Subscriber access provided by READING UNIV
Communication
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
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
Control of Polymorphism of Metal-Organic
2
Frameworks using Mixed-Metal Approach
3
Thanadporn Tanasaro,a Kanyaporn Adpakpang,a Somlak Ittisanronnachai,b Kajornsak
4
Faungnawakij, c Teera Butburee,c Suttipong Wannapaiboon,d Makoto Ogawa,a and Sareeya
5
Bureekaew*, a
6
a
7
Technology, 555 Moo 1 Payupnai, Wangchan, Rayong 21210, Thailand.
8
b
9
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,
12
Pathumthani 12120, Thailand.
13
d
14
University of Munich, Lichtenbergstr. 4, D-85748 Garching, Germany.
15
KEYWORDS:
16
Polymorphism
17
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
1
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 2 of 23
1
also the morphology and crystallinity of chromium(III) terephthalate MOF. This investigation
2
clearly indicates the crystal growth tailoring of polymorphic MOFs by means of the second metal
3
ionic competitor.
4
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
8
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,
10
size, and functionality of their cavities and the internal surfaces. Such microscopic attributes
11
could be controlled by choosing the desired metal ions and organic ligands. Hence, it is quite
12
common to synthesize isostructural MOFs consisting of different metal and/or organic linkers
13
but still exhibiting isoreticular crystalline structures with the similar space group.6-8 Moreover,
14
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
16
MOFs contain more than one type of metal cations while mixed-linker MOFs contains more than
17
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
ACS Paragon Plus Environment
2
Page 3 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
(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
3
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
6
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
8
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
10
parameters. The different frameworks with the same chemical compositions can be described as
11
framework isomers or polymorphs.21 Herein, we reveal an alternative way to control the MOFs’
12
polymorphism by means of the mixed-metal MOFs concept. Even though the coordination
13
geometries of different metal building units with respect to the organic linker are similar, one
14
metal may disrupt the construction of a scaffold built from another metal ions and consequently
15
leads to a controlled formation of different polymorphic MOFs.22 Insight of the influences of the
16
mixed metal ions on the crystallization process of microcrystalline MOFs is essential for fine
17
tuning the MOF characteristics.
18
Chromium terephthalate MOFs are typically found as MIL-101, MIL-88B and MIL-53.23-25
19
MIL-101 and MIL-88B are polymorphs composed of triangular Cr3O(COO)6 clusters while MIL-
20
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
ACS Paragon Plus Environment
3
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 4 of 23
1
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,
8
polymorphs is generally obtained under different synthetic conditions.23,
9
several reports related to MIL-101(Cr), the study of MIL-88B(Cr) is scarcely available; report on
10
the synthesis of MIL-88B(Cr) remains less informative.24 Furthermore, the established method
11
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
14
facile and green synthesis (HF-free) method for the phase-selective formation between MIL-101
15
and MIL-88B by adjusting only the concentration of the iron(III) competitor. Moreover, effects
16
of iron(III) on the morphology and crystallinity of chromium(III) terephthalate MOFs are
17
investigated. A way to fine tune the formation of isomeric chromium(III) terephthalate MOF by
18
means of the mixed-metal concept is discussed in detail.
19
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
21
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
ACS Paragon Plus Environment
4
Page 5 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
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,
14
18.6, 19.3, 20.8, 25.3, 26.6 and 29.8 degrees, which correspond to the simulated pattern of MIL-
15
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
ACS Paragon Plus Environment
5
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 6 of 23
1
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
6
conducted by adding only Fe(III) into the solution mixture and then followed the similar
7
synthetic procedure. The XRD result (Figure S1, supporting information) reveals that the
8
obtained material is not isostructural to MIL-88B(Fe). In other words, the crystalline MIL-
9
88B(Fe) phase cannot be achieved under this water-based synthetic condition used herein since
10
the standard procedure for MIL-88B(Fe) synthesis is usually performed in DMF solvent.35-37
11
This observation implies that the observed MIL-88B phase in the cases of mixed-metal
12
conditions is not the mixture of MIL-88B(Fe) with the MIL-101(Cr) but rather the formation of
13
mixed-metal MIL-88B(Cr, Fe) instead. Therefore, the influence on the phase-selective formation
14
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.
ACS Paragon Plus Environment
6
Page 7 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
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
4
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.
10
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
ACS Paragon Plus Environment
7
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 8 of 23
1
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,
6
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
10
the other contaminant. Even though the XRD results do not show the present of any additional
11
phases, the phase purity of MIL-88B can be carefully examined by TEM.
12
morphological observation is in a good agreement with the XRD data, highlighting a control of
13
polymorphism of chromium-terephthalate MOFs by the mixed-metal method.
Note that, the
ACS Paragon Plus Environment
8
Page 9 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1 2
Figure 3. FE-SEM images of synthesized materials (a) MIL-101(Cr) and the mixed-metal MOFs
3
(b) 1, (c) 2, (d) 3, (e) 4, and (f) 5.
4
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
8
throughout the structures of octahedral MIL-101 and hexagonal rod-shaped MIL-88B. This result
9
indicates the homogeneous incorporation of both Fe(III) and Cr(III) ions into both of the
ACS Paragon Plus Environment
9
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 10 of 23
1
structures, confirming the successful formation of mixed-metal frameworks of MIL-101(Cr, Fe)
2
and MIL-88B(Cr, Fe).
3
4 5
Figure 4. STEM images and STEM/EDS elemental maps of (a) 1, (b) 2, (c) 3, (d) 4 and (e) 5.
6
Cr and Fe are shown in red and blue, respectively.
ACS Paragon Plus Environment
10
Page 11 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
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
7
depicted in Figure S5, the STEM/EDS mapping result of the particles without the large rodes
8
shows homogeneous distribution of both elemental Cr and Fe. The result suggests that the area of
9
small particles is also composed of MIL-88B(Cr/Fe) with small size ascribing to the incomplete
10
formation as well as the disintegration of the large hexagonal rods of MIL-88B(Cr/Fe).
11
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
13
revealed by SEM and TEM, 4 and 5 are mixed phases (MIL-101/MIL-88B/Fe2O3 for 4 and MIL-
14
88B/Fe2O3 for 5), thus ICP-OES is not applicable for determining their Fe and Cr compositions.
15
The results from ICP-OES of 4 and 5 in Table 1 were omitted. The relative quantities of Cr and
16
Fe elemental components in all the synthesized materials are consistent with the synthesis
17
condition in which the ratio of Fe/Cr increases when the added amount of Fe(III) salt increases.
18
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,
20
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
ACS Paragon Plus Environment
11
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 12 of 23
1
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.
5
Hence, the more Fe/Cr ratio than 15 % in the synthetic condition, the more formation of MIL-
6
88B phase.
7
ACS Paragon Plus Environment
12
Page 13 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
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
6
characteristic isotherm of a typical MIL-101 phase.23 The expanded view for the isotherms of 4
7
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.
9
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
11
morphology, the obtained materials 1, 2 and 3 provide high surface areas (above 2300 m2/g)
12
which are comparable to that of the parent MIL-101(Cr). However, surface areas of 4 and 5
13
dramatically decrease to 497 and 174 m2/g, respectively. This is due to the presence of MIL-88B
14
which typically has less specific surface area compared with MIL-101.38
ACS Paragon Plus Environment
13
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 14 of 23
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
ACS Paragon Plus Environment
14
Page 15 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
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
ACS Paragon Plus Environment
15
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 16 of 23
1
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.
12 13
ASSOCIATED CONTENT
14
Supporting Information. Detailed synthesis and characterization with the powder XRD patterns
15
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.
18
AUTHOR INFORMATION
19
Corresponding Author
20
*Dr. Sareeya Bureekaew.
21
E-mail:
[email protected].
22
Tel.: (+66)33014256.
ACS Paragon Plus Environment
16
Page 17 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
ACKNOWLEDGMENT
2
This work was supported by student grant and postdoctoral fellowship from Vidyasirimedhi
3
Institute of Science and Technology and by the Thailand Research Fund (TRF) grant number
4
RSA6080068.
5
REFERENCES
6
(1) Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux,
7
D.; Clayette, P.; Kreuz, C.; Chang, J. S.; Hwang, Y. K.; Marsaud, V.; Bories, P. N.; Cynober, L.;
8
Gil, S.; Ferey, G.; Couvreur, P.; Gref, R., Porous metal-organic framework nanoscale carriers as
9
a potential platform for drug delivery and imaging. Nat. Mater. 2010, 9, 172-178.
10
(2) Millward, A. R.; Yaghi, O. M., Metal−organic frameworks with exceptionally high capacity
11
for storage of carbon dioxide at room temperature. J. Am. Chem. Soc. 2005, 127, 17998-17999.
12
(3) Yazaydın, A. Ö.; Snurr, R. Q.; Park, T.-H.; Koh, K.; Liu, J.; LeVan, M. D.; Benin, A. I.;
13
Jakubczak, P.; Lanuza, M.; Galloway, D. B.; Low, J. J.; Willis, R. R., Screening of
14
metal−organic frameworks for carbon dioxide capture from flue gas using a combined
15
experimental and modeling approach. J. Am. Chem. Soc. 2009, 131, 18198-18199.
16
(4) Corma, A.; García, H.; Llabrés i Xamena, F. X., Engineering metal-organic frameworks for
17
heterogeneous catalysis. Chem. Rev. 2010, 110, 4606-4655.
18
(5) Tranchemontagne, D. J.; Mendoza-Cortes, J. L.; O'Keeffe, M.; Yaghi, O. M., Secondary
19
building units, nets and bonding in the chemistry of metal-organic frameworks. Chem. Soc. Rev.
20
2009, 38, 1257-1283.
21
(6) Liu, Y.; Li, J. R.; Verdegaal, W. M.; Liu, T. F.; Zhou, H. C., Isostructural metal-organic
22
frameworks assembled from functionalized diisophthalate ligands through a ligand-truncation
23
strategy. Chemistry 2013, 19, 5637-5643.
ACS Paragon Plus Environment
17
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 18 of 23
1
(7) Kholdeeva, O. A.; Skobelev, I. Y.; Ivanchikova, I. D.; Kovalenko, K. A.; Fedin, V. P.;
2
Sorokin, A. B., Hydrocarbon oxidation over Fe- and Cr-containing metal-organic frameworks
3
MIL-100 and MIL-101 a comparative study. Catal. Today 2014, 238, 54-61.
4
(8) Furukawa, H.; Go, Y. B.; Ko, N.; Park, Y. K.; Uribe-Romo, F. J.; Kim, J.; O’Keeffe, M.;
5
Yaghi, O. M., Isoreticular expansion of metal–organic frameworks with triangular and square
6
building units and the lowest calculated density for porous crystals. Inorg. Chem. 2011, 50,
7
9147-9152.
8
(9) Liu, Q.; Cong, H.; Deng, H., Deciphering the spatial arrangement of metals and correla-tion
9
to reactivity in multivariate metal-organic frameworks. J. Am. Chem. Soc. 2016, 138, 13822-
10
13825.
11
(10) Deng, H.; Doonan, C. J.; Furukawa, H.; Ferreira, R. B.; Towne, J.; Knobler, C. B.; Wang,
12
B.; Yaghi, O. M., Multiple functional groups of varying ratios in metal-organic frameworks.
13
Science 2010, 327, 846-850.
14
(11) Yang, X.; Xu, Q., Bimetallic metal–organic frameworks for gas storage and separation.
15
Cryst. Growth Des. 2017, 17, 1450-1455.
16
(12) You, B.; Jiang, N.; Sheng, M.; Drisdell, W. S.; Yano, J.; Sun, Y., Bimetal–organic
17
framework self-adjusted synthesis of support-free nonprecious electrocatalysts for efficient
18
oxygen reduction. ACS Catal. 2015, 5, 7068-7076.
19
(13) Sun, D.; Sun, F.; Deng, X.; Li, Z., Mixed-metal strategy on metal-organic frameworks
20
(MOFs) for functionalities expansion: Co substitution induces aerobic oxidation of cyclohexene
21
over inactive Ni-MOF-74. Inorg. Chem. 2015, 54, 8639-8643.
ACS Paragon Plus Environment
18
Page 19 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
(14) Chen, Y. Z.; Wang, C.; Wu, Z. Y.; Xiong, Y.; Xu, Q.; Yu, S. H.; Jiang, H. L., From
2
bimetallic metal-organic framework to porous carbon: High surface area and multicomponent
3
active dopants for excellent electrocatalysis. Adv. Mater. 2015, 27, 5010-5016.
4
(15) Brozek, C. K.; Dinca, M., Ti(3+)-, V(2+/3+)-, Cr(2+/3+)-, Mn(2+)-, and Fe(2+)-substituted
5
MOF-5 and redox reactivity in Cr- and Fe-MOF-5. J. Am. Chem. Soc. 2013, 135, 12886-12891.
6
(15) Xin, C.; Zhan, H.; Huang, X.; Li, H.; Zhao, N.; Xiao, F.; Wei, W.; Sun, Y., Effect of various
7
alkaline agents on the size and morphology of nano-sized HKUST-1 for CO2 adsorption. RSC
8
Adv. 2015, 5, 27901-27911.
9
(16) Castillo-Blas, C.; de la Peña-O’Shea, V. A.; Puente-Orench, I.; de Paz, J. R.; Sáez-Puche,
10
R.; Gutiérrez-Puebla, E.; Gándara, F.; Monge, Á., Addressed realization of multication complex
11
arrangements in metal-organic frameworks. Science Advances 2017, 3.
12
(17) Xin, C.; Zhan, H.; Huang, X.; Li, H.; Zhao, N.; Xiao, F.; Wei, W.; Sun, Y., Effect of various
13
alkaline agents on the size and morphology of nano-sized HKUST-1 for CO2 adsorption. RSC
14
Adv. 2015, 5, 27901-27911.
15
(18) Liu, D.; Liu, Y.; Dai, F.; Zhao, J.; Yang, K.; Liu, C., Size- and morphology-controllable
16
synthesis of MIL-96(Al) by hydrolysis and coordination modulation of dual aluminium source
17
and ligand systems. Dalton Trans. 2015, 44, 16421-16429.
18
(19) Qi, Y.; Luan, Y.; Yu, J.; Peng, X.; Wang, G., Nanoscaled copper metal-organic framework
19
(MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic
20
epoxidation of olefins and oxidation of benzylic and allylic alcohols. Chemistry 2015, 21, 1589-
21
1597.
ACS Paragon Plus Environment
19
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 20 of 23
1
(20) Umemura, A.; Diring, S.; Furukawa, S.; Uehara, H.; Tsuruoka, T.; Kitagawa, S.,
2
Morphology design of porous coordination polymer crystals by coordination modulation. J. Am.
3
Chem. Soc. 2011, 133, 15506-15513.
4
(21) Karmakar, A.; Paul, A.; Pombeiro, A. J. L., Recent advances on supramolecular isomerism
5
in metal organic frameworks. Cryst. Eng. Comm. 2017, 19, 4666-4695.
6
(22) Castillo-Blas, C.; Snejko, N.; de la Pena-O'Shea, V. A.; Gallardo, J.; Gutierrez-Puebla, E.;
7
Monge, M. A.; Gandara, F., Crystal phase competition by addition of a second metal cation in
8
solid solution metal-organic frameworks. Dalton Trans. 2016, 45, 4327-37.
9
(23) Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki,
10
I., A chromium terephthalate-based solid with unusually large pore volumes and surface area.
11
Science 2005, 309, 2040-2042.
12
(24) Surble, S.; Serre, C.; Mellot-Draznieks, C.; Millange, F.; Ferey, G., A new isoreticular class
13
of metal-organic-frameworks with the MIL-88 topology. Chem. Commun. 2006, 284-6.
14
(25) Neimark, A. V.; Coudert, F.-X.; Triguero, C.; Boutin, A.; Fuchs, A. H.; Beurroies, I.;
15
Denoyel, R., Structural transitions in MIL-53(Cr): View from outside and inside. Langmuir
16
2011, 27, 4734-4741.
17
(26) Carson, F.; Su, J.; Platero-Prats, A. E.; Wan, W.; Yun, Y.; Samain, L.; Zou, X., Framework
18
isomerism in vanadium metal–organic frameworks: MIL-88B(V) and MIL-101(V). Cryst.
19
Growth Des. 2013, 13, 5036-5044.
20
(27) Taylor-Pashow, K. M. L.; Rocca, J. D.; Xie, Z.; Tran, S.; Lin, W., Postsynthetic
21
modifications of iron-carboxylate nanoscale metal−organic frameworks for imaging and drug
22
delivery. J. Am. Chem. Soc. 2009, 131, 14261-14263.
ACS Paragon Plus Environment
20
Page 21 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
1
(28) Serra-Crespo, P.; Ramos-Fernandez, E. V.; Gascon, J.; Kapteijn, F., Synthesis and
2
characterization of an amino functionalized MIL-101(Al): Separation and catalytic properties.
3
Chem. Matter. 2011, 23, 2565-2572.
4
(29) Mason, J. A.; Darago, L. E.; Lukens, W. W., Jr.; Long, J. R., Synthesis and O2 reactivity of
5
a titanium(III) metal-organic framework. Inorg. Chem. 2015, 54, 10096-10104.
6
(30) Maksimchuk, N. V.; Zalomaeva, O. V.; Skobelev, I. Y.; Kovalenko, K. A.; Fedin, V. P.;
7
Kholdeeva, O. A., Metal-organic frameworks of the MIL-101 family as heterogeneous single-
8
site catalysts. Proceedings of the Royal Society A: Mathematical, Physical and Engineering
9
Sciences 2012, 468, 2017-2034.
10
(31) Shih, Y.-H.; Lo, S.-H.; Yang, N.-S.; Singco, B.; Cheng, Y.-J.; Wu, C.-Y.; Chang, I. H.;
11
Huang, H.-Y.; Lin, C.-H., Trypsin-immobilized metal-organic framework as a biocatalyst in
12
proteomics analysis. ChemPlusChem 2012, 77, 982-986.
13
(32) Bromberg, L.; Diao, Y.; Wu, H.; Speakman, S. A.; Hatton, T. A., Chromium(III)
14
terephthalate metal organic framework (mil-101): HF-free synthesis, structure, polyoxometalate
15
composites, and catalytic properties. Chem. Mater. 2012, 24, 1664-1675.
16
(33) Leng, K.; Sun, Y.; Li, X.; Sun, S.; Xu, W., Rapid synthesis of metal–organic frameworks
17
mil-101(Cr) without the addition of solvent and hydrofluoric acid. Cryst. Growth Des. 2016, 16,
18
1168-1171.
19
(34) Liang, Z.; Marshall, M.; Ng, C. H.; Chaffee, A. L., Comparison of conventional and HF-
20
free-synthesized MIL-101 for CO2 adsorption separation and their water stabilities. Energy &
21
Fuels 2013, 27, 7612-7618.
22
(35) Cai, X.; Lin, J.; Pang, M., Facile synthesis of highly uniform Fe-MIL-88B particles. Cryst.
23
Growth Des. 2016, 16, 3565-3568.
ACS Paragon Plus Environment
21
Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 22 of 23
1
(36) McKinlay, A. C.; Eubank, J. F.; Wuttke, S.; Xiao, B.; Wheatley, P. S.; Bazin, P.; Lavalley,
2
J. C.; Daturi, M.; Vimont, A.; De Weireld, G.; Horcajada, P.; Serre, C.; Morris, R. E., Nitric
3
oxide adsorption and delivery in flexible MIL-88(Fe) metal–organic frameworks. Chem. Mater.
4
2013, 25, 1592-1599.
5
(37) Horcajada, P.; Salles, F.; Wuttke, S.; Devic, T.; Heurtaux, D.; Maurin, G.; Vimont, A.;
6
Daturi, M.; David, O.; Magnier, E.; Stock, N.; Filinchuk, Y.; Popov, D.; Riekel, C.; Ferey, G.;
7
Serre, C., How linker's modification controls swelling properties of highly flexible iron(III)
8
dicarboxylates MIL-88. J. Am. Chem. Soc. 2011, 133, 17839-17847.
9
(38) Wei, Y. S.; Zhang, M.; Liao, P. Q.; Lin, R. B.; Li, T. Y.; Shao, G.; Zhang, J. P.; Chen, X.
10
M., Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework.
11
Nat. Commun. 2015, 6, 8348.
12 13
ACS Paragon Plus Environment
22
Page 23 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Crystal Growth & Design
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
ACS Paragon Plus Environment
23