Elsevier

Journal of Chromatography A

Volume 1432, 5 February 2016, Pages 84-91
Journal of Chromatography A

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

https://doi.org/10.1016/j.chroma.2016.01.006Get rights and content

Highlights

  • Synthesis of novel shell–core microadsorbents based on the MOF MIL-100(Fe).

  • Water stable adsorbents with a crystalline active layer of only 650 nm thickness.

  • Baseline separation of substituted aromatics.

  • Extraction of equilibrium and mass transfer parameters by experiments and modeling.

  • Comparison of three common MOFs regarding their suitability for HPLC applications.

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 m2 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 = 3.55 mol L−1, q*MOFmax,styrene or p-xylene = 3.53 mol L−1, and q*MOFmax,anilines = 3.12 mol L−1 corresponding to approximately 842 toluene and 838 styrene or p-xylene, and 740 aniline molecules per MIL-100(Fe) unit cell, respectively.

Introduction

Metal-organic frameworks (MOFs), also called porous coordination polymers (PCPs), are an emerging class of crystalline porous materials constructed with inorganic metals ions and organic functional linkers [1], [2]. A key fascinating feature of MOFs is that their structures (pore sizes, geometrics and chemical properties) can be rationally designed for specific targets [3], a possibility which does not exist in other porous materials to the same degree. The versatility of different MOFs leads to a wide range of promising applications in gas storage [4], separation [5], [6], catalysis [7], biomedicine [8], and so on [9]. Besides their tunable structures, the absence of dead volume, high specific surface area, high loading capacity of guest species and inherent porosity make MOFs promising materials as chromatographic stationary phases [10], [11], [12]. Recently, several MOFs have been successfully employed as high-performance liquid chromatography (HPLC) stationary phases to separate dissolved molecules. For example, HKUST-1 packed columns showed good separation performance of chemical isomers [13], [14]. Yan and co-workers [15], [16], [17], [18], [19] demonstrated the use of different MOFs, especially MIL-101(Cr), for HPLC of substituted aromatics. In the last two years, the application of MOFs from the UiO series in HPLC has been brought into special attention due to their excellent thermal and chemical stability [20], [21]. However, most of the previous studies are focused on MOF synthesis and present the chromatographic performance as “proof-of-concept”. What is often missing is the fundamental information about the adsorption interaction between the dissolved solutes and the MOF-based stationary phase, especially the equilibrium isotherms and diffusion parameters. However, for practical applications and model based optimization of the use of MOF based columns in HPLC systems these parameters are of great importance and must be known for in-depth understanding. Instead of the broad size and shape distribution of MOF powders fabricated by traditional solvothermal methods, the recently developed layer-by-layer liquid-phase epitaxy (LPE) process [22], [23] is a promising method to prepare homogenous MOF coatings, so-called surface-mounted MOFs (SURMOFs), with controllable thickness on the surface of a suitable functionalized substrate [24], [25].

In present work, MIL-100(Fe) was selected from the wide range of possible MOFs due to its suitability to generate SURMOFs and its stability in the presence of water. The reaction of iron(III) chloride (FeCl3) and 1,3,5-tricarboxylic acid (BTC) leads to a rigid 3D crystal structure with large pores, named MOF-100(Fe) by Horcajada et al. in 2007 [26]. Compared to other metal ions, Fe(III) is an ideal candidate to be used as the metal nodes in the assembling of MOFs, because of its low toxicity, easy accessibility, and most importantly, its robust Lewis acidity, which gives rise to strong coordinate covalent bonds with the organic linkers to form more stable MOFs. The MIL-100(Fe) structure (Fig. 1, inset) consists of 2.5 nm and 2.9 nm mesoporous pores with window diameters of ca. 0.47–0.55 nm and 0.86 nm, respectively. Moreover, MIL-100(Fe) possesses large accessible and permanent pores, and exhibits a remarkable thermal (>270 °C) and chemical stability (organic solvents or water). Additionally, the presence of the accessible coordinately unsaturated metal sites in the walls of MIL-100(Fe) structure allows the strong coordination of guest molecules. MIL-100(Fe) has been intensively studied for applications in separation [27], [28], catalysis [29] and drug delivery [30].

In this work, we present the synthesis of homogenous MIL-100(Fe) coatings onto the surface of magnetic microparticles (MPs) by a LPE process in order to yield a core–shell architecture (Fig. 1). The core–shell structured MIL-100(Fe) MPs were used as HPLC stationary phase to illustrate the MOF separation performance and mechanism of mixed aromatic hydrocarbons. The interaction between the organic linkers of the inner surface of the MOF shell and aromatic compounds results in their different affinities toward the stationary phase. First, these affinities were determined independently by single component HPLC experiments. Afterwards, the separation of mixtures of three different aromatic compounds was demonstrated using isocratic and stepwise elution modes. In this context, the capability of a recently published chromatographic software ChromX [http://mab.blt.kit.edu/chromx.php] to predict the chromatographic behavior of mixtures on the basis of single component equilibrium and kinetic data is shown. This allows an in-silico optimization of the separation as well as an in-depth understanding of the limiting parameters, pointing the way for future developments of MOF based stationary phases.

Section snippets

Chemicals and reagents

Carboxyl-functionalized magnetic silica particles (SiO2-MAG-S1964-COOH), with narrow size distribution of 4.7 ± 0.14 μm were purchased from microParticles GmbH, Berlin, Germany. Empty stainless steel HPLC columns (200 mm long × 1.0 mm i.d., column volume 180 μL, order code: N1910 0000) were bought from VDS optilab Chromatographie Technik GmbH, Berlin, Germany.

All reagents were at least analytical grade and used without further purification. Iron(III) chloride hexahydrate (FeCl3·6H2O, 99%),

Characterization of synthesized MIL-100(Fe) MPs

The as-synthesized MIL-100(Fe) MPs were characterized by XRD and SEM experiments. The successful growth of a MIL-100(Fe) shell onto the MPs is validated by the good agreement between the XRD pattern of the obtained MIL-100(Fe) MPs and the simulated one (Fig. 3a). The SEM images of the raw MPs and the prepared MIL-100(Fe) MPs are shown in Fig. 3b and 3c, respectively. Fig. S1 shows the images of these uniform uncoated and coted MPs with more numbers under a lower magnification. Fig. 3c displays

Conclusions

Crystalline MIL-100 (Fe) SURMOF thin films were coated onto magnetic microparticles having a COOH-terminated surface using the process of liquid-phase epitaxy (LPE). Chromatographic columns packed with the as-synthesized MIL-100(Fe) magnetic particles offer improved separation performance for aromatic hydrocarbons with increasing water content of the mobile phases (MeOH/H2O), due to the change of the affinity strength between the analytes and the crystalline MOF-based solid phase. Additionally,

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