Metal–Organic Framework MIL-101(Cr) for High-Performance Liquid Chromatographic Separation of Substituted Aromatics

• Published in: Analytical chemistry (Washington) Vol. 83; no. 18; pp. 7144 - 7150
• Main Authors: Yang, Cheng-Xiong, Yan, Xiu-Ping
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 15.09.2011
• Subjects: Analytical chemistry; Benzene Derivatives - chemistry; Benzene Derivatives - isolation & purification; Chemistry; Chlorobenzenes - chemistry; Chlorobenzenes - isolation & purification; Chromatographic methods and physical methods associated with chromatography; Chromatography; Chromatography, High Pressure Liquid - methods; Dichlorobenzene; Exact sciences and technology; Isomerism; Metals; Metals - chemistry; Organic Chemicals - chemistry; Other chromatographic methods; Retention time; Slurries; Styrene; Styrene - chemistry; Styrene - isolation & purification; Temperature; Thermodynamics; Toluene; Toluene - chemistry; Toluene - isolation & purification; Xylene; Xylenes - chemistry; Xylenes - isolation & purification; High resolution; Peak resolution; Temperature; Cage; Impurity; Enthalpy; HPLC chromatography; Entropy; Metal; Replica method; Retention time; Mixture; Isomer; Ethylbenzene; Efficiency; Xylene; Standard deviation; Phase composition; Pore structure; Sample; Toluene; Plate; Styrene; Dichloromethane; Affinity; Surface area; Slurries; Packed column
• ISSN: 0003-2700; 1520-6882; 1520-6882
• DOI: 10.1021/ac201517c

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.