Control of Polymorphism of MetalâOrganic Frameworks Using Mixed

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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

2

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.

8

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

10

c

11

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

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Pathumthani 12120, Thailand.

13

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)

18

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

19

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

20

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,

ACS Paragon Plus Environment

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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

3

ionic competitor.

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

5

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

6

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

7

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

9

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

15

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

18

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

19

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

20

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

21

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

22

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

23

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


2

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

2

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.

4

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

5

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

7

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

9

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

17

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

21

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

22

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

23

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

2

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

3

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

4

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

5

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

6

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

7

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

12

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

13

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

20

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

22

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

23

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

24

Concerning the synthesis, the formation of these two 31

While there are


4

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

2

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

3

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

4

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

5

6 7

Figure 1. Photographs of the obtained product powders.

8

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

9

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

10

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

11

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

12

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

13

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

16

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

2

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

3

synthetic mixture.

4

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

5

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

15

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


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1 2

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

3

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-

5

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

6

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

7

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

8

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

9

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

11

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

12

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

2

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

3

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

4

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

5

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

7

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

8

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

9

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


8

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1 2

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

5

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

6

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

7

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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1

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

2

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

3

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

4

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

5

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

6

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

12

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

19

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,

21

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

22

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

23

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

2

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

3

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

4

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-

6

88B phase.

7


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

2

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

5

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

8

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

10

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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1 2

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

3

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

4


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1

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)

2

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

3

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

4

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

5

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

6

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

7

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

8

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

9

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

10

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

11

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

16

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

17

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

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AUTHOR INFORMATION

19

Corresponding Author

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*Dr. Sareeya Bureekaew.

21

E-mail: [email protected].

22

Tel.: (+66)33014256.


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1

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.

5

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1

For Table of Contents Use Only

2

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).

9


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Control of Polymorphism of MetalâOrganic Frameworks Using Mixed

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