A Double-Walled Thorium-Based Metal-Organic Framework as a Promising Dual-Function Absorbent for Efficiently Capturing Iodine and Dyes

Article abstract of DOI:10.1021/acs.cgd.9b00671

We prepared a rare thorium metal-organic framework (MOF) (Th-TATAB) with a double-walled tetrahedral cage structure and giant unit cell volume of 43 ?513 ?³, which is the largest of all reported thorium-based MOFs to our knowledge. The unique structural character allows the thorium-based MOF to exhibit exceptional adsorption properties toward I₂ and dyes with different charges. The experimental results show that in cyclohexane solution the absorption ability of Th-TATAB toward I₂ can reach about 750 mg/g, and especially the removal efficiency in cyclohexane solution (0.01 mol/L) can reach 90% in 3 h, which far exceeded that of reported [Zn₂(tptc)-(apy)_2-x(H₂O)_x]·H₂O (80%, 48 h) and MIL-101-NH₂ (90%, 30 h). Furthermore, the simultaneous removal of molecules with different charges is very challenging, while Th-TATAB displays excellent adsorption properties for anionic, neutral, and cationic dyes individually and simultaneously from aqueous solution. The exploration of the adsorption performance of MOF Th-TATAB for iodine in cyclohexane solution and dye contaminants in aqueous solution is of great significance for environmental aspects, which provides a new strategy for opening up the potential applications of thorium-based MOFs and understanding actinides chemistry.

Full text of DOI:10.1021/acs.cgd.9b00671

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Article
A Double-walled Thorium-based Metal-Organic
Framework (MOF) as a Promising Dual Functional
Absorbent for Efficiently Capturing Iodine and Dyes
Na Zhang, Li-Xian Sun, Yong-Heng Xing, and Feng-Ying Bai
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00671 • Publication Date (Web): 13 Aug 2019
Downloaded from pubs.acs.org on August 13, 2019
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A Double-walled Thorium-based Metal-Organic
Framework (MOF) as a Promising Dual Functional
Absorbent for Efficiently Capturing Iodine and Dyes
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Na Zhang,† Li-Xian Sun§,Yong-Heng Xing,*† and Feng-Ying Bai*†
† College of Chemistry and Chemical Engineering, Liaoning Normal University, Huanghe Road
850#, Dalian 116029, P. R. China.
§ Guangxi Key Laboratory of Information Materials, Guilin University of Electronic
Technology, Guilin 541004, P. R. China.
ABSTRACT: We prepared a rare Th-MOF (Th-TATAB) with a double-walled tetrahedral cage
structure and giant unit cell volume 43513 Å3 which is the largest of all reported thorium-based
MOFs to our knowledge. The unique structure characters make the thorium-based MOF exhibits
exceptionally adsorption properties toward I2 and dyes with different charges. The experimental
results show that in cyclohexane solution the absorption ability of Th-TATAB toward I2 can
reach about 750 mg/g, especially the removal efficiency in cyclohexane solution(0.01 mol/L)
can reach 90% in 3 hours, which far exceeded that of reported [Zn2(tptc)-(apy)2-x(H2O)x]H2O
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(80%, 48 h) and MIL-101-NH2 (90%, 30 h). Furthermore, the simultaneous removal of
molecules with different charges is very challenging, while Th-TATAB displays excellent
adsorption properties for anions, neutral and cations dyes individually and simultaneously from
aqueous solution. The exploration of the adsorption performance of MOF Th-TATAB for iodine
in cyclohexane solution and dye contaminants in aqueous solution is of great significance in
environmental aspect, which provided a new strategic idea for opening up the potential
applications of thorium-based MOF and understanding actinides chemistry.
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INTRODUCTION
Nowadays, metal-organic frameworks (MOFs) have attracted much interest due to its extensive
application in many realms such as adsorption,1 separation,2 sensing,3 proton conduction4 and
heterogeneous catalysis.5 Among them, the application of MOF as a functional adsorbent to
effectively capture various analysts such as drugs, explosives, dyes contaminants and radioactive
wastes, has a broad prospect.6-7 MOFs based thorium stand for a small part of the MOF family,
which are less developed and explored comparing to MOFs constructed by transition and
lanthanide. Compared with other high valent metal cations (such as zirconium (IV) or cerium
(IV), tetravalent acts such as thorium (IV) have wider coordination numbers and exhibit more
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various coordination environments.
Since O’Hare et al. firstly constructed Th-MOF
[(Th2F5)(NC7H5O4)2(H2O)][NO3] using Th(NO3)4·6H2O and pyridinedicarboxylate in 2003,10
researchers have made more efforts to develop Th-MOFs with rich structure to deeply
understand thorium chemistry for nuclear science, and the progress made in this field is very
10-18
encouraging.
Knope et al. prepared two isomorphous compounds Th6O4(OH)4(H2O)6(4-
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hydroxybenzoate)12]·nH2O and [U6O4(OH)4(H2O)6(4-hydroxybenzoate)12]·nH2O and studied the
effect of organic skeleton on the solution and solid-state structural chemistry of thorium-uranium
complexes.18 Christopher et al. synthesized a novel Th-MOF Th[4,4′-oxybis(benzoic) aci]2,
which exhibited excellent chemical and thermal stability.16
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Iodine, as one of the volatile radionuclides, is an important issue in nuclear waste
management. Efficiently capturing iodine is still very challenging due to high fluidity and low
adsorption capacity of its species. Recently, porous MOFs as a new kind of adsorbents, have
been utilized to capture I2, showing excellent adsorption capacity.19-20 Thallapally et al.
synthesized two microporous MOFs SBMOF-1 [Ca(4,4′-sulfonyldibenzoate)] and SBMOF-2
[Ca(1,2,4,5-tetrakis(4-carboxyphenyl)-benzene)] according to the literature and studied their
adsorption properties for iodine under humidity conditions.20 A feasible method for constructing
MOF with good affinity for I2 is to introduce conjugated π-electron organic linker, that can
generate stable charge-transfer (CT) complexes or halogen bonds with I2, therefore enhancing
the adsorption capacity for iodine adsorption.21 Moreover, some conjugated triazine-based
frameworks (CTFs), also called 1,3,5-triazine-based conjugated microporous polymers
(TCMPs), have also been developed for I2 capture.22 Since the existence of triazine heterocyclics
with rich nitrogen atoms in CMPs systems dramatically enhance their I2 binding affinity and
heighten the interaction between the adsorbates and adsorbents, TCMPs possess excellent iodine
capture capacities at ambient pressure.6, 22-24 So, it is significant to think over that the 1,3,5-
triazine heterocycle containing polycarboxylate groups with multiple conformations and bonding
modes in the selection or design of organic ligands. For one thing, it is an extraordinary
aromatic component that can lead to p–p stacking and anion–p interactions.23-24 For another, the
triazine ring contains three nitrogen atoms, which not only coordinate with metal ions, but also
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form a variable network structure.25-27 In the large family of triazine polycarboxylate acids,
trigonal tricarboxylate ligand H3TATAB containing amino functional group is a typical
representative. Compared with the other triangular tricarboxylic acid linkers, such as BTC, BTB
and TATB, its structure is more extended. (Scheme 1). Many novel high-porosity MOFs have
been formed by assembling TATAB ligands with transition metals and rare earth ions, which
exhibited excellent performance in areas such as luminescent sensing and adsorption.28-30 In
addition, organic dye contaminants in water are also a serious problem because they are usually
stable, toxic and potentially carcinogenic, even severely threatening to ecological environment.
Hence, the efficient adsorption removal of dye contaminants from water is crucial. Due to the
diverse topologies, high porosity, adjustable aperture, and unique host-guest interactions, MOFs
has been extensively investigated for the efficient removal of organic dye pollutants from
wastewater.25, 31-34 Especially many MOFs show excellent performance in selective adsorbing
dyes.34-37 For example, Hong et al. constructed an anionic uranium-based MOF
[(CH3)2NH2]4[(UO2)4(TCPE)3](solvent)x, showing excellent adsorption performance for cationic
dyes Ethyl Violet, Rhodamine B and Janus Green B.25 Liu et al. presented a 1D rare earth
compound {[(CH3)2NH2] [(H2abtc)2Ho(H2O)]}n, which showed a high removal efficiency of
positively charged dyes methylene blue.35 Xing et al. assembled a unique two-dimensional
uranyl complex [(CH3)2NH2][UO2(TATAB)]·2DMF·4H2O by using triazine tricarboxylic acid
ligand, which featured 2D graphene-like topological structure and displayed selective adsorption
ability to cationic dyes Safranine T and methylene blue.26 However, simultaneous removal of
anionic and cationic dyes/anionic, neutral and cationic dyes from water solutions is still a
challenge. The development of the dual functional absorbent for iodine and dye is very
promising and significant. Herein, we adopted high-valence Th(IV) cation and conjugated π-
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electron ligand H3TATAB to successfully assemble a novel dual-function MOF Th-TATAB and
firstly explored its sorption properties for I2 and dye molecules.
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Scheme 1. Structure of Some Trigonal Tricarboxylic Ligands.
EXPERIMENTAL SECTION
Caution! Thorium is a chemically toxic and radioactive element, standard precautionary
measures to handle radioactive substances ought to be followed.
Synthesis of Ligand 4,4',4"-s-triazine-1,3,5-triyltri-p-aminobenzoate (H3TATAB). Ligand
H3TATAB was synthesized according to the literature and slightly modified.28,38 4-aminobenzoic
acid (4.5 g, 33 mmol), NaOH (1.5 g, 37.5 mmol), and NaHCO3 (2.25 g, 27.5 mmol) were placed
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in 50 mL of deionized water. At 0 ºC, stir the mixed solution for 30 min. Cyanuric chloride (1.5
g, 8.25 mmol) was added to 1,4-dioxane (15 mL) and stirred until dissolved, then dripped into
the above mixed solution. The mixed solution was then refluxed for 24 h in an oil bath at 115 ºC.
The obtained solution was acidified with 20% hydrochloric acid to pH=3. The light yellow
product was obtained by filtration, washed with distilled water until neutral, and dried to gain
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ligand H3TATAB (4.5 g, yield: 80%). HNMR (d6-DMSO, 400 MHz): δ=7.88 (d, 6H), 7.97 (d,
6H), 9.84 (s, 3H), 12.64 (s, br, 3H). The 1H-NMR spectra of the ligand H3TATAB is presented
in Figure S1.
Synthesis of MOF Th-TATAB, Th6O4(OH)4(H2O)6(TATAB)2(HCO2)6. A mixture of
Th(NO3)4·6H2O (0.05 mmol), H3TATAB (0.05 mmol)m, DMF (4 mL) and H2O (1mL) was
stirred at room temperature for 20 min. The mixed solution was adjusted to pH=3 with nitric acid
(4 mol/L), then transferred to 20 mL Teflon-lined stainless steel autoclave and heated for 2 days
at 160 ºC. After cooling, filtering and washing with DMF, colorless octahedral crystals are
obtained, yield 57 % (14 mg, based on metal). The formula of the crystal is
Th6O4(OH)4(H2O)6(TATAB)2(HCO2)6, which was confirmed by X-ray single crystal diffraction
analysis, Elemental analysis (% calc/found: C 22.63/23.04, H 1.68/1.77, N 5.87/5.99), and TGA
(before 400 ºC weight loss of 30 wt% ).
Single Crystal X-ray diffraction Determination. Single crystals with appropriate sizes of
MOF Th-TATAB were mounted on glass fibers to collect X-ray diffraction data. The
determination of crystal structure were performed on a Bruker AXS SMART APEX II CCD
diffractometer with graphite monochromatized Mo Kα radiation (λ = 0.71073 Å) at room
temperature. A semiempirical absorption correction was applied by the program SADABS.39
Single crystal structure was solved by direct methods and refined by full-matrix least squares on
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F2 using the SHELX-97 program.40-41 All non-hydrogen atoms were refined with anisotropic
displacement parameters. The crystallographic data are summarized in Table 1. The selected
bond distances (Å) are given in Table 2.
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Table 1. The crystallographic data for Th-TATAB
Compound
Th-TATAB
Molecular formula
C54H48N12O38Th6
formula weight
2865.28
T (K)
293
Crystal system
cubic
Space group
Fd-3
a (Å)
35.1727(7)
b (Å)
35.1727(7)
c (Å)
35.1727(7)
α (°)
90
β (°)
90
γ (°)
90
V (Å3)
43512.8(15)
Z
16
D, g/cm32
1.750
F(000)
20800.0
Goodness of fit on F2
Final R indices [I > 2 σ(I)]
1.232
R1=0.0925 , wR2=0.1612
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Final R indices (all data)
R1=0.1538 , wR2=0.1828
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Table 2. Selected bond lengths (Å) for Th-TATAB
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Selected bond lengths (Å)
Th1-O1
Th1-O3
Th1-O5
Th1-O7W
2.459(12)
2.45(2)
Th1-O2
Th1-O4
Th1-O6
2.429(11)
2.381(8)
2.566(18)
2.806(16)
2.512(18)
Capture of iodine experiments in cyclohexane solution. At room temperature a few samples
100 mg of Th-TATAB were respectively added to cyclohexane solution dissolved with iodine
(0.01, 0.02, 0.03 and 0.04 mol/L). Ultraviolet-visible absorption spectroscopy was applied to
monitor the kinetics of iodine adsorption by MOF.
Release of iodine experiments in ethanol solution At room temperature, a few samples 20 mg
of Th-TATAB were put into iodine-dissolved cyclohexane solution (100 mgL-1, 5 mL) for 24
hours to prepare the iodine-loaded sample. Then 20 mg of composite I2@Th-TATAB were
soaked in ethanol (10 mL). The residual concentration of iodine solution was measured by
ultraviolet-visible spectrometer at room temperature.
Adsorption experiments in a single dye solution 5 mg of Th-TATAB were added into 5 mL of
the water solution containing methyl orange, Eosin Y, alizarin , rhodamine B and methylene blue
at room temperature, the initial concentration of which is 10 mgL-1. Supernatant solutions were
taken from the suspensions with a syringe as samples for analyses after 0, 1, 2, 3, 4, 6, 8 10 and
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23 h. Monitor the residual concentration of the dye-containing solution with ultraviolet-visible
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spectrophotometer at the absorbance (λmax) of each dye supernatant.
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Effect of initial concentrations on adsorptive removal of methyl orange. 5 mg of Th-TATAB
were immersed into 5 ml of aqueous solution containing methyl orange at different initial
concentrations (10, 20, 30 mgL-1). The maximum absorbance change of methyl orange dye
solution at different initial concentrations was respectively recorded by an ultraviolet-visible
spectrophotometer at room temperature. Subsequently, 5 mg of Th-MOF was separately soaked
in solution containing methyl orange (40, 60, 80 and 100 mgL-1). After a week, the residual
concentration of the above solution was respectively recorded by an ultraviolet-visible
spectrophotometer to obtain the dye removal efficiency and equilibrium adsorption amount. The
formula of the dye removal efficiency is expressed as follows:
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% Removal = [(C0 − Ct)/C0] × 100
where C0 is the initial concentration of the dyes, and Ct is the concentration of dyes at any
specified time.
RESULTS AND DISCUSSION
Crystal Structures. Solvothermal reaction of trigonal ligand H3TATAB and thorium nitrate in
the presence of DMF, H2O and HNO3 at 160 °C 48 h yielded colorless octahedral crystals of Th-
TATAB (Figure S2). Structural analysis shows that Th-TATAB crystalizes in the cubic system
with the space group Fd-3. It was formulated as Th6O4(OH)4(H2O)6(TATAB)2(HCO2)6 by the
characterization of IR, PXRD, TG, single-crystal X-ray diffraction, and elemental analysis. The
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crystal structure of MOF Th-TATAB is based upon inorganic building unit Th6O4(OH)4(CO2)12
(Figure 1b) which is similar to Zr6O4(OH)4(CO2)12 brick from UiO-66. Unlike UiO-66 with
linear linker BDC, this thorium-based MOF Th-TATAB is formed with the trigonal ligand
TATAB. The inorganic building brick is comprised of the inner Th6O4(OH)4 core (Figure 1a), in
which six thorium atoms form a Th6-octahedron and are located at the vertices of the octahedron.
All triangular faces of the octahedron are alternately capped by the µ3-O and µ3-OH which share
three thorium centers. The edges of octahedron are bridged by carboxylates (-CO2) from the
TATAB ligand and formic acid which is derived from DMF decomposition. Each thorium center
is coordinated by three types of oxygen atoms, defining a monocapped square antiprismatic
polyhedron. Four of them originate from carboxyl oxygen atoms of trigonal ligand TATAB and
formic acid; Four other oxygen atoms are supplied the groups of by µ3-O and µ3-OH; And the
terminal oxygen atom corresponds to the coordinated water molecule. The distances of Th-O
bond for Th-μ3O(H), Th-OTATAB, Th-OHCOO and Th-Owater of 2.3787, 2.4409, 2.5341, and
2.7967Å respectively, are typical in nine-coordinated complexes containing thorium(IV). The
presence of µ3-O(H) groups meet the requirements of charge balance, which has been previously
reported in other complexes with hexanuclear Th-cluster structures.12, 42 Average bond value for
Th-μ3(O,OH) (2.3787Å) is comparable with Th-μ3(O,OH) bond value of 2.391Å for the
previously reported compound Th6(OH)4O4(H2O)6(OAc)12·nH2O.42 Although Th-Owater bond
value of 2.7967Å is relatively long, it is comparable to that of several thorium(IV) complexes
reported in the literature.11, 13 Each trigonal tricarboxylate ligand are linked three inorganic brick
(Figure 1c), and each inorganic building brick is connect with six trigonal tricarboxylate ligand
TATAB(Figure 1d). The inorganic building brick are linked each other through the trigonal
tricarboxylate linker TATAB to form truncated tetrahedral cavities with a size of 17 Å（Figure
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1e and 1f ). Interestingly, Th-TATAB is a very rare double-walled MOF, the double-walled
tetrahedron cage of which is formed by the interlacing of two triangular ligands connected with
inorganic brick.
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Figure 1. Structural features of Th-TATAB: (a) The inner core Th6O4(OH)4 of Th-
TATAB; (b) The inorganic building brick; (c) Ligands TATAB connecting three
inorganic building brick; (d) The inorganic building brick linked six ligands TATAB. (e)
The truncated tetrahedral cage in Th-TATAB. (f) Graphical representation illustrating the
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interconnected cages with 17Å diameter. For clarity hydrogens atoms and solvent
molecules are omitted. Atom color codes: thorium, yellow; oxygen, pink; carbon, teal;
nitrogen, blue.
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Capture and Release of Iodine Iodine uptake of Th-TATAB was investigated in cyclohexane
solution. We first explored the effect of different initial concentrations on iodine removal
efficiency. (Figure S13). At room temperature a few samples 100 mg of Th-TATAB were
separately soaked in 5 mL cyclohexane solution dissolving iodine (0.01, 0.02, 0.03 and 0.04
mol/L). Iodine adsorption process was monitored by UV-visible spectroscopy. After 24 h, the
removal efficiencies of 99.9%, 99.1%, 97.2% and 93.1% were achieved respectively for iodine
cyclohexane solution of 0.01, 0.02, 0.03 and 0.04 mol/L, respectively (Figure 2a). The MOF
sample was immersed in a cyclohexane solution dissolving iodine at room temperature. After
about 24 hours, the dark purple solutions of iodine gradually faded to pale (Figure 2a insets),
which demonstrated that the I2 was encapsulated in the skeleton of Th-TATAB so that in
solution a system loaded with iodine is successfully produced.43 Especially, when I2 solution is
0.01 mol/L, the removal efficiency of iodine by Th-TATAB can reach 90% in 3 hours, which far
exceeded that of reported [Zn2(tptc)-(apy)2-x(H2O)x]H2O (80%, 48h) and MIL-101-NH2 (90%,
30h).44-45 As shown in Figure 2d, after 72 hours, the adsorption capacity of Th-TATAB for
iodine reached approximately 700 mg/g and 750 mg/g when 10 mL and 15 mL of iodine solution
(0.04 mol/L) were added, respectively, while the iodine-loaded crystals turned black (Figure 2d
inset). In order to study the influence of different contact time on iodine adsorption capacity, an
in-depth analysis can be performed by fitting pseudo-second-order model (Figure 2b).
Obviously, the kinetic process of iodine adsorption by MOF Th-TATAB is well described by
pseudo-second-order kinetic model. The affinity and strong adsorption capacity of MOF Th-
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TATAB for iodine can be put down to the plentiful phenyl rings, high porosity, and the structural
features of the π-electron walls constructed by TATAB, which can be explicated in the following
aspects. First, iodine is adsorbed inside the pores of MOF Th-TATAB through I−I···N bonds
and I−I···π halogen bonds.46 Moreover, the underlying intermolecular interactions between
iodine molecule and π-electron double-walls are crucial, because the single path for iodine
molecules is allowed to entry and be restricted in well-regulated narrow limits in the
nanochannels, resulting in n→σ*charge transfer (CT).47
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Figure 2. (a) The removal efficiency of MOF Th-TATAB for iodine when the initial
concentration of iodine in cyclohexane solution is 0.01, 0.02, 0.03 and 0.04 mol/L.; The insets
show the color change of iodine solution during iodine enrichment; (b) Plots of pseudo-second-
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order kinetics; (c) The adsorption capacity of MOF Th-TATAB for iodine when the initial
concentration of iodine in cyclohexane solution is 0.01, 0.02, 0.03 and 0.04 mol/L; (d) The
adsorption capacity of iodine when 10 mL and 15 mL iodine solution (0.04mol/L) was added
respectively.
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In the meantime, the release of iodine from iodine-loaded samples I2@Th-TATAB was
determined by UV-vis spectra (Figure 3 and S1). The release rate was rapid during the first day,
and no significant change was observed after 3 days, indicating that the release reached
equilibrium (Figure 3b ). After 7 days, about 85.64% of the initial I2 had been released from
I2@Th-TATAB, showing the adsorption process of MOF Th-TATAB toward I2 is reversible
(Figure 3b). We deem that host-guest interaction plays a key role in such release behavior.48
Strong π-electron-iodine and host-guest interactions promote I2 uptake, whereas it would also
undermine the desorption of I2 from I2@Th-TATAB, leading to the incomplete delivery of
iodine from I2@Th-TATAB composite system.49 Because of the skeleton collapse of the sample
after methanol activation (Figure S3b), the unactivated sample was used for the measurement of
nitrogen adsorption. It is possible that due to the guest molecule in the MOF pore could not be
removed effectively, the ideal result of nitrogen adsorption measurement was not obtained,
although the void space predicted by the PLATON calculation is 42.1%.
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Figure 3. Kinetic plot of iodine delivery from the composite I2@Th-TATAB measured by UV-
vis absorption spectra in ethanol solution.
Dye adsorption. Based on the pore size (17Å) of the tetrahedral cavity of MOF Th-TATAB,
five dyes with suitable dimensions for pore permeation (molecular size < 1.7 nm): negatively
charged methyl orange {4-[4-(Dimethylamino)phenylazo]benzenesulfonic acid sodium salt},
Eosin Y [disodium2-(2,4,5,7-tetrabromo-6-oxido-3-oxoxanthen-9-yl)benzoate]; electrically
neutral alizarin [1,2-Dihydroxyanthracene-9,10-dione]; and positively charged rhodamine B [9-
(2-carboxyphenyl)-3,6-bis(diethylamino)xanthylium chloride] and methylene blue [3,7-
Bis(dimethylamino)-5-phenothiazinium Chloride] (Figure S14) were chosen to evaluate the
adsorption ability of Th-TATAB in a dye-containing aqueous solution. The complex all exhibits
adsorption behavior to anionic, neutral and cationic dye molecules to some extent (Figure 4), in
which the removal efficiency of anionic dye MO (96%) is the highest. In the same charged dye
solution, the Th-MOF has higher adsorption efficiency for linear dye MO (96%) than the triangle
dye molecule Eosin Y (44%); the uptakes toward the linear MB (34%) were more efficient than
triangle dye molecule rhodamine B (20%). This observed result indicates that the anionic, neutral
and cationic dye molecules with appropriate size to accommodate nanotube channels of the Th-
TATAB frame can be adsorbed and entered into the pores of MOF. The adsorptive behavior of
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Th-TATAB on dyes does not only exhibit size and shape dependence, but also charge
dependence to a certain extent. In the same charged dye solution, the Th-MOF has higher
adsorption efficiency for linear dye molecule methyl orange than the triangle dye molecule Eosin
Y; the uptakes toward the linear methylene blue were more efficient than triangle dye molecule
rhodamine B. We believed that the difference in adsorption between dye molecules with the
same charge may be due to shape effects. In order to further confirm our inference, another linear
anionic dye Orange II [4-(2-Hydroxy-1-naphthylazo)benzenesulfonic acid sodium salt] was
selected for adsorption experiments. The experimental results show that the Th-MOF also
exhibits a high adsorption capacity for linear anionic dye molecule Orange II (Figure 4c), which
is comparable to that for linear dye molecule MO, and significantly higher than that for
triangular dye molecule Eosin Y. Therefore, the experimental results are consistent with
expectations. Compared with the triangular dye molecules, linear dye molecules are more
acceptable to access to the pore of the MOF; Whereas the difference in adsorption between dye
linear dye molecules MO, alizarin and MB may be due to charge dependence.
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Figure 4. UV-visible absorption spectrum of the single dye solution. (a) MO, (b) Eosin Y, (c)
alizarin, (d) MB and (e) rhodamine B. The insets show the change in color of the dye solution
after adsorption.
Considering the excellent adsorption performance of Th-TATAB for MO, we further
explored the influence of different initial concentration on the dye removal by Th-
TATAB (Figure S15). The removal efficiency of methyl orange solution at three different
initial concentrations (10, 20, and 30 mgL-1) can achieved 96%, 98% and 97%
respectively after 23 hours;the adsorption amount can reached 9.79, 19.97 and 29.99
mg/g, respectively after 23 hours (Figure 5b). Moreover, in order to further study the
influence of different contact time on adsorptive behavior of Th-TATAB toward MO,
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linear fit was conducted using the pseudo-second-order kinetic model (Figure 5a and
Table 3). Obviously, for methyl orange dye solution of different initial concentrations, the
pseudo-second-order kinetic equation has a good fitting degree, which can well describe
the kinetic process of Th-TATAB adsorbing methyl orange dyes.
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Figure 5. (a) Linear regressions of MO; (b) The adsorption ability of MOF Th-TATAB for MO
when the initial concentration of the solution is 10, 20 and 30 mgL-1.
Table 3. Adsorption kinetic parameters of MO on Th-TATAB
pseudo secondary-order kinetics
Dye
MO
C0 (mg L-1)
k2 (g mg min-1)
R2
qe (mg g-1)
10
20
30
9.724×10-2
4.643×10-2
2.919×10-2
0.9978
0.9981
0.9982
9.79
19.97
29.99
Subsequently, the adsorption capacity of the Th-MOF was monitored when the
initial concentration of methyl orange dye solution was 40, 60, 80 and 100 mgL-1
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respectively (Figure S17 and 6). It can be seen that the initial concentration of the solution
is a key factor affecting the amount of adsorption. As the initial concentration increases,
the equilibrium adsorption amount gradually increases, reaching a maximum value of
99.53 mg/g at the initial concentration of 100 mgL-1.
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Fig 6. The influence of different initial concentration on the adsorption capacity of Th-MOF
toward MO.
Many MOFs show selective adsorption behavior for cationic or anionic dyes, and there are
many reports about this aspect,32, 50 while the simultaneous removal of molecules with different
charges is still very challenging.51 In this paper, the adsorptive behavior of Th-MOF was further
examined in binary/ternary mixed solution ( MO + MB, MO + Rhb, MO + MB + alizarin and
MO + Rhb + alizarin ) containing dyes with different charges (Figure 7). Interestingly, the
removal of both the linear and triangular cationic dye molecules by Th-MOF in the mixed dye
solution is enhanced compared to the single dye solution, especially cationic dyes (Figure 8). We
deem that due to the large aperture characteristics of MOF Th-TATAB, dye molecules with
different charges co-existing in solution may undergo a co-adsorption process.51 It is because of
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this co-adsorption process that MOF Th-TATAB exhibits mutual enhancement of adsorption
capacity toward anions, neutral and cations dye molecules in the mixed solution.51 From the
above adsorption study, it can be concluded that Th-TATAB might be the better candidate for
simultaneous removal of anionic, neutral and cationic dyes.
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Fig 7. UV-visible absorption spectrum of the solution containing mixed dyes. (a) MO and MB;
(b) MO and Rhb; (c) MO, MB and alizarin; (d) MO, Rhb and alizarin. The insets show the
change in color of the mixed dye solution after adsorption.
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Fig 8. (a) Removal efficiency of MB in mixed solution (MB + MO + alizarin and MB + MO)
and single dye solution; (b) Removal efficiency of RhB in mixed solution (Rhb +MO and Rhb +
MO + alizarin ) single dye solution.
It is necessary to pointed out that, a large number of dye release experiments have been
carried out to study the desorption behavior of dyes, but no desorption behavior has been
observed. We infer that, similar to the incomplete desorption of iodine, the unique host-guest
interaction may facilitate the adsorption of the dye, but weaken dye desorption from dye-loaded
samples. In particular, the double-layered π-electron walls formed by TATAB ligands may also
hinder the dye release behavior.
In summary, a novel thorium-based MOF Th-TATAB with unique double-walled
tetrahedral cage structure was designed and synthesized by self-assembly method, and its
adsorption performance towards iodine and dye was investigated. The Th-MOF displays
excellent adsorption properties towards iodine in cyclohexane solution. Moreover, anionic,
neutral and cationic dye molecules can be adsorbed by this MOF from aqueous solution to some
extent, in which linear dye molecules are better adsorbed. In particular, anions, neutral and
cations dyes can be removed simultaneously in the mixed solution, and the adsorption capacity is
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mutually enhanced. The experimental results demonstrate that MOF Th-TATAB is a good
potential candidate for adsorption of iodine and dye pollutants, which provides a new strategic
idea for exploiting the physical and chemical properties and practical application of Th-MOF. In
addition, it is very meaningful to explore the adsorption performance of MOF on iodine under
humidity conditions, so we intend to conduct this research in the next step.
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ASSOCIATED CONTENT
Supporting Information.
This material is available free of charge via the Internet at http://pubs.acs.org.
Experimental and characterization data (PDF)
Supporting Figures S1-S17 (PDF)
Crystallographic data (CCDC No.1871747) (CIF)
AUTHOR INFORMATION
Corresponding Author
*Prof. Yong-Heng Xing. E-mail: xingyongheng2000@163.com
*Prof. Feng-Ying Bai. E-mail: baifengying2003@163.com.
ORCID
Yong-Heng Xing: 0000-0002-7550-2262
Feng-Ying Bai: 0000-0001-6202-054X
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Author Contributions
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†These authors contributed equally.
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ACKNOWLEDGMENT
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This work was supported by the grants of the National Natural Science Foundation of China (No.
21571091) and Commonweal Research Foundation of Liaoning province in China (No.
20170055) for financial assistance.
ABBREVIATIONS
Th-TATAB, Th6O4(OH)4(H2O)6(TATAB)2(HCO2)6; MB, methylene blue ; MO,methyl orange;
Rhb, rhodamine B.
REFERENCES
1.
Farha, O. K.; Yazaydin, A. O.; Eryazici, I.; Malliakas, C. D.; Hauser, B. G.; Kanatzidis,
M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T., De novo synthesis of a metal-organic framework
material featuring ultrahigh surface area and gas storage capacities. Nat. Chem. 2010, 2, 944-
948.
2.
Liu, K.; Ma, D.; Li, B.; Li, Y.; Yao, K.; Zhang, Z.; Han, Y.; Shi, Z., High storage
capacity and separation selectivity for C2 hydrocarbons over methane in the metal–organic
framework Cu–TDPAT. J. Mater. Chem. A 2014, 2, 15823-15828.
3.
Metal-organic framework materials as chemical sensors. Chem. Rev. 2012, 112, 1105-1125.
4. Sadakiyo, M.; Yamada, T.; Honda, K.; Matsui, H.; Kitagawa, H., Control of crystalline
Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T.,
proton-conducting pathways by water-induced transformations of hydrogen-bonding networks in
a metal-organic framework. J. Am. Chem. Soc. 2014, 136, 7701-7707.
5.
organic framework materials as catalysts. Chem. Soc. Rev. 2009, 38, 1450-1459.
6. Sanda, S.; Parshamoni, S.; Biswas, S.; Konar, S., Highly selective detection of palladium
Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T., Metal-
and picric acid by a luminescent MOF: a dual functional fluorescent sensor. Chem. Commun.
2015, 51, 6576-6579.
7.
Zhang, Q.; Yu, J.; Cai, J.; Song, R.; Cui, Y.; Yang, Y.; Chen, B.; Qian, G., A porous
metal-organic framework with -COOH groups for highly efficient pollutant removal. Chem.
Commun. 2014, 50, 14455-14458.
ACS Paragon Plus Environment
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Crystal Growth & Design
Page 24 of 28
1
2
3
4
5
6
7
8
9
8.
Tutson, C. D.; Gorden, A. E., Thorium coordination: A comprehensive review based on
coordination number. Coord. Chem. Rev. 2017, 333, 27-43.
9. Grenthe, I.; Drozdzynski, J.; Fujino, T.; Buck, E.; Albrecht-Schmitt, T.; Wolf, S., In The
Chemistry of the Actinide and Transactinide Elements, ; Morss, LR; Edelstein, NM; Fuger, J.,
Eds. Springer: Dordrecht, The Netherlands: 2006.
10.
organic open framework. J. Am. Chem. Soc. 2003, 125, 12688-12689.
11.
Kim, J. Y.; Norquist, A. J.; O'Hare, D., [(Th2F5)(NC7H5O4)2(H2O)][NO3]: an actinide-
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
Wang, Y.; Liu, W.; Bai, Z.; Zheng, T.; Silver, M. A.; Li, Y.; Wang, Y.; Wang, X.; Diwu,
J.; Chai, Z.; Wang, S., Employing an Unsaturated Th4+ Site in a Porous Thorium–Organic
Framework for Kr/Xe Uptake and Separation. Angew. Chem. Int. Ed. 2018, 57, 5783-5787.
12.
Falaise, C.; Charles, J. S.; Volkringer, C.; Loiseau, T., Thorium terephthalates
coordination polymers synthesized in solvothermal DMF/H2O system. Inorg. Chem. 2015, 54,
2235-2242.
13.
Li, Y.; Yang, Z.; Wang, Y.; Bai, Z.; Zheng, T.; Dai, X.; Liu, S.; Gui, D.; Liu, W.; Chen,
M.; Chen, L.; Diwu, J.; Zhu, L.; Zhou, R.; Chai, Z.; Albrecht-Schmitt, T. E.; Wang, S., A
mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic
pollutants. Nat. Commun. 2017, 8, 1354.
14.
Andreo, J.; Priola, E.; Alberto, G.; Benzi, P.; Marabello, D.; Proserpio, D. M.; Lamberti,
C.; Diana, E., Autoluminescent Metal–Organic Frameworks (MOFs): Self-Photoemission of a
Highly Stable Thorium MOF. J. Am. Chem. Soc. 2018, 140, 14144-14149.
15.
Supramolecular Assembly in the 5f Block. Chem. Eur J. 2018, 24, 12747-12756.
16. Carter, K. P.; Ridenour, J. A.; Kalaj, M.; Cahill, C. L., A Thorium Metal ‐ Organic
Carter, K. P.; Surbella III, R. G.; Kalaj, M.; Cahill, C. L., Restricted Speciation and
Framework with Outstanding Thermal and Chemical Stability. Chem. Eur J. 2019, 25, 7114-
7118.
17.
Hydrates and Their Hydrolysis and Condensation Products. Chem. Rev. 2013, 113, 944-994.
18. Vanagas, N. A.; Wacker, J. N.; Rom, C. L.; Glass, E. N.; Colliard, I.; Qiao, Y.; Bertke, J.
Knope, K. E.; Soderholm, L., Solution and Solid-State Structural Chemistry of Actinide
A.; Van Keuren, E.; Schelter, E. J.; Nyman, M., Solution and Solid State Structural Chemistry of
Th (IV) and U (IV) 4-Hydroxybenzoates. Inorg. Chem. 2018, 57, 7259-7269.
19.
Sava, D. F.; Rodriguez, M. A.; Chapman, K. W.; Chupas, P. J.; Greathouse, J. A.;
Crozier, P. S.; Nenoff, T. M., Capture of volatile iodine, a gaseous fission product, by zeolitic
imidazolate framework-8. J. Am. Chem. Soc. 2011, 133, 12398.
20.
Banerjee, D.; Chen, X.; Lobanov, S. S.; Plonka, A. M.; Chan, X.; Daly, J. A.; Kim, T.;
Thallapally, P. K.; Parise, J. B., Iodine adsorption in metal organic frameworks in the presence of
humidity. ACS Appl.Mater. Interfaces 2018, 10, 10622-10626.
21.
Chen, Y.; Sun, H.; Yang, R.; Wang, T.; Pei, C.; Xiang, Z.; Zhu, Z.; Liang, W.; Li, A.;
Deng, W., Synthesis of conjugated microporous polymer nanotubes with large surface areas as
absorbents for iodine and CO2 uptake. J. Mater. Chem. A 2014, 3, 87-91.
ACS Paragon Plus Environment
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Page 25 of 28
Crystal Growth & Design
1
2
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22.
Geng, T.; Ye, S.; Zhu, Z.; Zhang, W., Triazine-based conjugated microporous polymers
with N,N,N ′,N ′-tetraphenyl-1,4-phenylenediamine, 1,3,5-tris(diphenylamino)benzene and 1,3,5-
tris[(3-methylphenyl)-phenylamino]benzene as the core for high iodine capture and fluorescence
sensing of o-nitrophenol. J. Mater. Chem. A 2018, 6, 2808-2816.
23.
interpenetration of self-assembled coordination cages. J. Am. Chem. Soc. 2008, 130, 5832-5833.
24. Costa, J. S.; Castro, A. G.; Pievo, R.; Roubeau, O.; Modec, B.; Kozlevčar, B.; Teat, S. J.;
Yamauchi, Y.; Yoshizawa, M.; Fujita, M., Engineering stacks of aromatic rings by the
10
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59
60
Gamez, P.; Reedijk, J., Proficiency of the electron-deficient 1,3,5-triazine ring to generate anion–
π and lone pair–π interactions. Crystengcomm 2010, 12, 3057-3064.
25.
Hu, F.; Di, Z.; Peng, L.; Pan, H.; Wu, M.; Jiang, F.; Hong, M., An Anionic Uranium-
Based Metal–Organic Framework with Ultra Large Nano-Cages for Selective Dye Adsorption.
Crystal Growth & Design 2018, 18, 576-580.
26.
Zhang, N.; Xing, Y.-H.; Bai, F.-Y., A Uranyl-Organic Framework Featuring Two-
Dimensional Graphene-like Layered Topology for Efficient Iodine and Dyes Capture. Inorg.
Chem. 2019, 58, 6866-6876.
27.
Moreno-Lara, B.; Carabineiro, S. A.; Krishnamoorthy, P.; Rodríguez, A. M.; Mano, J. F.;
Manzano, B. R.; Jalón, F. A.; Gomes, P. T., Nickel (II) complexes of bidentate N–N ′ ligands
containing mixed pyrazole, pyrimidine and pyridine aromatic rings as catalysts for ethylene
polymerisation. J. Organomet. Chem. 2015, 799, 90-98.
28.
organic framework with permanent porosity. J. Am. Chem. Soc. 2006, 128, 16474-16475.
29. Pal, S.; Bhunia, A.; Jana, P. P.; Dey, S.; Mollmer, J.; Janiak, C.; Nayek, H. P.,
Wang, X. S.; Ma, S.; Sun, D.; Parkin, S.; Zhou, H. C.; Zhou, H. C., A mesoporous metal-
Microporous La-metal-organic framework (MOF) with large surface area. Chem. Eur J. 2015,
21, 2789-2792.
30.
Zhang, H.; Chen, D.; Ma, H.; Cheng, P., Real-Time Detection of Traces of Benzaldehyde
in Benzyl Alcohol as a Solvent by a Flexible Lanthanide Microporous Metal-Organic
Framework. Chem. Eur J. 2015, 21, 15854-15859.
31.
Hasan, Z.; Jhung, S. H., Removal of hazardous organics from water using metal-organic
frameworks (MOFs): plausible mechanisms for selective adsorptions. J. Hazard. Mater. 2015,
283, 329-339.
32.
Tan, J.; Zhou, B.; Liang, C.; Zinky, H.; Zhou, H.-L.; Zhang, Y.-B., Secondary-amine-
functionalized isoreticular metal–organic frameworks for controllable and selective dye capture.
Mater. Chem. Front. 2018, 2, 129-135.
33.
Li, P.; Vermeulen, N. A.; Gong, X.; Malliakas, C. D.; Stoddart, J. F.; Hupp, J. T.; Farha,
O. K., Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic
Framework (MOF) with Ultra Large Pores. Angew. Chem. Int. Ed. Engl. 2016, 128, 10514-
10518.
34.
Du, W.; Zhu, Z.; Bai, Y.-L.; Yang, Z.; Zhu, S.; Xu, J.; Xie, Z.; Fang, J., An anionic sod-
type terbium-MOF with extra-large cavities for effective anthocyanin extraction and methyl
viologen detection. Chem. Commun. 2018, 54, 5972-5975.
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Crystal Growth & Design
Page 26 of 28
1
2
3
4
5
6
7
8
9
35.
Du, P.-Y.; Li, H.; Fu, X.; Gu, W.; Liu, X., A 1D anionic lanthanide coordination polymer
as an adsorbent material for the selective uptake of cationic dyes from aqueous solutions. Dalton
Trans. 2015, 44, 13752-13759.
36.
cationic dyes by UiO-66-NH2. Appl. Surf. Sci. 2015, 327, 77-85.
37. Cui, Z.; Zhang, X.; Liu, S.; Zhou, L.; Li, W.; Zhang, J., Anionic Lanthanide Metal–
Chen, Q.; He, Q.; Lv, M.; Xu, Y.; Yang, H.; Liu, X.; Wei, F., Selective adsorption of
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
Organic Frameworks: Selective Separation of Cationic Dyes, Solvatochromic Behavior, and
Luminescent Sensing of Co (II) Ion. Inorg. Chem. 2018, 57, 11463-11473.
38.
Fang, Q. R.; Yuan, D. Q.; Sculley, J.; Li, J. R.; Han, Z. B.; Zhou, H. C., Functional
mesoporous metal-organic frameworks for the capture of heavy metal ions and size-selective
catalysis. Inorg. Chem. 2018, 57, 11463-11473.
39.
Crystallogr. 2008, 64, 112-122.
40. Sheldrick, G. M., Program for empirical absorption correction of area detector data.
SADABS 1996.
Sheldrick, G. M., A short history of SHELX. Acta Crystallogr. Sect. A: Found.
41.
Sheldrick, G., SHELX-97, program for the solution and refinement of crystal structures.
University of Göttingen, Germany 1997.
42.
molecular clusters with a hexanuclear Th core. Inorg. Chem. 2011, 50, 9696-704.
43. Yan, Z.; Yuan, Y.; Tian, Y.; Zhang, D.; Zhu, G., Highly Efficient Enrichment of Volatile
Knope, K. E.; Wilson, R. E.; Vasiliu, M.; Dixon, D. A.; Soderholm, L., Thorium(IV)
Iodine by Charged Porous Aromatic Frameworks with Three Sorption Sites. Angew. Chem. Int.
Ed. 2015, 54, 12733-12737.
44.
Yao, R. X.; Cui, X.; Jia, X. X.; Zhang, F. Q.; Zhang, X. M., A Luminescent Zinc(II)
Metal-Organic Framework (MOF) with Conjugated π-Electron Ligand for High Iodine Capture
and Nitro-Explosive Detection. Inorg. Chem. 2016, 55, 9270-9275.
45.
Falaise, C.; Volkringer, C.; Facqueur, J.; Bousquet, T.; Gasnot, L.; Loiseau, T., Capture
of iodine in highly stable metal–organic frameworks: a systematic study. Chem. Commun. 2013,
49, 10320-10322.
46.
frameworks. J. Mater. Chem. A 2014, 2, 7179-7187.
47. Deboer, G.; Burnett, J. W.; Young, M. A., Molecular product formation from the charge-
transfer state of C6H6I2. Chem. Phys. Lett. 1996, 259, 368-374.
48. Jeromenok, J.; Weber, J., Restricted access: on the nature of adsorption/desorption
hysteresis in amorphous, microporous polymeric materials. Langmuir 2013, 29, 12982-12989.
49. Liao, Y.; Weber, J.; Mills, B. M.; Ren, Z.; Faul, C. F. J., Highly Efficient and Reversible
Pei, C.; Ben, T.; Xu, S.; Qiu, S., Ultrahigh iodine adsorption in porous organic
Iodine Capture in Hexaphenylbenzene-Based Conjugated Microporous Polymers.
Macromolecules 2016, 49, 6322-6333.
50.
Li, P.; Vermeulen, N. A.; Gong, X.; Malliakas, C. D.; Stoddart, J. F.; Hupp, J. T.; Farha,
O. K., Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic
Framework (MOF) with Ultra Large Pores. Angew. Chem. 2016, 55, 10358-10362.
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51.
Li, H.; Cao, X.; Zhang, C.; Yu, Q.; Zhao, Z.; Niu, X.; Sun, X.; Liu, Y.; Ma, L.; Li, Z.,
Enhanced adsorptive removal of anionic and cationic dyes from single or mixed dye solutions
6
7
using MOF PCN-222. RSC Adv. 2017, 7, 16273-16281.
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For Table of Contents Use Only
A Double-walled Thorium-based Metal-Organic
Framework (MOF) as a Promising Dual Functional
Absorbent for Efficiently Capturing Iodine and Dyes
Na Zhang,† Li-Xian Sun§,Yong-Heng Xing,*† and Feng-Ying Bai*†
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Synopsis
A novel thorium-based MOF Th-TATAB with rare double-walled tetrahedral cage structure. The
thorium-based MOF can be used as an promising dual functional adsorbent for iodine capture in
cyclohexane solution and the adsorptive removal of dye contaminants in aqueous solution,
whcich provided a new strategic idea for opening up the potential applications of thorium-based
MOF and understanding actinides chemistry.
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