Monitoring the Effect of Different Metal Centers in Metal–Organic Frameworks and Their Adsorption of Aromatic Molecules using Experimental and Simulation Studies

Lirio, Stephen; Shih, Yung Han; Hsiao, Shu Ying; Chen, Jian Hong; Chen, Hsin‐Tsung; Liu, Wan Ling; Lin, Chia Her; Huang, Hsi Ya

doi:10.1002/chem.201802343

Cited by 5 publications

(4 citation statements)

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“…The study highlighted the complexity in achieving adequate predictions for the microextraction performance, with successful results mainly linked to the pore environment, pore size, and pore aperture widths of the MOF, together with a clear influence of the metal nature. The nature of the metal of the MOF and its influence in extraction studies have also been quite recently pointed out by Lirio et al [ 14 ], with high importance given to the radius of the metal.…”

Section: Introductionmentioning

confidence: 93%

“…UiO-66 has shown promising adsorption capacities for organic contaminants such as organic dyes [ 12 ] and for inorganic pollutants such as heavy metals [ 13 ]. However, the adsorption behavior of emerging pollutants, such as pharmaceutical and personal care products on UiO-66 has been scarcely studied [ 14 ], and to the best of our knowledge, there are not studies dealing with functionalized UiO-66 materials in microextraction.…”

Section: Introductionmentioning

confidence: 99%

“…It is important mentioning that, while existing an increasing number of studies with MOFs as sorbents in D-μSPE [ 16 ], few authors have paid close attention to study the nature of the interactions established between the MOF sorbent and the contaminants. Indeed, the type of interactions that take place during the extraction has not been established completely [ 14 , 23 , 24 ]. Thus, Rocío-Bautista et al evaluated the partitioning of target compounds to different MOFs in D-μSPE [ 24 ].…”

Section: Introductionmentioning

confidence: 99%

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Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants

et al. 2018

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Four metal-organic frameworks (MOFs), specifically UiO-66, UiO-66-NH2, UiO-66-NO2, and MIL-53(Al), were synthesized, characterized, and used as sorbents in a dispersive micro-solid phase extraction (D-µSPE) method for the determination of nine pollutants of different nature, including drugs, phenols, polycyclic aromatic hydrocarbons, and personal care products in environmental waters. The D-µSPE method, using these MOFs as sorbents and in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD), was optimized. The optimization study pointed out to UiO-66-NO2 as the best MOF to use in the multi-component determination. Furthermore, the utilization of isoreticular MOFs based on UiO-66 with the same topology but different functional groups, and MIL-53(Al) to compare with, allowed us for the first time to evaluate the influence of such functionalization of the ligand with regards to the efficiency of the D-µSPE-HPLC-DAD method. Optimum conditions included: 20 mg of UiO-66-NO2 MOF in 20 mL of the aqueous sample, 3 min of agitation by vortex and 5 min of centrifugation, followed by the use of only 500 µL of acetonitrile as desorption solvent (once the MOF containing analytes was separated), 5 min of vortex and 5 min of centrifugation. The validation of the D-µSPE-HPLC-DAD method showed limits of detection down to 1.5 ng·L−1, average relative recoveries of 107% for a spiked level of 1.50 µg·L−1, and inter-day precision values with relative standard deviations lower than 14%, for the group of pollutants considered.

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Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants

et al. 2018

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“…A number of studies using MOFs in D-µSPE have pointed out the complexity of the systems, indicating the pore environment, pore size, and pore aperture widths of the MOF as the most influential factors, together with a clear influence of the metal nature (particularly the presence of unsaturated metal sites) [11]. Lirio et al also pointed out the influence of the metal, particularly the radius of the metal [13]. Taima-Mancera et al showed the positive effects of incorporating polar functionalities in the organic ligand of the MOFs used in D-µSPE when intending to extract polar analytes of a small size [12], with this idea having been further expanded by Boontongto et al to other application studies for polar analytes [14].…”

Section: Introductionmentioning

confidence: 99%

Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal–Organic Frameworks for Tailored Microextraction

et al. 2019

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The mixed-ligand strategy was selected as an approach to tailor a metal–organic framework (MOF) with microextraction purposes. The strategy led to the synthesis of up to twelve UiO-66-based MOFs with different amounts of functionalized terephthalate ligands (H-bdc), including nitro (-NO2) and amino (-NH2) groups (NO2-bdc and NH2-bdc, respectively). Increases of 25% in ligands were used in each case, and different pore environments were thus obtained in the resulting crystals. Characterization of MOFs includes powder X-ray diffraction, infrared spectroscopy, and elemental analysis. The obtained MOFs with different degrees and natures of functionalization were tested as sorbents in a dispersive miniaturized solid-phase extraction (D-µSPE) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD), to evaluate the influence of mixed functionalization of the MOF on the analytical performance of the entire microextraction method. Eight organic pollutants of different natures were studied, using a concentration level of 5 µg· L−1 to mimic contaminated waters. Target pollutants included carbamazepine, 4-cumylphenol, benzophenone-3, 4-tert-octylphenol, 4-octylphenol, chrysene, indeno(1,2,3-cd)pyrene, and triclosan, as representatives of drugs, phenols, polycyclic aromatic hydrocarbons, and disinfectants. Structurally, they differ in size and some of them present polar groups able to form H-bond interactions, either as donors (-NH2) or acceptors (-NO2), permitting us to evaluate possible interactions between MOF pore functionalities and analytes’ groups. As a result, extraction efficiencies can reach values of up to 60%, despite employing a microextraction approach, with four main trends of behavior being observed, depending on the analyte and the MOF.

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Polystyrene‐Supported Core–Shell Beads with Aluminium MOF Coating for Extraction of Organic Pollutants

Kuo

Pal

et al. 2019

Chemistry An Asian Journal

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Aluminium-based metal-organic framework (MOF) coatings on polystyrene bead surfaces were easily synthesized by reacting an intermediate metal hydroxide coating with an organic linker.S everal different sizes of polystyrene beads were coated with aluminium metal hydroxide to construct Al@PS core-shell bead materials. The activated Al@PS core-shell beads were involved to make ah omogenous MOF-basedl ayer in the presence of the organic linker.B y using different sizes of the PS support the size of MOFs on the PS composites could be fine-tuned under specific reaction conditions. MOF-coated core-shell bead materials (Al-1,4-NDC@PS and MIL-53(Al)@PS) were characterized using variousa nalytical techniques. Al-1,4-NDC@PS and MIL-53(Al)@PS were evaluated fors olid-phase microextraction (SPME) of hydrophobic polycyclic aromatic hydrocarbons (PAHs) and hydrophilic non-steroidal anti-inflammatory drugs (NSAIDs),r espectively.A l-1,4-NDC@PS-1000 displayed high extraction recoveries ranging from 79.2 %t o9 9.8 %i n the SPME of PAHs. Meanwhile, MIL-53(Al)@PS-1000 showed 85.9-99.0 %e xtraction recoveries in the SPME of NSAIDs. These results show that the proposed approachh olds potential to extract organic analytes on an industrial scale.

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Monitoring the Effect of Different Metal Centers in Metal–Organic Frameworks and Their Adsorption of Aromatic Molecules using Experimental and Simulation Studies

Cited by 5 publications

References 49 publications

Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants

Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants

Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal–Organic Frameworks for Tailored Microextraction

Polystyrene‐Supported Core–Shell Beads with Aluminium MOF Coating for Extraction of Organic Pollutants

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