Postsynthetic Functionalization of Three-Dimensional Covalent Organic Frameworks for Selective Extraction of Lanthanide Ions

Article abstract of DOI:10.1002/anie.201712246

Chemical functionalization of covalent organic frameworks (COFs) is critical for tuning their properties and broadening their potential applications. However, the introduction of functional groups, especially to three-dimensional (3D) COFs, still remains

Full text of DOI:10.1002/anie.201712246

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Angewandte
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Accepted Article
Title: Postsynthetic Functionalization of Three-Dimensional Covalent
Organic Framework for Selective Extraction of Lanthanide Ions
Authors: Qianrong Fang, Qiuyu Lu, Yunchao Ma, Hui Li, Xinyu Guan,
Yusran Yusran, Ming Xue, Yushan Yan, Shilun Qiu, and
Valentin Valtchev
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201712246
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10.1002/anie.201712246
Angewandte Chemie International Edition
DOI: 10.1002/anie.200((will be filled in by the editorial staff))
Covalent Organic Frameworks
Postsynthetic Functionalization of Three-Dimensional Covalent Organic
Framework for Selective Extraction of Lanthanide Ions
Qiuyu Lu†, Yunchao Ma†, Hui Li, Xinyu Guan, Yusran Yusran, Ming Xue, Qianrong Fang*, Yushan
Yan, Shilun Qiu and Valentin Valtchev*
Abstract: Chemical Functionalization of covalent organic
frameworks (COFs) is critical to tune their properties and broaden
their potential applications. However, the introduction of functional
groups especially in three-dimensional (3D) COFs still
remains largely unexplored. Here we report a general strategy for
generating a 3D carboxyl-functionalized COF through postsynthetic
modification of a hydroxyl COF, and for the first time explore the 3D
carboxyl COF for selective extraction of lanthanide ions. The
obtained COF shows high crystalllinity, good chemical stability, and
large specific surface area. Furthermore, the carboxyl COF displays
high metal loading capacities together with excellent adsorption
selectivity for Nd3+ over Sr2+ and Fe3+ confirmed by the Langmuir
adsorption isotherms and ideal adsorbed solution theory (IAST)
calculations. This study not only provides a strategy for versatile
functionalization of 3D COFs, but also opens the route to their
environmental related applications.
Scheme 1. Schematic representation of the strategy for preparing 3D
Covalent organic frameworks (COFs) is a new class of crystalline
porous polymers based on the precise integration of organic building
blocks into periodic structures.[1] Because of their regular pore
structure, high surface area and tunable chemistry, the COF materials
are explored in various fields as energy storage,[2] optoelectronics,[3]
catalysis,[4] and a number of others.[5] Over the past decade, a large
number of two-dimensional (2D) COFs with nearly eclipsed
structures have been synthesized.[1-5] In contrast, few three-
dimensional (3D) COFs have been obtained,[6,7] and the
functionalization of 3D COFs still remains largely unexplored.[8]
Functionalization of the pores of 3D COFs is a straightforward way
to predetermine the properties and provide structurally and
chemically precise platforms for various applications. However, the
introduction of functional groups in 3D COFs is difficult due to the
absence of reactive groups, such as hydroxyls, in almost all 3D COFs
functionalized COF through postsynthetic decoration. (a) Molecular
structures of tetra(4-formylphenyl)methane (TFPM)) as a tetrahedral
building unit and 3,3′-dihydroxybenzidine (DHBD) as a linear linker.
(b) 3D COF with hydroxyl groups, 3D-OH-COF, constructed by the
condensation reaction of TFPM and DHBD. (c) 3D carboxyl-
functionalized COF, 3D-COOH-COF, obtained from the ring opening
reaction of 3D-OH-COF with succinic anhydride (SA). (d)
A
diamondoid (dia) net based on tetrahedral and linear building units.
reported to date. Thus, in contrast to zeolites and metal-organic
frameworks (MOFs) where the postsynthetic modification is readily
used,[9] the functionalization of 3D COFs is considered to be a great
challenge.
Herein, we report a general strategy for preparation of 3D
carboxyl-functionalized COF through postsynthetic modification of a
hydroxyl COF. The obtained 3D COF shows good crystalllinity, high
chemical stability, and large specific surface areas. More importantly,
the carboxyl COF displays high metal loading capability together
with outstanding adsorption selectivity for neodymium(III) over
strontium(II) and iron(III) ions as shown by the Langmuir adsorption
isotherms and ideal adsorbed solution theory (IAST) calculations. To
the best of our knowledge, this study is the first example of the
application of 3D COF material for selective extraction of metal ions.
[]
Q. Lu, Y. Ma, H. Li, X. Guan, Y. Yusran, Prof. M. Xue, Prof.
Q. Fang, Prof. S. Qiu
State Key Laboratory of Inorganic Synthesis and
Preparative Chemistry,
Jilin University, Changchun 130012, China
E-mail: qrfang@jlu.edu.cn
Prof. Y. Yan
Department of Chemical and Biomolecular Engineering,
Center for Catalytic Science and Technology,
University of Delaware, Newark, DE 19716, USA
Prof. V. Valtchev
Normandie Univ, ENSICAEN, UNICAEN, CNRS,
Laboratoire Catalyse et Spectrochimie, 6 Marechal Juin,
14050 Caen, France
Our strategy for preparation of a carboxyl-functionalized COF,
denoted 3D-COOH-COF, is based on the ring opening reaction
approach.[5h] As shown in Scheme 1a, tetra(4-formylphenyl)methane
(TFPM) was designed as a tetrahedral building unit, and 3,3′-
dihydroxybenzidine (DHBD) was chosen as an ideal linear linker
comprising hydroxyl groups. The condensation of TFPM and DHBD
E-mail: valentin.valtchev@ensicaen.fr
[†] These authors contributed equally to this work.
produces
a 3D hydroxyl COF, 3D-OH-COF (Scheme 1b).
Supporting information for this article is available on the
WWW under http://www.angewandte.org or from the
author.
Subsequently, the hydroxyl groups in 3D-OH-COF are reacted with
succinic anhydride (SA) resulting in a ring opening and formation of
1
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10.1002/anie.201712246
Angewandte Chemie International Edition
3D-COOH-COF (Scheme 1c). In light of the linking of tetrahedral
and linear building units, the structure of both COFs is expected to be
based on the diamondoid (dia) net (Scheme 1d). Since the tetrahedral
TFPM centers are connected by long linear DHBD (10.7 Å), the
resulting structure tends to be multi-interpenetrated network.[10]
DFT fitting of the adsorption branches showed pore size distributions
mainly at 13.1 Å in agreement with that of the proposed model
(Figure 3a inset).
Figure 1. SEM images of 3D-OH-COF (a) and 3D-COOH-COF (b).
PXRD patterns (c) of experimentally observed 3D-COOH-COF and 3D-
OH-COF, refined 3D-OH-COF, their difference, and calculated 3D-OH-
COF based on the 9-fold dia net.
The synthesis of 3D-OH-COF was carried out by suspending
TFPM and DHBD in the mixed solvent of anhydrous dioxane and
mesitylene in the presence of acetic acid followed by heating at
120 °C for 3 days, yielding a crystalline solid. A variety of methods
were employed for structural characterizations. The morphology of
3D-OH-COF was examined by scanning electron microscopy (SEM,
Figure 1a), which showed isometric crystals with size 1-2 m. The
Fourier transform infrared (FT-IR) spectrum of 3D-OH-COF
exhibited a peak at 1626 cm−1 which is characteristic of C=N bond.
The concomitant disappearance of the C=O stretching vibration (1693
cm−1) of TFPM and the N-H stretching vibration (3285 and 3354 cm−1)
of DHBD, confirmed that a condensation reaction takes place (Figure
S1). The solid-state 13C cross-polarization magic-angle-spinning
(CP/MAS) NMR spectroscopy of 3D-OH-COF confirmed the
presence of carbons from the imine groups by the peak at 156 ppm
(Figure S2). It is worth noting that the high thermal stability (450 °C)
displayed by 3D-OH-COF, as shown by the thermogravimetric
analysis (TGA, Figure S3).
Figure 2. Extended structures of 3D-OH-COF (a) and 3D-COOH-COF
(b). Single dia network (c) and 9-fold interpenetrated dia topology (d)
in 3D-COOH-COF.
Inspired by its high crystallinity and abundant presence of
hydroxyls, we converted the 3D-OH-COF into a carboxyl-
functionalized 3D-COOH-COF based on the ring opening reaction.
Typically, 3D-COOH-COF was obtained by suspending 3D-OH-
COF in SA (8.0 mL, 1.0 M solution in anhydrous acetone) at 60 °C
for 24 h. 3D-COOH-COF and 3D-OH-COF exhibit similar PXRD
pattern and morphology, indicating that no noticeable morphological
and structural changes occurred during chemical modification (Figure
1b and 1c). Nitrogen sorption measurement revealed substantially
reduced BET surface area (540 m2 g−1) and pore size (6.8 Å) of
carboxyl grafted 3D-COOH-COF (Figure 3b and Figure S5). On the
other hand the 3D-COOH-COF shows thermal stability (450 °C)
similar with the parent material (Figure S6). The successful grafting
of carboxyl groups onto the 3D-OH-COF was confirmed by FT-IR,
solid-state 13C NMR studies, liquid 1H NMR spectroscopy of
hydrolyzed samples and elemental analysis. The FT-IR spectrum of
the 3D-COOH-COF showed the characteristic band of -COOH at
3649 cm−1, confirming the existence of free-standing carboxyl groups
(Figure S7). The carboxyl-functionalized transformation was
determined by the concomitant emergence of peak at 164.2 ppm
ascribed to the carboxyl groups in the 13C MAS NMR spectrum of
3D-COOH-COF (Figure S8). Furthermore, elemental analysis and
liquid 1H NMR spectroscopy of hydrolyzed 3D-COOH-COF sample
revealed that 50% of available hydroxyls were grafted/replaced with
carboxylic groups. This result is attributed to the steric limitations in
micropore space (Table S2). The set of experimental data shows that
carboxylic groups were successfully incorporated without
significantly altering the crystalline structure of 3D-OH-COF (Figure
2 and Table S3). The framework of 3D-COOH-COF was stable in
ambient air and retained its crystallinity after soaking in a variety of
The crystalline nature of 3D-OH-COF was revealed by powder
X-ray diffraction (PXRD) analysis. PXRD peaks at 5.85, 8.70, 12.41,
14.82, 18.94, 19.81, 21.45, 22.25, 24.45 and 26.52° 2 can be
assigned to the (200), (310), (101), (510), (431), (521), (611), (730),
(202) and (402) Bragg peaks (Figure 1c, black curve). The Pawley
refinement yielded a PXRD that is in good agreement with the
experimentally observed pattern, as evident by their negligible
difference and very low values of wRp = 3.48% and Rp = 7.41%
(Figure 1c, red and green curves). Considering that the length of these
linkers is similar to those of COF-320,[11] a 9-fold dia net for 3D-OH-
COF was constructed from TFPM and DHBD by using the Materials
Studio Software package (Table S1).[12] Simulated PXRD pattern
shows good match with the experimental one (Figure 1c, pink curve).
On the basis of these results, 3D-OH-COF was proposed to have the
expected architecture with a 9-fold dia net, which shows the
microporous rectangular pores with the largest diameter of about 13.5
Å (Figure 2a). The BET surface area was determined to be 1077 m2
g-1 from N2 sorption isotherms at 77 K (Figure 3a, and Figure S4).
2
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10.1002/anie.201712246
Angewandte Chemie International Edition
organic solvents and water, as well as in acid (3.0 M HCl) and base
(3.0 M NaOH) aqueous solutions (Figures S9-12).
binding pockets within 3D-COOH-COF involving multiple carboxyl
groups. While Nd3+ has the highest uptake at low concentration, Fe3+
has the highest uptake at saturation owing to its smaller size, which is
consistent with the nsat parameters (0.71 mmol/g for Nd3+, 0.72
mmol/g for Sr2+ and 4.86 mmol/g for Fe3+). 3D-OH-COF was used as
a reference to extract the above metal ions; however, it shows very
low uptakes which can be attributed to the absence of strong exchange
sites and thus low extraction power (Figure S15).
Figure 3. N2 adsorption-desorption isotherms for 3D-OH-COF (a) and
3D-COOH-COF (b) at 77 K. Solid and open circles represent
adsorption and desorption branches, respectively. Inset: pore-size
distribution calculated by fitting on the NLDFT model to the adsorption
data.
After confirming the porosity, stability, and high density of
carboxyl groups available for metal chelating sites, we examined the
ability of 3D-COOH-COF to effectively extract lanthanide ions from
aqueous solution, as urgent required in the treatment of radioactive
waste.[13] As an initial investigation, the Nd3+, Sr2+ and Fe3+ ions were
chosen as representative ions for group separation of lanthanide
fission products, other fission products, and the corrosion products in
nuclear waste streams, respectively.[14] Typically, the uptakes of
metal ions by 3D-COOH-COF were measured at room temperature,
and the concentrations of metal ions were monitored by using UV-
Vis spectrometer. After the reactions, the SEM and PXRD inspection
confirmed the structural integrity of 3D-COOH-COF, thus revealing
its high stability (Figures S13 and S14).
Figure 4. Metal ion adsorption isotherms (a) of 3D-COOH-COF at room
temperature. IAST selectivity (b) and purities (c) of 3D-COOH-COF for
Nd3+/Fe3+ and Nd3+/Sr2+ mixtures.
The extraction capability of 3D-COOH-COF was studied by the
adsorption isotherms for metal ion uptakes (Figure 4a). To estimate
selectivity, the data were fitted with Langmuir equation, n = nsatbC/(1
+ bC), where n is the total amount adsorbed, C is the concentration,
nsat is the saturation capacity, and b is the Langmuir parameter that
represents the affinity of metal ions for the binding sites. As shown in
Table 1, the b parameter for Nd3+ (15.87 mM−1) is much higher than
those of Sr2+ (0.85 mM−1) and Fe3+ (0.08 mM−1) ions, which suggests
that adsorption of Nd3+ is stronger than Sr2+ and Fe3+ adsorption in
3D-COOH-COF. Indeed, this is highlighted by the steep adsorption
isotherm at low concentration. The near vertical rise of the Nd3+
adsorption isotherm indicates that Nd3+ binds the framework most
strongly, followed by Sr2+ and Fe3+. These results can be ascribed to
the greater charge density of Nd3+ relative to Sr2+ and the larger ionic
radius relative to Fe3+, which provides a better match for certain rigid
The IAST method has been well established for evaluation of
metal ion uptakes by variety of adsorbents.[15] Consequently we
employed this method to predict the mixture behavior of 3D-COOH-
COF. Since the relative concentrations of Nd3+, Fe3+ and Sr2+ ions can
fluctuate in a radioactive waste stream, IAST selectivity was
calculated over a wide range of compositions for a total concentration
of 0.1 mM. As shown in Figure 4b, 3D-COOH-COF exhibits a high
selectivity for Nd3+ over Sr2+ and Fe3+. For instance, for a solution
containing 5% Nd3+ and 95% Fe3+ or Sr2+, 3D-COOH-COF
selectively adsorbs Nd3+ with an IAST selectivity of 27 and 18,
respectively. IAST purity predictions presented in Figure 4c illustrate
the effectiveness of metal ion selectivity in 3D-COOH-COF. They
show that Nd3+ can be isolated from Sr2+ and Fe3+ solutions at a high
3
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10.1002/anie.201712246
Angewandte Chemie International Edition
purity, reaching 86% over Fe3+ and 80% over Sr2+ at a composition
of only 5% Nd3+ in their mixtures. This suggests that the coordination
environment and strength of the metal ion−framework interactions
are very uniform in 3D-COOH-COF, and preferential binding is
consistent across all sites.
13 cm. The reaction mixture was heated at 120 °C for 3 days to afford
a white precipitate which was isolated by filtration over a medium glass
frit and washed with anhydrous tetrahydrofuran (THF, 20.0 mL). The
product was immersed in anhydrous THF (20.0 mL) for 8 h, after that
the activation solvent was decanted and freshly replenished four times.
The solvent was removed under vacuum at 80 °C to afford the
corresponding product as white powder in isolated yield of 81% for 3D-
OH-COF.
Table 1. Langmuir fit parameters for single-component adsorption
isotherms
Nd3+
15.87
0.71
Sr2+
0.85
0.72
Fe3+
0.08
4.86
Postsynthetic functionalization. 3D-OH-COF (46.8 mg, 0.1
mmol) was weighed into a 10-mL glass vial, to which SA (8.0 mL, 1.0
M solution in anhydrous acetone) was added. The reaction mixture was
shaken at 60 °C for 24 h. The precipitate was collected by
centrifugation, and three times washed with anhydrous THF. The crude
product was rinsed with THF for 24 h using a Soxhlet extractor. The
powder was dried at 80 °C under vacuum overnight to give the 3D-
COOH-COF in yield of 83%.
b (mM−1)
n (mmol/g)
To gain further insights into the structure−performance
relationship of 3D-COOH-COF in the selective detection and
effective removal of Nd3+, we applied solid-state 13C NMR
spectroscopy to evaluate the interaction between Nd3+ and carboxyl
groups (Figure S16). After adsorption of Nd3+, the 13C NMR signal at
164.2 ppm, which is ascribed to the carbons of the carboxyl groups in
the 3D-COOH-COF, is downfield shifted to 167.1 ppm, while other
signals remain unchanged. This result points out the strong interaction
between Nd3+ and the carboxyl groups in Nd/3D-COOH-COF. As a
control, the obtained Sr/3D-COOH-COF and Fe/3D-COOH-COF
gave almost identical 13C CP/MAS NMR spectra as 3D-COOH-COF,
indicating that no distinct interaction existed between Sr2+ (or Fe3+)
and 3D-COOH-COF. Moreover, X-ray photoelectron spectroscopy
(XPS) provides further evidence for the strong interaction between
Nd3+ and the carboxyl groups. Compared with the binding energy (BE,
983.7 eV) of Nd 3d5/2 in Nd(NO3)3, the BE of Nd/3D-COOH-COF
was shifted to 980.1 eV (Figure S17). The negative shift by 3.6 eV
evidenced the interaction between Nd3+ and the carboxyl groups in
Nd/3D-COOH-COF: electrons were further donated to Nd3+, which
makes the Nd an electron-excess atom.[16] We further explored the
recycle use of 3D-COOH-COF; the Nd3+ adsorption−desorption
cycle could be repeated at least three times with almost no loss of
activity (Figures S18 and S19).
Further detailed experimental procedures and characterization are
described in the Supporting Information.
Acknowledgments
This work was supported by National Natural Science Foundation of
China (21571079, 21621001, 21261130584, 21390394, 21571076,
and 21571078), “111” project (B07016 and B17020), Guangdong and
Zhuhai
(2013B090200052 and 2012D0501990028), Ministry of Education,
Science and Technology Development Center Project
Science
and
Technology
Department
Project
(20120061130012), and the program for JLU Science and Technology
Innovative Research Team. V.V. and Q.F. acknowledge the Thousand
Talents program (China). V.V., Q.F. and S.Q. acknowledge the
collaboration in the framework of China-French joint laboratory
"Zeolites".
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Published online on ((will be filled in by the editorial staff))
In summary, we report a strategy for functionalizing 3D COFs
through postsynthetic modification. The carboxyl-functionalized 3D-
COOH-COF showed exceptional lantanide selectivity (Nd3+) based
on the Langmuir adsorption isotherms and IAST calculations. XPS
and solid-state NMR investigations verified the strong and selective
interaction between Nd3+ ions and carboxyl groups in 3D-COOH-
COF. Recyclability experiments demonstrated that multiple
adsorption/stripping cycles could be performed with minimal
degradation of the adsorption capacity of 3D-COOH-COF. This study
not only develops a general method for a facile and efficient
functionalization of 3D COFs, but also promotes functionalized COF
materials into an excellent scaffold for environmental related
applications.
Keywords: covalent organic frameworks · postsynthetic
functionalization · porous materials · separation · selective adsorption
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Experimental Section
Synthesis of 3D-OH-COF. A Pyrex tube measuring o.d. × i.d. = 10
× 8 mm2 was charged with TFPM (21.6 mg, 0.05 mmol) and DHBD
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Angewandte Chemie International Edition
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This article is protected by copyright. All rights reserved.

10.1002/anie.201712246
Angewandte Chemie International Edition
Covalent Organic Frameworks
Here we report a general strategy for
generating a 3D carboxyl-functionalized
COF through postsynthetic modification
of a hydroxyl COF, and for the first time
explore the 3D carboxyl COF for
Qiuyu Lu†, Yunchao Ma†, Hui Li, Xinyu
Guan, Yusran Yusran, Ming Xue,
Qianrong Fang*, Yushan Yan, Shilun
Qiu and Valentin Valtchev*
selective extraction of lanthanide ions.
__________ Page – Page
Postsynthetic Functionalization of
Three-Dimensional Covalent Organic
Framework for Selective Extraction of
Lanthanide Ions
6
This article is protected by copyright. All rights reserved.