Control of Polymorphism of Metal–Organic Frameworks Using Mixed

Dec 13, 2017 - Herein, we report the influence of iron(III) on the crystallization of chromium(III) terephthalate metal–organic framework. The selec...
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Control of Polymorphism of Metal-Organic Frameworks using Mixed-Metal Approach Thanadporn Tanasaro, Kanyaporn Adpakpang, Somlak Ittisanronnachai, Kajornsak Faungnawakij, Teera Butburee, Suttipong Wannapaiboon, Makoto Ogawa, and Sareeya Bureekaew Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01193 • Publication Date (Web): 13 Dec 2017 Downloaded from http://pubs.acs.org on December 13, 2017

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Crystal Growth & Design

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Control of Polymorphism of Metal-Organic

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Frameworks using Mixed-Metal Approach

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Thanadporn Tanasaro,a Kanyaporn Adpakpang,a Somlak Ittisanronnachai,b Kajornsak

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Faungnawakij, c Teera Butburee,c Suttipong Wannapaiboon,d Makoto Ogawa,a and Sareeya

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Bureekaew*, a

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a

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Technology, 555 Moo 1 Payupnai, Wangchan, Rayong 21210, Thailand.

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b

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1 Payupnai, Wangchan, Rayong 21210, Thailand.

School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and

Frontier Research Center (FRC), Vidyasirimedhi Institute of Science and Technology, 555 Moo

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c

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Development Agency (NSTDA), 111 Thailand Science Park, Pahonyothin Rd., Klong Laung,

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Pathumthani 12120, Thailand.

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d

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University of Munich, Lichtenbergstr. 4, D-85748 Garching, Germany.

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KEYWORDS:

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Polymorphism

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ABSTRACT: Herein, we report the influence of iron(III) on the crystallization of chromium(III)

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terephthalate metal–organic framework. The selective phase formation of polymorphs MIL-101

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and MIL-88B can be systematically controlled by varying the concentration of metal-cationic

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competitor, iron(III). The addition of iron(III) affects not only the selective phase formation but

National Nanotechnology Center (NANOTEC), National Science and Technology

Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, Technical

Metal-organic

frameworks,

HF-free,

Framework

isomerism,

Mixed-metal,

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also the morphology and crystallinity of chromium(III) terephthalate MOF. This investigation

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clearly indicates the crystal growth tailoring of polymorphic MOFs by means of the second metal

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ionic competitor.

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Metal-organic frameworks (MOFs) possess versatile composition attributed to the combination

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between various transition metals and organic linkers with diverse connectivity of the building

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units. Therefore, MOFs can provide unique physical and chemical properties which are

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applicable in several research fields such as gas storage, sensors, heterogeneous catalysts and

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drug delivery.1-4 One of the unique features of MOFs is the versatility in design and synthesis

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based on the concept of controlled building units,5 which provides a possibility to tune the shape,

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size, and functionality of their cavities and the internal surfaces. Such microscopic attributes

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could be controlled by choosing the desired metal ions and organic ligands. Hence, it is quite

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common to synthesize isostructural MOFs consisting of different metal and/or organic linkers

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but still exhibiting isoreticular crystalline structures with the similar space group.6-8 Moreover,

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various kinds of isostructural metal (metal clusters) and organic linkers can be integrated into a

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single framework to produce multicomponent or so-called multivariant MOFs9; mixed-metal

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MOFs contain more than one type of metal cations while mixed-linker MOFs contains more than

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one type of linkers.10 Herein, we focus on controlled synthesis of mixed-metal MOFs. Up to

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date, there are many studies reported the outstanding properties of the mixed-metal MOFs for

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various applications.11-16 For instance, the incorporation of Co(II) in Ni(II)-MOF-74 via post-

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synthetic metal exchange (PSE) method greatly enhances the catalytic activity in cyclohexene

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oxidation.13 The substitution of Zn(II) with Co(II) in ZIF-67(Co) by one-pot synthesis increases

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its water stability and exhibits higher CO2 and H2 adsorption capacity than the parent

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compounds, ZIF-67(Co) and ZIF-8(Zn).14 The incorporation of Fe(II) into non-reactive MOF-5

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(Zn4O(bdc)3, bdc = 1,4-benzenedicarboxylate) frameworks increases the redox reactivity when

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reacted with NO.15 In all, it emphasizes that novel functions as well as superior properties apart

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from the single-component, parent MOFs could be emerged in the mixed-metal MOFs.

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Properties of MOFs depend not only on microscopic attributes (crystal structures) but also on

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macroscopic attributes (size and morphology). An attempt to control the macroscopic features of

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MOFs has been achieved by using coordination modulators as well as modifying the synthetic

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procedures, which consequently modulate the MOFs properties such as adsorption capacity and

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selectivity.17-20 Moreover, the self-assembly of similar metal clusters and organic linkers can

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construct MOFs with different network structures and properties, depending on the synthetic

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parameters. The different frameworks with the same chemical compositions can be described as

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framework isomers or polymorphs.21 Herein, we reveal an alternative way to control the MOFs’

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polymorphism by means of the mixed-metal MOFs concept. Even though the coordination

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geometries of different metal building units with respect to the organic linker are similar, one

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metal may disrupt the construction of a scaffold built from another metal ions and consequently

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leads to a controlled formation of different polymorphic MOFs.22 Insight of the influences of the

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mixed metal ions on the crystallization process of microcrystalline MOFs is essential for fine

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tuning the MOF characteristics.

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Chromium terephthalate MOFs are typically found as MIL-101, MIL-88B and MIL-53.23-25

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MIL-101 and MIL-88B are polymorphs composed of triangular Cr3O(COO)6 clusters while MIL-

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53 is constructed from infinite chains of corner-sharing metal octahedra and bdc linkers. These

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three MOFs can be also obtained from other metals such as V, Cr, Fe, Al, or Ti.23, 26-29 Isomeric

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MIL-101 and MIL-88B are found with the underlying topologies of mtn and acs, respectively.

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On one hand, these isomeric MOFs are thermally (up to 300°C) and chemically stable.23, 24 In

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addition, after removing the solvent by thermal treatment under vacuum, they present active

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coordinatively unsaturated sites (CUSs) which are the accessible sites for guest molecules acting

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as a key feature in catalytic and adsorption applications.30 On the other hand, the distinct

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connectivity (different topology) between metal clusters and organic ligands of these two MOFs

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results in the different attributes. Specifically, MIL-101 is rigid and possesses higher surface area

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and pore volume while MIL-88B exhibits framework flexibility as a response to introduction and

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removal of guest molecules.23,

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polymorphs is generally obtained under different synthetic conditions.23,

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several reports related to MIL-101(Cr), the study of MIL-88B(Cr) is scarcely available; report on

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the synthesis of MIL-88B(Cr) remains less informative.24 Furthermore, the established method

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for the preparation of chromium(III) terephthalate MOFs can be obtained under hydrothermal

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conditions with hazardous hydrofluoric acid (HF) at high temperatures.23 Therefore, the

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avoidance of HF can provide an easier and less harmful preparation.32, 33 Herein, we report the

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facile and green synthesis (HF-free) method for the phase-selective formation between MIL-101

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and MIL-88B by adjusting only the concentration of the iron(III) competitor. Moreover, effects

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of iron(III) on the morphology and crystallinity of chromium(III) terephthalate MOFs are

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investigated. A way to fine tune the formation of isomeric chromium(III) terephthalate MOF by

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means of the mixed-metal concept is discussed in detail.

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All products were obtained based on the synthesis procedure of MIL-101(Cr) with some

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modification34 as described in the Supporting Information. The molar ratios of Cr(NO3)3 and

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Fe(NO3)3 were varied as 4.75:0.25 (5 %Fe), 4.5:0.5 (10 %Fe), 4.25:0.75 (15 %Fe), 3.75:1.25 (25

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%Fe) and 3.33:1.67 (33.3 %Fe) mmol resulting in the products 1, 2, 3, 4 and 5, respectively. For

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comparison, the material without the addition of Fe(III) was also synthesized. Figure 1 depicts

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Concerning the synthesis, the formation of these two 31

While there are

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photographs of the obtained powders from all synthetic conditions. The product obtained by

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using only Cr(III) shows bright green color; the color changes towards brown color

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corresponding with the incorporated Fe(III) amount (products 1, 2, 3 exhibit brown-green color

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and products 4 and 5 show orange-brown color).

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6 7

Figure 1. Photographs of the obtained product powders.

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In order to confirm the phase and purity, powder X-ray diffraction (XRD) technique was used

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and the XRD patterns of the obtained compounds were indexed in comparison with the simulated

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pattern of the chromium-based parent MOFs (Figure 2, Figure S2 and S3, supporting

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information).23 The XRD patterns of MIL-101(Cr), 1, 2 and 3 resemble to the simulated pattern

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of MIL-101(Cr) indicating that the addition of Fe up to 15 % has no influence on the structural

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disintegration. However, the XRD pattern of 4 shows the additional peaks at 2θ = 10.4, 13.2,

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18.6, 19.3, 20.8, 25.3, 26.6 and 29.8 degrees, which correspond to the simulated pattern of MIL-

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88B(Cr), together with the less pronounced diffraction peaks from MIL-101(Cr). This

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observation indicates that 4 contains mixed phases of MIL-101 and MIL-88B. In case of 5, the

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XRD pattern shows only the diffraction peaks corresponded to MIL-88B, indicating the

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complete formation of mixed-metal MIL-88B(Cr, Fe) by addition of 33.3% Fe(III) into the

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synthetic mixture.

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To understand the effect on the formation of MIL-88B phase by adding Fe(III) with high

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concentration (33.3 %) into the Cr-based MOF synthesis, an additional experiment was

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conducted by adding only Fe(III) into the solution mixture and then followed the similar

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synthetic procedure. The XRD result (Figure S1, supporting information) reveals that the

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obtained material is not isostructural to MIL-88B(Fe). In other words, the crystalline MIL-

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88B(Fe) phase cannot be achieved under this water-based synthetic condition used herein since

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the standard procedure for MIL-88B(Fe) synthesis is usually performed in DMF solvent.35-37

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This observation implies that the observed MIL-88B phase in the cases of mixed-metal

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conditions is not the mixture of MIL-88B(Fe) with the MIL-101(Cr) but rather the formation of

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mixed-metal MIL-88B(Cr, Fe) instead. Therefore, the influence on the phase-selective formation

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and particle size of the chromium-based MIL-101 and MIL-88B phases are affected by the

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incorporation of Fe(III) together with Cr(III) only.

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Figure 2. XRD patterns of as-synthesized mixed-metal MOFs(Cr, Fe) compared with those of

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MIL-101(Cr) and MIL-88B(Cr) generated from simulation.23

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Morphological study was performed by using field-emission scanning electron microscopy (FE-

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SEM). FE-SEM images of the obtained products are presented in Figure 3. To be noted that

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morphologies of MIL-101 and MIL-88B are typically octahedron and hexagonal rod,

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respectively.23, 24 Figure 3a shows uniform octahedral morphology corresponded to MIL-101(Cr)

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with particle size of ~ 100 nm. As depicted in Figure 3b-c, 1 (5 %Fe) and 2 (10 %Fe) show

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octahedral morphology with the particle sizes of 400 - 500 nm and 500 - 600 nm, respectively.

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This evidence is well-agreed with the XRD result that the incorporation of Fe up to 10 % has no

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alteration on the phase formation of MIL-101 crystal. When %Fe increases to 15 % (for 3),

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particles with octahedral shape are observed together with a small content of hexagonal rod

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particles, corresponded to MIL-88B (Figure 3d). Even though there is no evidence for the

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formation of MIL-88B phase from the XRD of 3, the presence of hexagonal rod particle implies

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that MIL-88B starts to form under this condition, however, its small amount cannot be detected

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by XRD. As increasing %Fe to 25 for 4, the hexagonal rods of MIL-88B is major component

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with minor octahedral MIL-101 particles (Figure 3e). When %Fe reaches 33.3 % for 5,

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octahedral MIL-101 particle is absent and only hexagonal rods of MIL-88B with small particle

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are observed. Herein, the homogeneity of the particle shapes obtained in product 5 indicates the

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formation of crystalline phase-pure MIL-88B(Cr,Fe). Additionally, the presence of some small

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particles is possibly due to the incomplete formation of the long hexagonal rods of MIL-88B or

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the other contaminant. Even though the XRD results do not show the present of any additional

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phases, the phase purity of MIL-88B can be carefully examined by TEM.

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morphological observation is in a good agreement with the XRD data, highlighting a control of

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polymorphism of chromium-terephthalate MOFs by the mixed-metal method.

Note that, the

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Figure 3. FE-SEM images of synthesized materials (a) MIL-101(Cr) and the mixed-metal MOFs

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(b) 1, (c) 2, (d) 3, (e) 4, and (f) 5.

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The distribution of the incorporated Fe in chromium-terephthalate framework was also

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investigated via the energy-dispersive X-ray spectroscopy (EDS) equipped with transmission

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electron microscopy (TEM). As illustrated in Figure 4, the scanning transmission electron

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microscope (STEM)/EDS of all the materials shows a good distribution of Fe and Cr elements

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throughout the structures of octahedral MIL-101 and hexagonal rod-shaped MIL-88B. This result

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indicates the homogeneous incorporation of both Fe(III) and Cr(III) ions into both of the

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structures, confirming the successful formation of mixed-metal frameworks of MIL-101(Cr, Fe)

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and MIL-88B(Cr, Fe).

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4 5

Figure 4. STEM images and STEM/EDS elemental maps of (a) 1, (b) 2, (c) 3, (d) 4 and (e) 5.

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Cr and Fe are shown in red and blue, respectively.

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Further investigation on the crystal phase of 5 by TEM reveals that the small particles found

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together with the rod-shaped morphology can be identified as impured Fe2O3 phase. As can be

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seen in Figure S4, the lattice image from high resolution TEM together with the nanobeam-

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electron diffraction pattern of the small particles on the surface of the large rod match well with

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the d-spacing of Fe2O3 phase. However, the Fe2O3 phase is considered as a minor contaminant

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since an attempt for the EDS mapping measurement of the small particles had been made. As

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depicted in Figure S5, the STEM/EDS mapping result of the particles without the large rodes

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shows homogeneous distribution of both elemental Cr and Fe. The result suggests that the area of

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small particles is also composed of MIL-88B(Cr/Fe) with small size ascribing to the incomplete

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formation as well as the disintegration of the large hexagonal rods of MIL-88B(Cr/Fe).

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Chemical composition of mixed-metal MOFs(Cr, Fe) was analyzed by inductively coupled

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plasma optical emission spectrometer (ICP-OES). The results are listed in Table 1. Note that, as

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revealed by SEM and TEM, 4 and 5 are mixed phases (MIL-101/MIL-88B/Fe2O3 for 4 and MIL-

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88B/Fe2O3 for 5), thus ICP-OES is not applicable for determining their Fe and Cr compositions.

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The results from ICP-OES of 4 and 5 in Table 1 were omitted. The relative quantities of Cr and

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Fe elemental components in all the synthesized materials are consistent with the synthesis

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condition in which the ratio of Fe/Cr increases when the added amount of Fe(III) salt increases.

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To be noted that the observed contents of Cr are less than that of the calculated ones. It is clearly

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seen in 1, 2, and 3 for the Fe addition of 5, 10, and 15 %, the incorporation of Cr should be 95,

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90, and 85 %, respectively. However, the observed contents of Cr in these materials are 82.2,

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75.7, and 68.2 % for 1, 2, and 3, respectively. This can be an evidence of a competitive behavior

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of Fe(III) ion with Cr(III) ion to the formation of MIL-101. The presence of Fe(III) up to 15 %

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can decelerate the incorporation of Cr(III) for the crystal growth of MIL-101, leading to the

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formation of larger particle size of octahedral crystal as compared to that of 0 %Fe (or in other

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word, 100 %Cr condition). According to the FE-SEM evidence, MIL-88B starts to form when

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adding Fe(III) of at least 15 %. Note that, this ratio may be the point that the concentration

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reached the favorable condition for the formation equilibrium of MIL-88B instead of MIL-101.

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Hence, the more Fe/Cr ratio than 15 % in the synthetic condition, the more formation of MIL-

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88B phase.

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Table 1. ICP elemental analysis of mixed-metal MOFs(Cr, Fe) as compared to the calculated

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values based on the synthetic conditions.

Material

Initial content (mol)

Resulting content (mol)

%Fe

%Cr

%Fe

%Cr

1

5.0

95.0

17.8

82.2

2

10.0

90.0

24.3

75.7

3

15.0

85.0

31.8

68.2

4

25.0

75.0

-

-

5

33.3

66.7

-

-

3 4

N2 sorption isotherms analysis was performed for the determination of pore structure and surface

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area of all the obtained materials (Figure 5). The shape of the isotherms for 1, 2, and 3 shows the

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characteristic isotherm of a typical MIL-101 phase.23 The expanded view for the isotherms of 4

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and 5 are illustrated in Figure 6. It can be clearly seen that 4 still possesses the characteristic

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isotherm of MIL-101 while 5 does not.

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Specific surface area calculated from the Brunauer–Emmett–Teller (BET) equation for all the

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synthesized materials are presented in Table 2. According to their similar crystal structure and

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morphology, the obtained materials 1, 2 and 3 provide high surface areas (above 2300 m2/g)

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which are comparable to that of the parent MIL-101(Cr). However, surface areas of 4 and 5

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dramatically decrease to 497 and 174 m2/g, respectively. This is due to the presence of MIL-88B

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which typically has less specific surface area compared with MIL-101.38

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Figure 5. N2 sorption isotherms of all the synthesized mixed-metal MOFs(Cr, Fe) as compared

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to MIL-101(Cr). The measurement was performed at 77 K.

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2 3 4

Figure 6. Expanded view from Figure 5 for the N2 sorption isotherms of 4 and 5 at 77 K. Table 2. BET surface area of mixed-metal MOFs(Cr, Fe) from N2 sorption isotherm. Sample

BET surface area (m2/g)

MIL-101(Cr)

2691

1

2378

2

2678

3

2864

4

493

5

174

5

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In summary, the effect of the Fe(III) addition on the phase, size, and shape of chromium(III)

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terephthalate microcrystals by using environmental friendly water-based and HF-free synthesis

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route was systematically investigated. Through the isomeric characteristic, mixed-metal MIL-

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101(Cr, Fe) and MIL-88B(Cr, Fe) are achieved from this synthesis approach depending on the

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molar ratio of the two metal ions. Octahedral crystal MIL-101(Cr, Fe) with increased particle

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sizes as compared to the parent MIL-101(Cr) are obtained when the concentrations of Fe(III) are

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5, 10, and 15 %. While the concentration of Fe(III) exceeds 15 %, the formation of hexagonal

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rod MIL-88B is enhanced. This finding clearly highlights a critical role of the metal-cationic

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competitor on the crystal growth of MOFs via the polymorphism. It is believed that the present

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approach may be a useful tool for further study on the crystal design and synthesis of multi-

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component MOFs with diverse functionalities.

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ASSOCIATED CONTENT

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Supporting Information. Detailed synthesis and characterization with the powder XRD patterns

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of material with 100 %Fe and simulated MIL-88B(Fe) together with SEM/TEM micrographs

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with the electron diffraction pattern and EDS mapping data. This material is available free of

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charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

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Corresponding Author

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*Dr. Sareeya Bureekaew.

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E-mail: [email protected].

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Tel.: (+66)33014256.

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ACKNOWLEDGMENT

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This work was supported by student grant and postdoctoral fellowship from Vidyasirimedhi

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Institute of Science and Technology and by the Thailand Research Fund (TRF) grant number

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RSA6080068.

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REFERENCES

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(1) Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux,

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D.; Clayette, P.; Kreuz, C.; Chang, J. S.; Hwang, Y. K.; Marsaud, V.; Bories, P. N.; Cynober, L.;

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Gil, S.; Ferey, G.; Couvreur, P.; Gref, R., Porous metal-organic framework nanoscale carriers as

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a potential platform for drug delivery and imaging. Nat. Mater. 2010, 9, 172-178.

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(2) Millward, A. R.; Yaghi, O. M., Metal−organic frameworks with exceptionally high capacity

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for storage of carbon dioxide at room temperature. J. Am. Chem. Soc. 2005, 127, 17998-17999.

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(3) Yazaydın, A. Ö.; Snurr, R. Q.; Park, T.-H.; Koh, K.; Liu, J.; LeVan, M. D.; Benin, A. I.;

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Crystal Growth & Design

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For Table of Contents Use Only

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Control of Polymorphism of Metal-Organic Frameworks using Mixed-Metal Approach

3

Thanadporn

4

Faungnawakij,c Teera Butburee,c Suttipong Wannapaiboon,d Makoto Ogawa,a and Sareeya

5

Bureekaew*,a

Tanasaro,a

Kanyaporn

Adpakpang,a

Somlak

Ittisanronnachai,b

Kajornsak

6 7

Two polymorphs, MIL-101 and MIL-88(B) were selectively synthesized using mixed-metal

8

approach. The phase selectivity highly depends on the molar ratio of the metal ions (Cr and Fe).

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