Cheng-Xiong Yang

Metal-organic frameworks for analytical chemistry: from sample collection to chromatographic separation.

In modern analytical chemistry researchers pursue novel materials to meet analytical challenges such as improvements in sensitivity, selectivity, and detection limit. Metal-organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as high surface area, good thermal stability, uniform structured nanoscale cavities, and the availability of in-pore functionality and outer-surface modification are attractive for diverse analytical applications. This Account summarizes our research on the analytical applications of MOFs ranging from sampling to chromatographic separation. MOFs have been either directly used or engineered to meet the demands of various analytical applications. Bulk MOFs with microsized crystals are convenient sorbents for direct application to in-field sampling and solid-phase extraction. Quartz tubes packed with MOF-5 have shown excellent stability, adsorption efficiency, and reproducibility for in-field sampling and trapping of atmospheric formaldehyde. The 2D copper(II) isonicotinate packed microcolumn has demonstrated large enhancement factors and good shape- and size-selectivity when applied to on-line solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. We have explored the molecular sieving effect of MOFs for the efficient enrichment of peptides with simultaneous exclusion of proteins from biological fluids. These results show promise for the future of MOFs in peptidomics research. Moreover, nanosized MOFs and engineered thin films of MOFs are promising materials as novel coatings for solid-phase microextraction. We have developed an in situ hydrothermal growth approach to fabricate thin films of MOF-199 on etched stainless steel wire for solid-phase microextraction of volatile benzene homologues with large enhancement factors and wide linearity. Their high thermal stability and easy-to-engineer nanocrystals make MOFs attractive as new stationary phases to fabricate MOF-coated capillaries for high-resolution gas chromatography (GC). We have explored a dynamic coating approach to fabricate a MOF-coated capillary for the GC separation of important raw chemicals and persistent organic pollutants with high resolution and excellent selectivity. We have combined a MOF-coated fiber for solid-phase microextraction with a MOF-coated capillary for GC separation, which provides an effective MOF-based tandem molecular sieve platform for selective microextraction and high-resolution GC separation of target analytes in complex samples. Microsized MOFs with good solvent stability are attractive stationary phases for high-performance liquid chromatography (HPLC). These materials have shown high resolution and good selectivity and reproducibility in both the normal-phase HPLC separation of fullerenes and substituted aromatics on MIL-101 packed columns and position isomers on a MIL-53(Al) packed column and the reversed-phase HPLC separation of a wide range of analytes from nonpolar to polar and acidic to basic solutes. Despite the above achievements, further exploration of MOFs in analytical chemistry is needed. Especially, analytical application-oriented engineering of MOFs is imperative for specific applications.

Fluorescent Metal–Organic Framework MIL-53(Al) for Highly Selective and Sensitive Detection of Fe3+ in Aqueous Solution

Fluorescent metal-organic frameworks (MOFs) have received great attention in sensing application. Here, we report the exploration of fluorescent MIL-53(Al) for highly selective and sensitive detection of Fe(3+) in aqueous solution. The cation exchange between Fe(3+) and the framework metal ion Al(3+) in MIL-53(Al) led to the quenching of the fluorescence of MIL-53(Al) due to the transformation of strong-fluorescent MIL-53(Al) to weak-fluorescent MIL-53(Fe), allowing highly selective and sensitive detection of Fe(3+) in aqueous solution with a linear range of 3-200 μM and a detection limit of 0.9 μM. No interferences from 0.8 M Na(+); 0.35 M K(+); 11 mM Cu(2+); 10 mM Ni(2+); 6 mM Ca(2+), Pb(2+), and Al(3+); 5.5 mM Mn(2+); 5 mM Co(2+) and Cr(3+); 4 mM Hg(2+), Cd(2+), Zn(2+), and Mg(2+); 3 mM Fe(2+); 0.8 M Cl(-); 60 mM NO2(-) and NO3(-); 10 mM HPO4(2-), H2PO4(-), SO3(2-), SO4(2-), and HCOO(-); 8 mM CO3(2-), HCO3(-), and C2O4(2-); and 5 mM CH3COO(-) were found for the detection of 150 μM Fe(3+). The possible mechanism for the quenching effect of Fe(3+) on the fluorescence of MIL-53(Al) was elucidated by inductively coupled plasma-mass spectrometry, X-ray diffraction spectrometry, and Fourier transform infrared spectrometry. The specific cation exchange behavior between Fe(3+) and the framework Al(3+) along with the excellent stability of MIL-53(Al) allows highly selective and sensitive detection of Fe(3+) in aqueous solution. The developed method was applied to the determination of Fe(3+) in human urine samples with the quantitative spike recoveries from 98.2% to 106.2%.

Metal-organic framework MIL-101(Cr) for high-performance liquid chromatographic separation of substituted aromatics.

The diverse structures and pore topologies, accessible cages and tunnels, and high surface areas make metal-organic frameworks attractive as novel media in separation sciences. Here we report the slurry-packed MIL-101(Cr) column for high-performance liquid chromatographic separation of substituted aromatics. The MIL-101(Cr) packed column (5 cm long × 4.6 mm i.d.) offered high-resolution separation of ethylbenzene (EB) and xylene, dichlorobenzene and chlorotoluene isomers, and EB and styrene. The typical impurities of toluene and o-xylene in EB and styrene mixtures were also efficiently separated on the MIL-101(Cr) packed column. The column efficiencies for EB, m-dichlorobenzene, and m-chlorotoluene are 20000, 13000, and 10000 plates m(-1), respectively. The relative standard deviation for five replicate separations of the substituted aromatics was 0.2-0.7%, 0.9-2.9%, 0.5-2.1%, and 0.6-2.7% for the retention time, peak area, peak height, and half peak width, respectively. The MIL-101(Cr) offered high affinity for the ortho-isomer, allowing fast and selective separation of the ortho-isomer from the other isomers within 3 min using dichloromethane as the mobile phase. The effects of the mobile phase composition, injected sample mass, and temperature were investigated. The separation of xylene, dichlorobenzene, and chlorotoluene on MIL-101(Cr) was controlled by entropy change, while the separation of EB and styrene on MIL-101(Cr) was governed by enthalpy change.

Zeolitic Imidazolate Framework-8 for Fast Adsorption and Removal of Benzotriazoles from Aqueous Solution

1H-benzotriazole (BTri) and 5-tolyltriazole (5-TTri) are emerging pollutants; the development of novel materials for their efficient adsorption and removal is thus of great significance in environmental sciences. Here, we report the application of zeolitic imidazolate framework-8 (ZIF-8) as a novel adsorbent for fast removal of BTri and 5-TTri in aqueous solution in view of adsorption isotherms, kinetics and thermodynamics, desorption, and adsorbent regeneration. The adsorption of BTri and 5-TTri on ZIF-8 was very fast, and most of BTri and 5-TTri were adsorbed in the first 2 min. The adsorption for BTri and 5-TTri follows a pseudo-second-order kinetics and fits the Langmuir adsorption model with the adsorption capacity of 298.5 and 396.8 mg g(-1) for BTri and 5-TTri at 30 °C, respectively. The adsorption was a spontaneous and endothermic process controlled by positive entropy change. No remarkable effects of pH, ionic strength, and dissolved organic matter on the adsorption of BTri and 5-TTri on ZIF-8 were observed. The used ZIF-8 could be regenerated effectively and recycled at least three times without significant loss of adsorption capacity. In addition, ZIF-8 provided much larger adsorption capacity and faster adsorption kinetics than activated carbon and ZIF-7. The hydrophobic and π-π interaction between the aromatic rings of the BTri and 5-TTri and the aromatic imizole rings of the ZIF-8, and the coordination of the nitrogen atoms in BTri and 5-TTri molecules to the Zn(2+) ions in the ZIF-8 framework was responsible for the efficient adsorption. The fast adsorption kinetics, large adsorption capacity, excellent reusability as well as the pH, ionic strength, and dissolved organic matter insensitive adsorption create potential for ZIF-8 to be effective at removing benzotriazoles from aqueous solution.

Fabrication of metal-organic framework MIL-88B films on stainless steel fibers for solid-phase microextraction of polychlorinated biphenyls.

Metal-organic frameworks (MOFs) have received considerable attention as novel sorbents for sample preparation due to their fascinating structures and functionalities such as large surface area, good thermal stability, and uniform structured nanoscale cavities. Here, we report the application of a thermal and solvent stable MOF MIL-88B with nanosized bipyramidal cages and large surface area for solid-phase microextraction (SPME) of polychlorinated biphenyls (PCBs). Novel MIL-88B coated fiber was fabricated via an in situ hydrothermal growth of MIL-88B film on etched stainless steel fiber. The MIL-88B coated fiber gave large enhancement factors (757-2243), low detection limits (0.45-1.32ngL(-1)), and good linearity (5-200ngL(-1)) for PCBs. The relative standard deviation (RSD) for six replicate extractions of PCBs at 100ngL(-1) on MIL-88B coated fiber ranged from 4.2% to 8.7%. The recoveries for spiked PCBs (10ngL(-1)) in water and soil samples were in the range of 79.7-103.2%. Besides, the MIL-88B coated fiber was stable enough for 150 extraction cycles without significant loss of extraction efficiency. The developed method was successfully applied to the determination of PCBs in water samples and soil samples.

High-performance separation of fullerenes on metal-organic framework MIL-101(Cr).

The discovery of C60 and C70 has evoked a series of investigations in chemistry, physics, and materials sciences, and has stimulated the development of new separation and purification methods for fullerenes. High-performance liquid chromatography (HPLC) is the best technique of choice, and has been widely used for the separation and purification of fullerenes on various stationary phases. Metal–organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as permanent nanoscale porosity, high surface area, uniform structured cavities, and the availability of in-pore functionality and outer-surface modification are advantageous for diverse applications including gas adsorption and storage, catalysis, drug delivery, sensing, and imaging. Large diversity in structure, adsorption affinity, pore size, high surface area, and pore volume next to the minimal dead volumes make MOFs suitable advanced chromatographic separation media. Recently, several MOFs, such as MOF-5, HKUST-1, MIL-47, and MIL-53 have been successfully used as the stationary phases for HPLC separation of small molecules. Potential applications of MOFs for HPLC separation of carbon nanomaterials like fullerenes should be considerable, but has not been explored so far. Herein we report the exploration of MOFs as the stationary phase for HPLC separation of fullerenes with excellent selectivity and high throughput. To demonstrate the proofof-concept, we used MIL-101(Cr) as the stationary phase for HPLC because of its high surface area, large windows (12 and 16 14.5 ), mesoporous pores (29 to 34 ), and excellent chemical and solvents stability. MIL-101(Cr) is built up from a hybrid supertetrahedral building unit, which is formed by terephthalate ligands and trimeric chromium octahedral clusters. Even though its excellent properties, MIL-101(Cr) has never been explored as HPLC stationary phase before. MIL-101(Cr) was synthesized according to F rey et al. (See the Supporting Information). The successful preparation of MIL-101(Cr) was confirmed by X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM) (Figure S1–S3 in the Supporting Information). The suspension of MIL-101(Cr) in dichloromethane (CH2Cl2) was slurry-packed into a stainless steel column (5 cm long 4.6 mm i.d.) under 6000 psi for 10 min. The performance of the MIL-101(Cr) packed column was firstly demonstrated for the separation of C60 and C70. As shown in Figure 1, the MIL-101(Cr) packed column (5 cm

Incorporation of metal–organic framework UiO-66 into porous polymer monoliths to enhance the liquid chromatographic separation of small molecules

UiO-66 incorporated monoliths were fabricated to enhance the liquid chromatographic separation of small molecules with high column efficiency and good reproducibility.

Zeolite imidazolate framework-8 as sorbent for on-line solid-phase extraction coupled with high-performance liquid chromatography for the determination of tetracyclines in water and milk samples

Zeolite imidazolate framework-8 (ZIF-8) was used as the novel sorbent for on-line solid-phase extraction coupled with high-performance liquid chromatography (HPLC) for the determination of oxytetracycline (OTC), tetracycline (TC) and chlorotetracycline (CTC) in water and milk samples. 390mg of ZIF-8 was packed into a stainless steel column (3cm long×4.6mm i.d.) which was mounted on the HPLC injector valve to replace the sample loop. On-line solid-phase extraction of OTC, TC and CTC was achieved by loading sample solution at a flow rate of 3.0mLmin(-1) for 10min with the aid of a flow-injection system. The extracted analytes were subsequently eluted into a C18 analytical column (25cm long×4.6mm i.d.) for HPLC separation under isocratic condition with a mobile phase (10% MeOH-20% ACN-70% 0.02molL(-1) oxalic acid solution) at a flow rate of 1.0mLmin(-1). Under optimized conditions, the developed method gave the enhancement factors of 35-61, the linearity range of 5-1000μgL(-1), the detection limits of 1.5-8.0μgL(-1), quantification limits of 5.0-26.7μgL(-1), uncertainties of 0.9-1.1μgL(-1), and the sample throughput of 4 samples h(-1). The recoveries of OTC, TC and CTC at 50μgL(-1) in water and milk samples ranged from 70.3% to 107.4%.

Metal-organic framework UiO-66 coated stainless steel fiber for solid-phase microextraction of phenols in water samples.

Effective solid-phase microextraction (SPME) of polar phenols from water samples is usually difficult due to the strong interaction between polar phenols and aqueous matrix. Here, we report the fabrication of a metal-organic framework UiO-66 coated stainless steel fiber via physical adhesion for the SPME of polar phenols (phenol, o-cresol, p-cresol, 2,6-dimethylphenol, 2,4-dichlorophenol and 2,6-dichlorophenol) in water samples before gas chromatographic separation with flame ionic detection. Headspace SPME of 10mL sample solution with the fabricated UiO-66 coated fiber gave the enhancement factors of 160 (phenol) - 3769 (2,4-dichlorophenol), and the linear ranges of 1-1000μgL(-1) (2,6-dimethylphenol, 2,4-dichlorophenol and 2,6-dichlorophenol), 1-500μgL(-1) (o-cresol and p-cresol) and 5-500μgL(-1) (phenol). The detection limits ranged from 0.11μgL(-1) (2,6-dimethylphenol) to 1.23μgL(-1) (phenol). The precision (relative standard deviations, RSDs) for six replicate determinations of the analytes at 100μgL(-1) using a single UiO-66 coated fiber ranged from 2.8% to 6.2%. The fiber-to-fiber reproducibility (RSDs) for three parallel UiO-66 coated fibers varied from 5.9% to 10%. The recoveries obtained by spiking 5μgL(-1) of the phenols in the water samples ranged from 80% to 115%.

Fabrication of ZIF-8@SiO2 core-shell microspheres as the stationary phase for high-performance liquid chromatography.

The unique features of high porosity, shape selectivity, and multiple active sites make metal-organic frameworks (MOFs) promising as novel stationary phases for high-performance liquid chromatography (HPLC). However, the wide particle size distribution and irregular shape of conventional MOFs lead to lower column efficiency of such MOF-packed columns. Herein, the fabrication of monodisperse MOF@SiO2 core-shell microspheres as the stationary phase for HPLC to overcome the above-mentioned problems is reported. Zeolitic imidazolate framework 8 (ZIF-8) was used as an example of MOFs due to its permanent porosity, uniform pore size, and exceptional chemical stability. Unique carboxyl-modified silica spheres were used as the support to grow the ZIF-8 shell. The fabricated monodisperse ZIF-8@SiO2 packed columns (5 cm long × 4.6 mm i.d.) show high column efficiency (23,000 plates m(-1) for bisphenol A) for the HPLC separation of endocrine-disrupting chemicals (bisphenol A, β-estradiol, and p-(tert-octyl)phenol) and pesticides (thiamethoxam, hexaflumuron, chlorantraniliprole, and pymetrozine) within 7 min with good relative standard deviations for 11 replicate separations of the analytes (0.01-0.39, 0.65-1.7, 0.70-1.3, and 0.17-0.91% for retention time, peak area, peak height, and half peak width, respectively). The ZIF-8@SiO2 microspheres combine the advantages of the good column packing properties of the uniform monodisperse silica microspheres and the separation ability of the ZIF-8 crystals.