A one building block approach for defect-enhanced conjugated microporous polymers: Defect utilization for recyclable and catalytic biomass conversion

Article abstract of DOI:10.1039/c8ta06273k

A one building block approach was studied for preparation of defect-enhanced and terminal alkyne-rich hollow conjugated microporous polymers (H-TA-CMPs). The enriched terminal alkynes were utilized in post-synthetic modification of H-TA-CMPs with aliphatic sulfonic acids (H-TA-CMP-ASO₃H). The obtained H-TA-CMP-ASO₃H showed excellent reactivity and recyclability in biomass conversion to 5-hydroxymethylfurfural, compared with CMPs with aromatic sulfonic acids (H-control-SO₃H).

Full text of DOI:10.1039/c8ta06273k

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ISSN 2050-7488
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Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
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DOI: 10.1039/C8TA06273K
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One building block approach for defect-enhanced conjugated
microporous polymer: Defect utilization for recyclable and
catalytic biomass conversion
cReceived 00th January 20xx,
Accepted 00th January 20xx
Kyoungil Cho,a Sang Moon Lee,b Hae Jin Kim,b Yoon-Joo Ko,c and Seung Uk Son*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
One building block approach was studied for preparation of defect- alkynes and can be free from the network-induced suppression
enhanced and terminal alkyne rich hollow conjugated microporous of chemical reactivity. It is noteworthy that defect utilization has
polymers (H-TA-CMPs). The enriched terminal alkynes were utilized been realized in microporous inorganic materials or metal-
in post-synthetic modification to H-TA-CMPs with aliphatic sulfonic organic frameworks.7 Thus, we have devised a synthetic strategy
acids (H-TA-CMP-ASO3H). The obtained H-TA-CMP-ASO3H showed to enhance defects in CMPs.
excellent reactivity and recyclability in biomass conversion to 5-
Infrared absorption (IR) spectroscopy is useful for
hydroxymethylfurfural, compared with CMPs with aromatic characterizing terminal alkynes in CMP materials.8 According to
sulfonic acids (H-control-SO3H).
IR analysis, conventional CMPs showed trace vibration peaks of
terminal alkyne groups.8 To induce more defects in CMPs, we
have devised one building block approach using diethynyldihalo
arene. (Refer to possible chemical structure of CMPs in Fig. 1)
Enriched terminal alkyne groups through enhanced defects in
CMPs can be utilized to introduce additional functional groups.
For example, aliphatic sulfonic acid can be introduced by the
thiol-yne click reaction of CMPs with aliphatic sulfonate thiol.
Solid sulfonic acids have been used as Brønsted acid catalysts
The representative properties of conjugated microporous
polymers (CMPs) are their high surface areas and
microporosity.1 Based on these properties, the CMPs have been
applied as adsorbents for small molecules such as gases and
water pollutants.2 To introduce additional functionalities, post-
synthetic modification of CMPs has been studied.3
Generally, CMPs have been prepared by the Sonogashira
coupling of multiethynyl arenes and multihalo arenes.1 Thus,
conventional CMPs are rich in alkyne groups. The alkynes are
very versatile moieties for chemical reactions including the thiol-
yne click reaction.4 Post-synthetic modification of CMPs based
on the thiol-yne click reaction has been reported.3a,d,f However,
in our studies, functional moieties introduced by this method
were not sufficient in quantity.5 We speculate that this might be
due to two factors. First, diaryl internal alkynes in CMPs may
have relatively low reactivity toward the click-based thiol
addition. Second, the reactivity of internal alkynes can be
suppressed in the network due to the so called, network effect.6
We considered that the possible terminal alkyne groups in
defects of network may have higher reactivity than internal
for
carbohydrate-based
biomass
conversion
to
5-
hydroxymethylfurfural (HMF) through water abstraction.9 Our
research group has studied sulfonated microporous organic
polymers10 and their application as catalysts for carbohydrate
conversion to HMF. However, we found that although the
sulfonated CMPs showed good reactivity in the first run, they
gradually lost their catalytic reactivity in the successive cycles.
As well documented,11 aryl sulfonic acids are not thermally
stable in the presence of water to result in facile cleavage of C-S
bonds, leading to poor recyclability of aryl sulfonic acid
catalysts. In contrast, it has been known that aliphatic sulfonic
acids are thermally stable to show good recyclability in
dehydration reaction of sugar-based biomass to furan
derivatives.12 Thus, CMPs with aliphatic sulfonic acids are
promising solid catalysts for biomass conversion to HMF.
However, as far as we are aware, the CMPs with aliphatic
sulfonic acids have not been reported yet.
a.Department of Chemistry, Sungkyunkwan University, Suwon 16419,
Korea E-mail: sson@skku.edu
b.Korea Basic Science Institute, Daejeon 34133, Korea
c. Laboratory of Nuclear Magnetic Resonance, NCIRF, Seoul National
University, Seoul 08826, Korea
In this work, we report one building block approach for hollow
terminal alkyne rich CMPs (H-TA-CMP), chemical management
of enhanced defects to prepare hollow CMPs with aliphatic
sulfonic acids (H-TA-CMP-ASO3H), and their catalytic
performance in biomass conversion to HMF.
† Electronic Supplementary Information (ESI) available: Experimental
procedures, additional characterization data of CMP materials, recycled
CMP materials, and H-control-SO3H. See DOI: 10.1039/x0xx00000x
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Fig. 1 shows the synthetic scheme for H-TA-CMP.
IR spectra of H-TA-CMPs obtained by Synthesis A showed
DOI: 10.1039/C8TA06273K
strong vibration peaks of terminal alkyne at 3295 cm . (Fig. 2b)
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-1
Even after reaction for 12 h, the H-TA-CMP showed a significant
vibration peak of terminal alkynes, indicating the enhanced
defects and the terminal alkyne rich nature of H-TA-CMPs. In
contrast, in the case of Synthesis B, vibration peaks of terminal
alkyne in CMPs gradually decreased with increasing reaction
time.16 (Fig. 2c) While surface areas of H-TA-CMPs obtained by
Synthesis A for 4, 6, and 12 h were measured to be 677, 661, and
590 m2/g, respectively, those of CMPs obtained by Synthesis B
for 4, 6, and 12 h were measured to be 698, 660, and 589 m2/g,
respectively. (Fig. S1 in the ESI)
(a)
(b)
Synthesis A
2 h
Synthesis B
2 h
4 h
6 h
*
200 nm
200 nm
4 h
4 h
12 h
200 nm
200 nm
200 nm
200 nm (c)
6 h
6 h
4 h
6 h
*
Fig. 1 Synthetic schemes for hollow terminal alkyne rich CMPs (H-TA-
CMPs) based on one building block approach (Synthesis A) and CMPs
based on two building blocks approach (Synthesis B).
200 nm
12 h
12 h
12 h
First, we prepared 1,4-dibromo-2,5-diethynylbenzene13 to use
as a building block for the one building block approach. To use
as templates, we prepared silica spheres with an average
diameter of 254 nm.14 CMP layers with a thickness of 20~25 nm
(vide infra) were formed on the silica spheres by the Sonogashira
coupling of 1,4-dibromo-2,5-diethynylbenzene. Etching of silica
templates resulted in H-TA-CMP. (Synthesis A shown in Fig. 1)
In comparison, we tried to prepare comparative hollow CMP
12 h
200 nm
Fig. 2 (a) SEM images of H-TA-CMP and CMP materials prepared for
2, 4, 6, and 12 h by the one building block approach (Synthesis A) and
two building blocks approach (Synthesis B), respectively. IR spectra
of (b) H-TA-CMP and (c) CMP materials prepared by the Synthesis A
and B for 4, 6, and 12 h, respectively.
materials
using
1,3,5-triethynylbenzene
and
1,4-
dibromobenzene. (Synthesis B shown in Fig. 1)
Considering the terminal alkyne rich nature of H-TA-CMP
materials, we introduced aliphatic sulfonic acid by the thiol-yne
click reaction to form H-TA-CMP-ASO3H. (Fig. 3a) As
described in the introduction part, solid sulfonic acid is an
important catalyst for sugar-based biomass conversion to HMF.9
It has been known that while aryl sulfonic acids are thermally
unstable11, aliphatic sulfonic acids are quite stable.12 According
to transmission electron microscopy (TEM), after incorporation
of aliphatic sulfonic acids to H-TA-CMP, the original hollow
structure was completely retained. (Fig. 3b-c). Elemental
mapping based on energy dispersive X-ray spectroscopy (EDS)
showed homogeneous distributions of S and O in H-TA-CMP-
ASO3H, supporting the successful incorporation of aliphatic
sulfonic acid to H-TA-CMP. (Fig. 3d)
Formation processes of H-TA-CMP were investigated by
scanning electron microscopy (SEM), IR spectroscopy, and the
analysis of N2 sorption isotherm curves. As shown in Fig. 2a, we
found that in the case of one building block approach (Synthesis
A), CMP materials were quickly formed on silica spheres. After
4 h, complete hollow CMPs were obtained after silica etching. In
contrast, in the two building blocks approach (Synthesis B) with
1,3,5-triethynylbenzene and 1,4-dibromobenzene, the formation
of CMPs was relatively slow and the good quality hollow CMPs
could not be obtained eventually. Instead, conventional
nonhollow CMPs were obtained after 12 h. (Fig. 2a) We
speculate that the Sonogashira coupling between 1,4-dibromo-
2,5-diethynylbenzene might be more facile than that between
1,3,5-triethynylbenzene and 1,4-dibromobenzene. In the one
building block approach, isolated yields of H-TA-CMP obtained
after 2, 4, 6, and 12 h were 127, 179, 173, and 182%,
respectively.15 In contrast, in the two building blocks approach,
isolated yields of CMP obtained after 2, 4, 6, and 12 h were 31,
70, 86, and 83%, respectively.
According to analysis of N2 sorption isotherm curves based on
the Brunauer-Emmett-Teller theory, surface areas and micropore
volumes decreased from 677 m2/g and 0.20 cm3/g (H-TA-CMP)
to 387 m2/g and 0.11 cm3/g (H-TA-CMP-ASO3H), respectively,
through incorporation of aliphatic sulfonic groups, matching
2 | J. Name., 2012, 00, 1-3
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well with the observed trends in post-synthetic modification of
COMMUNICATION
Interestingly, in the 13C NMR spectrum of H-TA-CMP-ASO3H,
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13
CMP materials in the literature.3 (Fig. 3e) While H-TA-CMPs while the C peak of internal alkynes aDt O9I3: 10p.p10m39w/Ca8sTAm06o2s7t3lyK
showed major vibration peaks at 3295, 1460, and 886 cm-1, retained (indicated by a black-dotted arrow in Fig. 3g), that of
corresponding to terminal alkyne and aromatic C=C and C-H terminal alkynes at 80 ppm significantly disappeared (indicated
vibrations, respectively, H-TA-CMP-ASO3H showed new by a green-dotted arrow in Fig. 3g), indicating higher reactivity
strong vibration peaks at 3442, 1633, and 1203 cm-1, of terminal alkynes than that of internal alkynes. New aliphatic
corresponding to vibrations of O-H (SO3H), C=C (alkene 13C peaks of H-TA-CMP-ASO3H were observed at 50 and 25~31
neighboring to sulfide), and S=O (SO3H), respectively.8 (Fig. 3f) ppm, indicating successful incorporation of aliphatic sulfonic
Solid state 13C nuclear magnetic resonance spectroscopy groups. According to elemental analysis, the content of sulfonic
(NMR) of H-TA-CMP showed aromatic 13C peaks at 136 and acids in H-TA-CMP-ASO3H was measured to be 0.713 mmol/g
125 ppm. (Fig. 3g) In addition, two kinds of alkyne 13C peaks (S: 4.56wt%).17 According to powder X-ray diffraction studies,
were clearly observed at 93 and 80 ppm, corresponding to both H-TA-CMP and H-TA-CMP-ASO3H were amorphous,
internal and terminal alkyne moieties, respectively, indicating matching well with the conventional properties of CMP
the terminal alkyne rich nature of H-TA-CMPs.
materials in the literature.1 (Fig. S2 in the ESI)
Considering aliphatic sulfonic groups in H-TA-CMP-ASO3H,
we studied its catalytic activity in the model biomass conversion
of fructose to HMF. (Fig. 4a) Fig. 4 summarizes the results.
(a)
(a)
(c)
(d)
(b)
(b)
(c)
C
S
140oC
H-control
-SO3H
H-TA-CMP
-ASO3H
120oC
100oC
O
80oC
200 nm
200 nm
1 mm
(e)
(f)
60oC
H-TA-CMP
Run1 Run2 Run3 Run4 Run5
(d)
(e)
205oC
H-TA-CMP
-ASO3H
Before
H-TA-CMP
H-TA-CMP
-ASO3H
H-TA-CMP
-ASO3H
H-control
-SO3H
200 nm
After
(g)
C2-3
C1
C5-6
C4
200 nm
C1-2,6
C3,5
Fig. 4 (a) Scheme of catalytic fructose conversion to HMF by H-TA-
CMP-ASO3H. (b) Temperature dependent catalytic conversion of
fructose to HMF by H-TA-CMP-ASO3H (2 mol% SO3H to fructose).
Biphenyl was used as an internal standard. (c) Recyclability tests of
H-TA-CMP-ASO3H and H-control-SO3H (Temperature: 100oC, time: 5
h for H-TA-CMP-ASO3H, 2 h for H-control-SO3H, 2 mol% SO3H to
fructose). H-control-SO3H with aromatic SO3H was prepared by direct
sulfonation of H-TA-CMP with ClSO3H. (Refer to the Experimental
Sections in the ESI) (d) TGA curves of H-TA-CMP, H-TA-CMP-ASO3H,
and H-control-SO3H. (e) SEM images of H-TA-CMP-ASO3H retrieved
before and after five successive reactions.
C9 C7-8
C4
Fig. 3 (a) Synthetic scheme for H-TA-CMP-ASO3H by post-synthetic
modifcation based on the thiol-yne click reaction. TEM images of (b)
H-TA-CMP and (c) H-TA-CMP-ASO3H. (d) SEM and TEM-EDS
elemental mapping images of H-TA-CMP-ASO3H. (e) N2 adsorption-
desorption isotherm curves obtained at 77K, pore size distribution
diagrams (based on the DFT method), (f) IR absorption spectra, (g)
solid state 13C NMR spectra of H-TA-CMP and H-TA-CMP-ASO3H.
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Y. Z. Khimyak and A. I. Cooper, J. Am. Chem. SVoicew. 2A0rti0c8le,O1n3lin0e
,
In the literature, the conversion of fructose to HMF was mostly
studied at high temperature of ~150oC.9 To lower the reaction
temperature, we studied temperature dependent catalytic activity
of H-TA-CMP-ASO3H (2 mol% SO3H to fructose). As shown in
Fig. 4a, while the H-TA-CMP-ASO3H showed good conversion
of fructose to HMF (91~92% yields after 5 h) at 120 and 140oC,
it maintained good catalytic activity (85% yield of HMF after 5
h) at 100oC. It is noteworthy that microporous organic polymers
with sulfonic groups have been recently developed as a solid
catalyst for fructose conversion to HMF, showing catalytic
turnover numbers (TONs) of 5.83 and 6.11 at 120 and 140oC.18
In comparison, the H-TA-CMP-ASO3H showed superior TONs
of 42.5 and 45.5 at 100 and 120oC, respectively. We think that
the excellent performance of H-TA-CMP-ASO3H is attributable
to its microporosity and thin hollow structure.19 Importantly, the
H-TA-CMP-ASO3H showed excellent recyclability in the five
successive catalytic reactions with 85, 84, 85, 83, and 82% yields
of HMF for the first, second, third, fourth, and fifth run,
respectively. (Fig. 4b) According to thermogravimetric analysis
(TGA), the H-TA-CMP and H-TA-CMP-ASO3H were stable up
to 247 and 205oC, respectively. (Figs. 4c and S3 in the ESI) SEM
and IR analysis showed that the H-TA-CMP-ASO3H recovered
after the fifth run maintained its original hollow structure and
aliphatic sulfonic acids. (Fig. 4d and S4 in the ESI)
7710-7720.
DOI: 10.1039/C8TA06273K
2
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4
5
In comparison, we prepared hollow aromatic sulfonic acids
(H-control-SO3H) as control materials by reaction of H-TA-
CMP with ClSO3H. (Experimental Section and Fig. S5 in the ESI)
As shown in Figs. 4b-c, the H-control-SO3H with aromatic SO3H
showed poor recyclability,20 poor thermal stability, and a gradual
desulfonation in IR analysis (Fig. S6 in the ESI), matching with
thermal instability of aromatic sulfonic acids in the literature.12
In conclusion, this work shows that defects can be enhanced
and utilized for functionalization of CMP materials. Versatile
defective terminal alkynes can be incorporated to CMP materials
by the Sonogashira coupling of 1,4-dibromo-2,5-
diethynybenzene. Aliphatic sulfonic acids can be easily
introduced into H-TA-CMPs by the thiol-yne click reaction of
terminal alkyne groups. The resultant H-TA-CMP-ASO3H
showed recyclable catalytic performance in fructose conversion
to HMF. We believe that more diverse functional groups can be
incorporated by the reaction of terminal alkynes of H-TA-CMP
with tailored functional reactants.
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4
Conflicts of interest
There are no conflicts to declare.
7
13 D. Wang and T. Michinobu, J. Polym. Sci., Part A: Polym. Chem.
2011, 49, 72-81.
Acknowledgements
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,
This work was supported by “Next Generation Carbon
Upcycling Project” (Project No. 2017M1A2A2042517) through
the National Research Foundation (NRF) funded by the Ministry
of Science and ICT, Republic of Korea.
62-69.
15 The quantitative yield (100%) was defined assuming complete and
nondefective networking.
16 For H-TA-CMPs, intensity ratios of the terminal alkyne peaks at
3295 cm-1 to vibration peaks at 1468 cm-1 were 0.76 (4 h), 0.63 (6
h), and 0.55 (12 h). In comparison, for CMP materials, intensity
ratios of the terminal alkyne peaks at 3296 cm-1 to vibration peaks
at 1484 cm-1 were 0.52 (4 h), 0.36 (6 h), and 0.27 (12 h).
17 Acid-based titration of H-TA-CMP-ASO3H with 0.10 M NaOH
confirmed the same amount of sulfonic acids in the materials.
Notes and references
1
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J. -X. Jiang, F. Su, A. Trewin, C. D. Wood, H. Niu, J. T. A. Jones,
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18 S. Mondal, J. Modal and A. Bhaumik, ChemCatChem 2015, 7,
View Article Online
3570-3578.
DOI: 10.1039/C8TA06273K
19 K. Cho, J. Yoo, H. -W. Noh, S. M. Lee, H. J. Kim, Y. -J. Ko, H. -
Y. Jang and S. U. Son, J. Mater. Chem. A 2017, , 8922-8926.
5
20 When we tested the hollow microporous organic polymer with aryl
sulfonic acids in ref. 10 as a catalyst for fructose conversion to
HMF, it also showed poor recyclability due to desulfonation12.
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Table of Contents
One building block approach for conjugated microporous polymers resulted in enhanced defects which were utilized for the
development of solid acid catalysts.
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