Preparation of a Yb(III)-Incorporated porous polymer by post-Coordination: Enhancement of gas adsorption and catalytic activity

Article abstract of DOI:10.1002/pola.26962

We synthesized a Yb(III)-incorporated microporous polymer (Yb-ADA) and studied its gas adsorption property and catalytic activity. The adamantane-based porous polymer (ADA) was obtained from an ethynyl-functionalized adamantane derivative and 2,5-dibromoterephthalic acid through Sonogashira-Hagihara cross-coupling. ADA had two carboxyl groups which were used for Yb(III) coordination under basic conditions. The Brunauer-Emmett-Teller (BET) surface area of ADA was 970 m² g^-1. As Yb(III) ions were incorporated into ADA, the surface area of the polymer (Yb-ADA) was reduced to 885 m² g^-1. However, Yb-ADA exhibited a significantly enhanced CO₂ adsorption capacity despite the reduction of surface area. The CO₂ uptakes of ADA and Yb-ADA were 1.56 and 2.36 mmol g^-1 at 298 K, respectively. The H₂ uptake of ADA also increased after coordination with Yb(III) from 1.15 to 1.40 wt % at 77 K. Yb-ADA showed high catalytic activity in the acetalization of 4-bromobenzaldehyde and furfural with trimethyl orthoformate and could be reused after recovery without severe loss of activity.

Full text of DOI:10.1002/pola.26962

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Preparation of a Yb(III)-Incorporated Porous Polymer by Post-
Coordination: Enhancement of Gas Adsorption and Catalytic Activity
Hyungwoo Kim, Min Chul Cha, Hyun Woo Park, Ji Young Chang
Department of Materials Science and Engineering, College of Engineering, Seoul National University, Seoul 151-744, Korea
Correspondence to: J. Y. Chang (E-mail: jichang@snu.ac.kr)
Received 21 May 2013; accepted 16 September 2013; published online 10 October 2013
DOI: 10.1002/pola.26962
ABSTRACT: We synthesized a Yb(III)-incorporated microporous
polymer (Yb-ADA) and studied its gas adsorption property and
catalytic activity. The adamantane-based porous polymer
face area. The CO
2
uptakes of ADA and Yb-ADA were 1.56 and
21
2.36 mmol g
at 298 K, respectively. The H uptake of ADA
2
also increased after coordination with Yb(III) from 1.15 to
1.40 wt % at 77 K. Yb-ADA showed high catalytic activity in the
acetalization of 4-bromobenzaldehyde and furfural with tri-
methyl orthoformate and could be reused after recovery with-
(
ADA) was obtained from an ethynyl-functionalized adaman-
tane derivative and 2,5-dibromoterephthalic acid through
Sonogashira–Hagihara cross-coupling. ADA had two carboxyl
groups which were used for Yb(III) coordination under basic
conditions. The Brunauer-Emmett-Teller (BET) surface area of
out severe loss of activity. V
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C
Polym. Sci., Part A: Polym. Chem. 2013, 51, 5291–5297
2
21
ADA was 970 m
g
. As Yb(III) ions were incorporated into
ADA, the surface area of the polymer (Yb-ADA) was reduced to
2
21
885
m
g
.
However, Yb-ADA exhibited
a
significantly
KEYWORDS: microporous polymers; networks; microstructure;
enhanced CO
2
adsorption capacity despite the reduction of sur-
metal-polymer complexes; catalysis
INTRODUCTION Microporous organic polymers (MOPs) with
In this work, we synthesized a Yb(III)-incorporated micropo-
rous polymer (Yb-ADA) from adamantane derivative and 2,5-
dibromoterephthalic acid. Yb is an element in the lanthanide
series that has the most common oxidation state of 13. An
Yb(III) ion normally has a coordination number of six to
nine. Depending on coordination conditions, it has labile
small molecules such as water as ligands that are easily
eliminated to form open metal sites. The cationic open metal
high surface area and physicochemical stability have
1
attracted considerable attention as gas adsorbents. Com-
pared to traditionally used porous materials such as zeolites
and activated carbons, MOPs have an advantage in their syn-
thesis and modification. A variety of building blocks and syn-
thetic methodologies are available for MOPs. In addition,
MOPs can be further functionalized using diverse chemical
methods which, combined with an appropriately selected
building block, will provide the MOPs with the desired prop-
erty for a specific application.
sites are known to induce chemical binding with H
as CO
as well
. Furthermore, Yb(III) complexes are widely used as
2
2
6
a Lewis catalyst in organic reactions such as aldol condensa-
7
tion, cyanation, and Michael reaction. Yb(III) catalysts sup-
Several factors govern the gas adsorption behaviors of MOPs,
including surface area, pore shape and size, and functionality
of the framework. Many efforts to enhance gas adsorption
ported on ion exchange resins were also reported to show a
similar catalytic activity. Herein we present the synthesis of
Yb-ADA and its enhanced gas adsorption and catalytic
activity.
8
properties of MOPs, particularly for carbon dioxide (CO )
2
2
–4
and hydrogen (H ), have been reported.
For example, sev-
2
eral studies demonstrated that an introduction of a polar
functional group into an MOP enhanced its CO2 uptake sig-
nificantly. The effects of metal ions on the gas adsorption of
EXPERIMENTAL
3
Materials
MOPs have also been studied. Lithium ion-doped porous
polymers showed an increase in CO2 and H2 adsorptions.
1,3,5,7-Tetrakis(4-ethynylphenyl)adamantane was synthe-
sized by according to the literature. All chemicals purchased
4
9
High expectations have also been given for metal-containing
MOPs for their use in the catalysis of an organic reaction.
from Aldrich and TCI were used without any further purifi-
cation. Other reagent grade solvents were used as received.
5
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Measurement
ytterbium(III) chloride hexahydrate (103.33 mg, 0.27 mmol)
in water (2 mL) was added dropwise to the polymer suspen-
sion. After stirring for 10 h at rt, the product was isolated
by filtration and washed with water, ethanol, and acetone.
1
H NMR spectra were recorded on a Bruker Avance 300
spectrometer (300 MHz). Solid state C CP/MAS NMR spec-
tra were recorded on a Bruker Avance 400 WB spectrometer
1
3
ꢀ
(
100 MHz) equipped with CP-MAS. Fourier transform infra-
The polymer was dried in vacuum at 150 C. Yield: 92%. IR
2
1
red (FT-IR) measurements were made on a PERKIN ELMER
Spectrum GX I using KBr pellets. Thermogravimetric analy-
ses (TGA) were performed on a TA modulated TGA2050
(KBr, cm ): 3747, 3620, 3394, 2931, 2855, 2195, 1698,
1636, 1522, 1405, 1363, 1272, 1118, 1017, 835, 779, 675,
569.
ꢀ
with a heating rate of 10 C/min under nitrogen. N
2
and CO
2
uptakes were measured by using a Belsorp-Max (BEL Japan)
apparatus. Ultra-high purity grade N , H , and CO gases
were used for all adsorption measurements. X-ray photoelec-
tron spectroscopy (XPS) measurements were performed on a
General Procedure for Acetalization
2
2
2
To a solution of an aldehyde (0.1 mmol) and trimethyl ortho-
formate (0.03 mL, 0.3 mmol) in MeOH (10 mL) was added a
catalyst (30 mg). The reaction mixture was stirred for 12 h
at rt. The catalyst was removed by filtration. After evapora-
KRATOS AXIS-Hsi spectrometer equipped with a Mg K X-ray
a
1
source.
tion of the solvent, the residue was analyzed by H NMR
spectroscopy.
Preparation of the Adamantane-Based Porous Polymer
To a solution of 1,3,5,7-tetrakis(4-ethynylphenyl)adamantane
RESULTS AND DISCUSSION
(
100 mg, 0.19 mmol) and 2,5-dibromoterephthalic acid (80
mg, 0.25 mmol) in DMF (3 mL) were added PdCl (PPh ) (30
2
3 2
Synthesis and Characterization
mg, 0.04 mmol) and CuI (10 mg, 0.05 mmol). After degassing
for 10 min, diisopropylamine (3 mL) was added dropwise to
the reaction mixture. After stirring for 24 h at 90 C, the pre-
The ADA was synthesized from an ethynyl-functionalized
adamantane derivative and 2,5-dibromoterephthalic acid
through Sonogashira–Hagihara cross-coupling. A slight excess
amount of the ethynyl-functionalized adamantane monomer
with respect to 2,5-dibromoterephthalic acid was used
because of side reactions such as homocoupling between
ethynyl groups. ADA had two carboxyl groups which could
be utilized for Yb(III) coordination. Under basic conditions,
the carboxyl group was deprotonated and the resulting car-
boxylate was reacted with Yb(III) chloride hexahydrate to
form a Yb(III) complex. A synthetic pathway of ADA and
Yb(III)-coordinated ADA (Yb-ADA) is shown in Scheme 1.
ꢀ
cipitated polymer was isolated by filtration and acidified in an
aqueous HCl solution (1 N, 10 mL). The resulting polymer
was filtered, washed with water, DMF, and acetone, and Soxh-
let extracted with MeOH. The polymer was dried in vacuum
1
0
ꢀ
21
at 150 C. Yield: 84%. IR (KBr, cm ): 3394, 3035, 2933,
2
1
901, 2855, 2198, 1684, 1606, 1507, 1447, 1406, 1359, 1207,
190, 1117, 1017, 834, 784, 730, 564.
Preparation of the Yb(III)-Coordinated ADA Polymer
Adamantane-based porous polymer (ADA) (60 mg) was
dispersed in EtOH (50 mL) and then the pH was adjusted
to 8 with an aqueous NaOH solution (2 M). A solution of
The incorporation of Yb(III) ions in ADA was confirmed by
XPS measurements. The O 1s and C 1s peaks appeared at
SCHEME 1 Synthesis of ADA and Yb-ADA.
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FIGURE 1 XPS spectra of ADA and Yb-ADA.
1
3
FIGURE 2 Solid-state C NMR spectra of ADA and Yb-ADA.
The asterisk marks a rotational sideband.
the binding energy of 530 and 283 eV, respectively in ADA
(
(
Fig. 1). After coordination with Yb(III), the polymer
Yb-ADA) emitted Yb 4d photoelectrons with the correspond-
observed in Yb-ADA, indicating that the ADA structure was
preserved while coordinated.
ing binding energy at 185 eV in addition to O 1s and C 1s
photoelectrons. The Cl 2p photoelectrons were also detected
at 198 eV because an Cl anion could remain as a counter ion
for Yb(III). On the assumption that Yb(III) ions were distrib-
uted homogeneously in Yb-ADA, we estimated atomic ratios
of C, O, and Yb using XPS elemental analysis. The ratio of
C:O:Yb was found to be 86.36:13.64:0 in ADA and
Thermal properties of ADA and Yb-ADA were investigated by
TGA (Fig. 3). Both ADA and Yb-ADA were thermally stable
ꢀ
up to 200 C and degraded gradually as the temperature
increased further. ADA and Yb-ADA had char yields of 65
ꢀ
and 73 wt %, respectively at 800 C. The higher char yield
69.88:27.79:2.33 in Yb-ADA. The concentration of Yb was
of Yb-ADA could be caused by the coordinated Yb(III) ions.
smaller than the value calculated from the ideal structure
probably because various coordination structures could be
formed. The XPS elemental analysis results and theoretical
compositions are summarized in Table 1.
Gas Adsorption Properties
The N2 adsorption/desorption isotherms and pore distribu-
tions of ADA and Yb-ADA are shown in Figure 4. The
Brunauer-Emmett-Teller (BET) surface area of ADA calculated
1
3
Figure 2 shows the C NMR spectra of ADA and Yb-ADA. In
ADA, the carbon peaks from the carboxyl and ethynyl groups
appeared at 165 and 80 ppm, respectively. The peak for aro-
matic carbons adjacent to the adamantane ring appeared at
2
21
from the N adsorption isotherm at 77 K was 970 m g . As
2
the Yb(III) ions were incorporated into ADA, the surface area
of the polymer (Yb-ADA) was reduced to 885 m
The incorporation of Yb(III) ions into ADA also appeared
to change the pore size distribution when calculated by
2
21
g
.
149 ppm and the peaks for other aromatic carbons appeared
at 130 and 123 ppm. The admantane carbon peaks were
shown at 38 and 44 ppm. All these peaks were also
TABLE 1 Atomic Composition of ADA and Yb-ADA Determined
by XPS
Atomic Composition (%)
Polymer
ADA
C
O
Yb
a
Theoretical
88.57
86.36
68.89
69.88
11.43
13.64
26.67
27.79
–
XPS analysis
–
a
Yb-ADA
Theoretical
4.44
2.33
XPS analysis
a
Theoretical values were calculated on the assumption that all ethynyl
groups were participated in the coupling reaction and Yb(III) was coor-
dinated with one carboxylate group.
FIGURE 3 TGA thermograms of ADA and Yb-ADA.
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2
FIGURE 4 N adsorption/desorption isotherms at 77 K for ADA and Yb-ADA (a) and their pore size distributions calculated using
NLDFT (b).
1
1
nonlocal density function theory (NLDFT) with a cylindrical
model. Given the calculation, the proportion of ultrafine
micropores (<1 nm) was reduced after coordination and
larger micropores were observed more in Yb-ADA. One pos-
sible explanation for this result was that the pore structure
was changed by coordination and deviated from the cylindri-
cal model. The micropore volume decreased from 0.36 to
metal sites of Yb(III) interacted with CO2 electrostatically.
The interaction between Yb(III) and CO was further proved
2
by the heat of adsorption measurement [Fig. 5(b)]. The heat
of adsorption was obtained from the CO2 adsorption iso-
therms at 273 and 298 K. Yb-ADA showed a larger initial
2
1
heat of adsorption (31.7 KJ mol ) than ADA (28.5 KJ
2
1
mol ).
3
21
0.34 cm g after coordination, leading to the surface area
2
The capture of CO from flue gas is of great interest because
CO is considered one of the main causes of global warming.
decrease.
2
The CO adsorptions were measured up to 1 bar at 273 and
Flue gas usually comprises mostly nitrogen and about 15%
CO2. Accordingly, the high selectivity of CO over N at low
2 2
2
1
2
2
98 K [Fig. 5(a)]. ADA showed the CO adsorption of 2.57
2
2
1
and 1.56 mmol g at 273 and 298 K, respectively. Yb-ADA
pressures is essential for the efficient separation of CO2 in
flue gas. The initial CO and N adsorption isotherms at 298
exhibited significantly enhanced CO adsorption capacity of
2
2
2
2
1
3
.49 and 2.36 mmol g at 273 and 298 K, respectively even
K are compared in Figure 6. The comparison of initial
adsorptions has been reasonably used to investigate the
interaction between a gas and a porous polymer while
though it had a smaller surface area compared to ADA. This
result was attributable to the fact that the cationic open
2 2
FIGURE 5 CO adsorptions at 273 and 298 K for ADA and Yb-ADA (a) and their isosteric heats of adsorption for CO (b).
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the N adsorption. The selectivity of CO over N was calcu-
2
2
2
lated based on the initial uptake slopes. The CO
2 2
/N selectiv-
ity of Yb-ADA was 38, which was 2.7 times higher than that
of ADA (14).
Figure 7 shows the H adsorption isotherms at 77 and 87 K.
2
The H uptake of ADA also increased after coordination with
2
Yb(III) from 1.15 to 1.40 wt % at 77 K and from 0.81 to
0.95 wt % at 87 K. The initial heats of adsorption of Yb-ADA
and ADA, calculated from adsorption isotherms at 77 and 87
2
1
K, were 11.5 and 7.7 KJ mol , respectively. The CO and H2
2
adsorption properties of the polymers are summarized in
Table 2.
Catalytic Activity
2 2
FIGURE 6 CO and N adsorption isotherms of ADA and Yb-
The catalytic activity of ADA and Yb-ADA in a condensation
reaction was investigated. We used an acetal formation reac-
tion of 4-bromobenzaldehyde and furfural with trimethyl
orthoformate as a model reaction. ADA with catalytic car-
boxyl groups produced acetals in very low yields of 5% and
ADA at 298 K within the pressure range of 0.0–0.1 bar.
excluding other factors such as gas-gas interactions and pore
1
3
shapes. The CO and N adsorption isotherms showed lin-
2
2
ear slopes within the pressure range of 0.0–0.1 bar. The ini-
28 % for 4-bromobenzaldehyde and furfural, respectively. In
tial CO adsorption slope of Yb-ADA was steeper than that of
ADA, while two polymers showed a similar initial slope in
2
contrast, in the presence of Yb-ADA, 4-bromobenzaldehyde
and furfural were completely converted to the corresponding
2 2
FIGURE 7 H adsorption isotherms at 77 and 87 K for ADA and Yb-ADA (a) and their isosteric heats of adsorption for H (b).
2 2
TABLE 2 Surface Areas, Pore Volumes, and CO and H Uptakes of ADA and Yb-ADA
V
micro
3
V
total
3
CO
2
uptake at
2
H uptake at
2
21 a
)
21 b
)
21 b
)
21 c
)
d
Polymer
S
BET (m
g
(cm g
(cm g
V
0.1/total
1 bar (mmol g
1 bar (wt %)
ADA
970
885
0.36
0.34
0.82
0.85
0.44
0.40
2.57 (1.56)
3.49 (2.36)
1.15 (0.81)
1.40 (0.95)
Yb-ADA
a
c
Surface areas were calculated by the BET method from N
2
adsorption
CO
2
uptakes measured at 273 K and at 298 K in parenthesis.
d
isotherms at 77 K.
b
2
H uptakes measured at 77 K and 87 K in parenthesis.
Micropore volume and total pore volume were determined at P/
5 0.1 and P/P 5 0.995, respectively.
P
0
0
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TABLE 3 Conversion Yields in Acetalization of
tioned as a heterogeneous catalyst in acetalization. These
results suggested that cationic open metal sites of Yb(III) in
the polymer strongly interacted with electron rich parts of
H2 and CO2 for adsorption, and with an unshared electron
pair on the oxygen atom for catalysis. This work demon-
strates that the introduction of metal ions of interest into
MOPs is an efficient way to further optimize their properties.
a
4-Bromobenzaldehyde and Furfural
ACKNOWLEDGMENTS
This research was supported by grants from the Mid-career
Researcher Program through NRF grant (No. 2010-0017552)
funded by the Ministry of Education, Science, and Technology.
b
Yield (%)
Catalyst
4-Bromobenzaldehyde
Furfural
Without the catalyst
ADA
0
0
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