面性质,从而得到具有优异特性的材料。SPE是一种分析技术,将样品溶液加入到SPE柱中;使样品溶液通过固定相,然后用有机溶剂洗脱收集目标化合物进行分析。因此,合适的固定相材料对SPE至关重要。由于MOFs和COFs具有大比表面积和丰富的活性位点,它们在SPE中表现出出色的吸附容量和选择性,能够有效地从复杂样品中富集目标分析物。基于DES的MOFs和COFs已在广泛的应用中显示出潜在用途,如环境分析、食品检测和生物样品分析。尽管用于SPE的基于DES的MOFs和COFs仍处于开发初期,但它们高效富集和高选择性等性质为实际应用提供了良好的前景。未来的研究应继续深入探索基于DES的合成方法,以制备具有所需性质的其他MOFs和COFs,并研究它们在各个领域的潜在应用。这些努力有望将这些新型材料应用于商业化的固相萃取方法中,为分析化学领域带来新的发展机遇。