High performance liquid chromatography of substituted aromatics with the metal-organic framework MIL-100(Fe): Mechanism analysis and model-based prediction

J Chromatogr A. 2016 Feb 5:1432:84-91. doi: 10.1016/j.chroma.2016.01.006. Epub 2016 Jan 7.

Abstract

Metal-organic framework (MOF) MIL-100(Fe) with well-defined thickness was homogenously coated onto the outer surface of magnetic microparticles via a liquid-phase epitaxy method. The as-synthesized MIL-100(Fe) was used as stationary phase for high-performance liquid chromatography (HPLC) and separations of two groups of mixed aromatic hydrocarbons (toluene, styrene and p-xylene; acetanilide, 2-nirtoaniline and 1-naphthylamine) using methanol/water as mobile phase were performed to evaluate its performance. Increasing water content of the mobile phase composition can greatly improve the separations on the expense of a longer elution time. Stepwise elution significantly shortens the elution time of acetanilide, 2-nirtoaniline and 1-naphthylamine mixtures, while still achieving a baseline separation. Combining the experimental results and in-depth modeling using a recently developed chromatographic software (ChromX), adsorption equilibrium parameters, including the affinities and maximum capacities, for each analyte toward the MIL-100(Fe) are obtained. In addition, the pore diffusivity of aromatic hydrocarbons within MIL-100(Fe) was determined to be 5×10(-12)m(2)s(-1). While the affinities of MIL-100(Fe) toward the analyte molecules differs much, the maximum capacities of the analytes are in a narrow range with q*MOFmax,toluene=3.55molL(-1), q*MOFmax,styrene or p-xylene=3.53molL(-1), and q*MOFmax,anilines=3.12molL(-1) corresponding to approximately 842 toluene and 838 styrene or p-xylene, and 740 aniline molecules per MIL-100(Fe) unit cell, respectively.

Keywords: Isotherm parameter; Liquid chromatography; Metal–organic framework (MOF); Modeling; Separation.

MeSH terms

  • 1-Naphthylamine / analysis
  • Acetanilides / analysis
  • Aniline Compounds / analysis
  • Chromatography, High Pressure Liquid
  • Hydrocarbons, Aromatic / analysis*
  • Iron*
  • Metal Nanoparticles*
  • Organometallic Compounds / chemistry*
  • Styrene / analysis
  • Toluene / analysis
  • Xylenes / analysis

Substances

  • Acetanilides
  • Aniline Compounds
  • Hydrocarbons, Aromatic
  • Organometallic Compounds
  • Xylenes
  • 2-nitroaniline
  • Toluene
  • Styrene
  • 4-xylene
  • 1-Naphthylamine
  • Iron
  • aniline
  • acetanilide