Metal-organic frameworks as advanced sorbents for the extraction and determination of pollutants from environmental, biological, and food media
Graphical abstract
Introduction
Monitoring and determination of pollutants in the different matrices is of great importance due to their harmful impacts not only on humans but also on ecological systems. Therefore, development of simple, fast, and efficient pretreatment techniques to support the separation and analysis of hazardous chemicals at trace levels has become a critical issue for both analytical chemists and environmental scientists. To date, the use of such pretreatment methods has commonly become an indispensable step to measure pollutants contained in complicated matrices.
Solid phase extraction (SPE) has been employed preferably for enrichment and subsequent determination of pollutants from different samples for several decades. The use of SPE can make one avoid a number of major drawbacks of liquid–liquid extraction (LLE) (e.g., consumption of large organic solvents, incomplete phase separation, obtaining low quantitative recoveries, and unnecessary time consumption). However, it requires several stages of pretreatment including washing, conditioning, sample loading, and eluting. Recent developments in this research field have been achieved with the aid of new and advanced materials (as sorbents) along with the introduction of novel miniaturized SPE techniques so as to fulfill the principals of green analytical chemistry.
As another preferable pretreatment option, solid phase microextraction (SPME) is recognized as one of the most efficient extraction approaches. In this approach, the analytes of interest are extracted from the sample into the thin layer of extraction phase coated onto the fiber. In SPME, extraction of target compounds can be performed in ether direct immersion (DI-SPME) or headspace (HS-SPME) mode. After extraction process, analytes can be separated by thermal desorption. This technique is simple, rapid, sensitive, and environment friendly [1]. As such, many developments have been introduced to improve the extraction efficiency of pretreatment technique like SPME toward green chemistry [2], [3], [4], [5]. However, some drawbacks associated with SPME including high cost of fibers, limited life time of fibers (especially in case of direct immersion), fiber instability in organic solvents, and stripping of the coated fibers are the targets to overcome. As an alternative to avoid some of these disadvantages, micro-solid phase extraction (μ-SPE) was developed in 2006 [6]. In this technique, the sorbent is placed in a porous membrane. Therefore, the interference of large molecules and particles is prevented so that analytes can be separated from complex matrices. This method is simpler, faster, and less costly with analytes extraction accompanied by simultaneous clean-up process. After enrichment process, target analytes can be eluted using a small amount of solvent.
During the last decade, a considerable scientific emphasis has been placed on the applications of porous solid materials in several analytical fields such as adsorption, purification, and catalysis [7], [8]. These materials are categorized in several ways such as natural, synthetic, inorganic, organic, crystalline as well as amorphous. Very recently, different types of organic–inorganic hybrid solids named, metal-organic frameworks (MOFs) have been introduced. These novel substances, made up of metal ions (or clusters) and organic linkers, have drawn a great deal of attention from analytical chemist due to their ability to function as hosts. In other words, the available pores of these compounds can perform as a reactor in which adsorbates can be adsorbed and separated from mixture. MOFs are well known for several extraordinary properties, e.g., high porosity, large surface area, uniform structured cavities, and thermal/chemical stability [9]. The diversity of either metal ions or organic linkers permitted chemists to design and prepare new and different types of MOFs in terms of topology, structure, and porosity [10], [11], [12], [13]. Because of the large surface area and rich porosity, the adsorption of the target molecules on the surface of MOFs will be facilitated with high efficiency. Consequently, MOFs have been preferably recommended as a reliable and novel solid sorbent in sample preparation procedures. Fig. 1 shows the development of MOFs in various fields of applications including analytical instrumentation.
The objective of this review article is to focus on potential ability of MOFs as one of the recently developed porous solid materials that can be applied effectively for the extraction and separation of diverse organic and inorganic pollutants from a variety of samples representing environmental, food, and biological media. As such, the goal of this study is to help accomplish the accurate quantitation of these pollutants based on MOF technology (Fig. 2). As MOFs are known as highly advanced porous materials, their potential applicability in separation and purification processes in modern analytical chemistry has been demonstrated. Here we present a comprehensive study about MOFs and their promising applications as sorbents in SPE, μ-SPE, and SPME. In addition, in this review, the limitations related to the applications of MOFs as sorbents in solid phase-based separations are also discussed as well to give directions to overcome such issues. Finally, the future possibilities and potentials of MOFs as solid sorbents will be discussed.
Section snippets
The concept of green analytical chemistry
Recently, environmental pollution and related issues have attracted a lot of attention among scientists to motivate the development of greener chemicals and techniques. The term of green chemistry was first introduced to give new perspective on the importance of using more environmentally benign procedures in research [14]. Based on definition, green chemistry refers to approaches in which consumption of chemicals and energy is carried out with the least production of waste. The concept of
Design and synthesis of MOFs
More recently, coordination polymers (CPs) generally known as MOFs have been introduced in diverse fields of analytical chemistry. These porous solid materials encompass a variety of applications due to their outstanding features including designability in both structure and properties, low framework density, open metal sites for interactions, and high surface area [9], [11], [24], [25], [26]. Generally speaking, MOFs are self-assembled from organic linkers and metal ions through coordination
Current trends for MOFs-based analysis
Nowadays, environmental issues (e.g. pollution, degradation, and climate change) have become one of the most significant global concerns to attract a great deal of attention not only from environmentalists but also from analytical chemists. Determination of pollutants – either organic or inorganic species – has become critically important; therefore, enormous efforts have been put to monitor and study the levels of different contaminations in a variety of matrices (e.g. food, soil, water, air,
MOFs as new adsorbent in separation science and their applications
The outstanding features of MOFs make these hybrid organic–inorganic materials suitable sorbents for sample pretreatment in separation science. The adsorption process on MOFs is highly dependent on the pore distribution of the solid porous compound. In fact, guest molecules can be kept in a uniform restricted space in which all reactions are performed or conducted [24], [25], [26]. According to the recent research, MOFs can be rigid or flexible in structure [24], and both of these features are
Basics of QA for MOF-based pretreatment
It is well established that the adsorption of analytes from a matrix is a more preferable option for sample treatment than others in light of many variables involved in experimental and QA steps (e.g., simple operational conditions, low energy consumption, high extraction efficiency, and avoiding side products). As such, the obtained results can offer less biased information on the status of pollution in each target medium. Various conventional adsorbents (including activated carbon, carbon
Conclusions
Owing to the serious threats posed to humans and ecological systems by organic and inorganic contaminants, continuous monitoring and precise determinations of these pollutants is inevitable. Noticeably, the complex mixtures of hazardous chemicals with trace quantities afford many critical issues to analytical chemists and environmental scientists in terms of separation and their ultimate measurement. Regarding the necessity of separation, purification, concentration, and subsequent
Acknowledgements
This study was supported by a grant from the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (No. 2016R1E1A1A01940995). This study was also supported by a grant (14182MFDS977) from the Ministry of Food and Drug Safety, Korea in 2017 and by a grant from “Cooperative Research Program for Agriculture Science and Technology Development (Project No. PJ012521032017)” Rural Development Administration, Republic of Korea.
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