Zheng De-Sheng, Tang Wen-Qi, Zhu Jian-Ping, Gu Zhi-Yuan
School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Se Pu. 2024 Jun;42(6):524-532. doi: 10.3724/SP.J.1123.2024.01022.
The stationary phase is the heart of chromatographic separation technology and a critical contributor to the overall separation performance of a chromatographic separation technique. However, traditional silicon-based materials designed for this purpose usually feature complex preparation processes, suboptimal permeability, pronounced mass-transfer resistance, and limited pH-range compatibility. These limitations have spurred ongoing research efforts aimed at developing new chromatographic stationary phases characterized by higher separation efficiency, adaptable selectivity, and a broader scope of applicability. In this context, the scientific community has made significant strides toward the development of new-generation materials suitable for use as chromatographic stationary phases. These materials include carbon-based nanomaterial arrays, carbon quantum dots, and two-dimensional (2D) materials. 2D-materials are characterized by nanometer-scale thicknesses, extensive specific surface areas, distinctive layered structures, and outstanding mechanical properties under standard conditions. Thus, these materials demonstrate excellent utility in various applications, such as electrical and thermal conductivity enhancements, gas storage and separation solutions, membrane separation technologies, and catalysis. Graphene, which is arguably the most popular 2D-material used for chromatographic separation, consists of a 2D-lattice of carbon atoms arranged in a single layer, with a large specific surface area and efficient adsorption properties. Its widespread adoption in research and various industries is a testament to its versatility and effectiveness. In addition to graphene, the scientific community has developed various 2D-materials that mirror the layered structures of graphene, such as boron nitride, transition-metal sulfides, and 2D porous organic frameworks, all of which offer unique advantages. 2D porous organic frameworks, in particular, have received attention because of their nanosheet morphology, one-dimensional pores, and special interlayer forces; thus, these frameworks are considered promising candidate chromatographic stationary phase materials. Such recognition is especially true for 2D-metal organic frameworks (MOFs) and 2D-covalent organic frameworks (COFs), which exhibit low densities, high porosities, and substantial specific surface areas. The modifiability of these materials, in terms of pore size, shape, functional groups, and layer-stacking arrangements allows for excellent separation selectivity, highlighting their promising potential in chromatographic separation. Compared with their three-dimensional counterparts, 2D-MOFs feature a simple pore structure that offers reduced mass-transfer resistance and enhanced column efficiency. These attributes highlight the advantages of 2D-MOF nanosheets as chromatographic stationary phases. Similarly, 2D-COFs, given their high specific surface area and porosity, not only exhibit great thermal stability and chemical tolerance but also support a wide selection of solvents and operational conditions. Therefore, their role in the preparation of chromatographic stationary phases is considered highly promising. This review discusses the latest research developments in 2D porous organic framework materials in the context of gas- and liquid-chromatographic stationary phases. It introduces the synthesis methods for these novel materials, elucidates their retention mechanisms, and describes the applications of other 2D-materials, such as graphene, its derivatives, graphitic carbon nitride, and boron nitride, in chromatography. This review aims to shed light on the promising development prospects and future directions of 2D-materials in the field of chromatographic separation, offering valuable insights into the rational design and application of new 2D-materials in chromatography.
固定相是色谱分离技术的核心,对色谱分离技术的整体分离性能起着关键作用。然而,为此目的设计的传统硅基材料通常具有制备过程复杂、渗透率欠佳、传质阻力显著以及pH范围兼容性有限等特点。这些局限性促使人们不断开展研究工作,旨在开发具有更高分离效率、可调节选择性和更广泛适用范围的新型色谱固定相。在此背景下,科学界在开发适用于色谱固定相的新一代材料方面取得了重大进展。这些材料包括碳基纳米材料阵列、碳量子点和二维(2D)材料。二维材料的特点是具有纳米级厚度、广泛的比表面积、独特的层状结构以及在标准条件下出色的机械性能。因此,这些材料在各种应用中都展现出优异的效用,如增强电导率和热导率、气体存储和分离解决方案、膜分离技术以及催化作用。石墨烯可以说是用于色谱分离的最受欢迎的二维材料,它由单层排列的二维碳原子晶格组成,具有大的比表面积和高效的吸附性能。它在研究和各个行业中的广泛应用证明了其多功能性和有效性。除了石墨烯,科学界还开发了各种模仿石墨烯层状结构的二维材料,如氮化硼、过渡金属硫化物和二维多孔有机框架,它们都具有独特的优势。二维多孔有机框架尤其受到关注,因为它们具有纳米片形态、一维孔隙和特殊的层间作用力;因此,这些框架被认为是有前途的色谱固定相材料候选者。对于二维金属有机框架(MOF)和二维共价有机框架(COF)来说尤其如此,它们具有低密度、高孔隙率和大的比表面积。这些材料在孔径、形状、官能团和层堆叠排列方面的可改性使得它们具有出色的分离选择性,突出了它们在色谱分离中的潜在应用前景。与三维对应物相比,二维MOF具有简单的孔结构,传质阻力降低,柱效提高。这些特性突出了二维MOF纳米片作为色谱固定相的优势。同样,二维COF由于其高比表面积和孔隙率,不仅表现出出色的热稳定性和化学耐受性,还支持多种溶剂和操作条件的选择。因此,它们在色谱固定相制备中的作用被认为非常有前景。本综述讨论了二维多孔有机框架材料在气相色谱和液相色谱固定相背景下的最新研究进展。介绍了这些新型材料的合成方法,阐明了它们的保留机制,并描述了其他二维材料,如石墨烯及其衍生物、石墨相氮化碳和氮化硼在色谱中的应用。本综述旨在阐明二维材料在色谱分离领域的广阔发展前景和未来方向,为新型二维材料在色谱中的合理设计和应用提供有价值的见解。