[Research progress in application of metal-organic framework-derived materials to sample pretreatment]

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.