Sample pretreatment technology plays a vital role throughout the analysis of complex samples. Sample pretreatment can not only increase the concentration of trace targets in the sample, but also effectively eliminate interference from the sample matrix in instrumental analysis. Adsorbent materials are a key component of sample pretreatment technology. Therefore, the development of efficient and stable new adsorbent materials has acquired significance in research on pretreatment technology. Porous materials are advantageous for use in diverse applications, such as in adsorbents, when they possess controllable nanostructures, a tailored pore surface chemistry, and abundant porosity, and are inexpensive. Particularly in recent years, porous materials derived from metal-organic frameworks (MOFs) feature excellent properties, such as diverse morphology and structure, adjustable pore size, high specific surface area, good thermal stability, and chemical resistance. MOF-derived materials, when used as adsorbents for sample pretreatment, offer the following advantages: (1) The porous materials derived from MOFs typically possess a larger specific surface area than other porous materials. This characteristic is beneficial to improve the extraction capacity and extraction efficiency via an increase in the contact area between the materials and targets; (2) The microscopic porous structure of MOF-derived materials can be easily tuned (by controlling the temperature and time during pyrolysis, gas atmosphere, and heating rate), which is conducive to improve the selectivity of sample pretreatment methods; (3) The metal active sites can be evenly distributed. Owing to the ordered distribution of metal ions in the precursor MOFs and a good periodic framework structure, the metal active sites of the derivatives formed can still maintain a corresponding distance. These metal active sites will not form agglomerates and affect the extraction performance; conversely, other porous materials often require extremely complicated processes to achieve a uniform distribution; (4) Heteroatoms such as nitrogen and sulfur can be easily doped on the framework of MOF-derived porous materials. This doping enables the materials to induce additional interactions such as hydrogen bonding and π-π stacking for adsorbing target analytes. The excellent properties of MOF-derived materials make them promising for use in sample pretreatment. Novel sample pretreatment methods that use MOF-derived materials are constantly being developed. However, the use of MOF-derived materials is limited by the complex preparation process and high production cost of MOF precursors, along with difficulties in mass production. Further, the precise design or functionalization of MOF-derived materials according to the characteristics of targets is a new direction with immense challenges as well as application potential. This review summarizes the application of MOF-derived materials in sample pretreatment methods, including dispersive solid phase extraction (dSPE), magnetic solid phase extraction (MSPE), solid phase microextraction (SPME), stir bar sorptive extraction (SBSE), and dispersive micro solid phase extraction (DMSPE). The preparation methods, functional control, and enrichment efficiencies of various MOF-derived materials are also reviewed. Finally, the application prospects of MOF-derived materials in sample pretreatment are discussed to provide a clear outlook and reference for further related research.
样品前处理技术在复杂样品的整个分析过程中起着至关重要的作用,其不仅可以提高痕量目标物在样品中的浓度,而且能有效消除样品基质对分析的干扰。对于样品前处理技术而言,吸附剂是其最为核心部分。因此开发高效、稳定的新型吸附剂已成为前处理技术领域的研究热点。近年来,由金属有机骨架(metal-organic frameworks, MOFs)衍生的多孔材料因其形貌结构多样、孔径可调、比表面积高、热稳定性良好、耐化学腐蚀等优异性能,使其在样品前处理领域拥有广阔的应用前景,基于MOFs衍生材料的样品前处理新方法也层出不穷。然而,MOFs衍生材料仍存在MOFs前驱体合成工艺复杂、生产成本高、量产困难等问题。该文总结了近几年来MOFs衍生材料在分散固相萃取(dSPE)、磁固相萃取(MSPE)、固相微萃取(SPME)、搅拌棒固相萃取(SBSE)和分散微固相萃取(DMSPE)等样品前处理技术中的研究进展,并对多种MOFs衍生材料的制备方法、功能化调控、富集效率等方面进行了评述。最后,展望了MOFs衍生材料在该领域中的应用前景,为进一步研究MOFs衍生材料的应用提供了参考。
Keywords: derivative materials; metal-organic frameworks; pretreatment technique; review.