Phosphine oxide-based conjugated microporous polymers with excellent CO2 capture properties

Article abstract of DOI:10.1039/c4nj01477d

Three novel phosphine oxide-based conjugated microporous polymers TEPO-1, TEPO-2 and TEPO-3 are designed and synthesized, which are constructed using the phosphine-based building unit tris(4-ethynylphenyl)phosphine oxide with linkers tris(4-ethynylphenyl)

Full text of DOI:10.1039/c4nj01477d

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Phosphine oxide-based conjugated microporous
polymers with excellent CO capture properties†
2
Cite this:DOI: 10.1039/c4nj01477d
a
ab
a
a
c
Shanlin Qiao,‡ Wei Huang,‡ Zhengkun Du, Xianghui Chen, Fa-Kuen Shieh
a
and Renqiang Yang*
Three novel phosphine oxide-based conjugated microporous polymers TEPO-1, TEPO-2 and TEPO-3
are designed and synthesized, which are constructed using the phosphine-based building unit tris-
(
4-ethynylphenyl)phosphine oxide with linkers tris(4-ethynylphenyl)phosphine oxide, triphenylphosphine
oxide and tri(thiophen-2-yl)phosphine oxide via Sonogashira–Hagihara homo-coupling or cross-
coupling condensation reaction. The adsorption isotherms of N reveal that the Brunauer–Emmett–
Teller (BET) specific surface areas of TEPO-1, TEPO-2 and TEPO-3 are 485 m
2
2
À1
2
À1
g
, 534 m
, respectively. However, these three polymers have strong affinity for CO , which exhibit
relatively high sorption abilities for CO (273 K/1.0 bar: 6.52 wt%, 7.62 wt%, and 8.40 wt%). Meanwhile,
the TEPOs demonstrate ultrahigh hydrogen uptake and outstanding CO /CH selectivity compared to
g
and
2
À1
5
92 m
g
2
Received (in Montpellier, France)
1st September 2014,
2
Accepted 26th September 2014
2
4
analogous materials with similar BET surface areas using C, Si and N as the nodes. This work reveals
clearly that the gas uptake capacity of material is highly dependent on the length of the rigid skeleton
and the modification of functional groups in the monomer structure.
DOI: 10.1039/c4nj01477d
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Microporous organic polymers (MOPs) have spurred tremendous
scientific interest in functional materials research owing to their
Introduction
Global climate change caused by greenhouse gas emissions has intrinsic properties of large surface area, narrow pore size
attracted widespread public concern in recent decades. Excessive distribution, high flexibility in the structure design, excellent
CO emission resulting from the combustion of fossil fuels is physical and chemical stability, and low skeleton density. MOPs
2
considered as a primary factor in the greenhouse effect. Different have shown great potential in various technological and energy-
1
–3
4–7
8–10
governments and environmental agencies have encouraged the related applications, including gas storage, separation,
1
1–15
development of exploring new economic technologies to deal with heterogeneous catalysis
this issue. Capture of CO depending on physical adsorption is an for reactions. MOPs such as covalent organic frameworks
polymers of intrinsic microporosity (PIM),
addition, the utilization and storage of new environmentally porous aromatic frameworks (PAFs),
and as confined environments
1
6
2
1
7–19
20,21
effective way to fight against the global climate warming. In (COFs),
7
,22
hypercrosslinked poly-
2
3,24
friendly fuels are also potential methods to meet the environ- mers (HCPs),
mental demands. Hydrogen, owing to its zero pollution and high (CTFs),
crystalline triazine-based organic frameworks
2
5,26
9,27
and conjugated microporous polymers (CMPs)
capture and separation capacities in
calorific value of combustion, is a good candidate as star fuel have exhibited high CO
2
which has attracted great interest nowadays. However, the short- reported research studies. Normally, aqueous amine–ammonia
comings of its application are the storage and transportation solution is used to separate CO2 on a large scale relying on
resulting from its lightweight nature and fast diffusion speed. the chemical adsorption. The downside of this technology is
Therefore, finding a good way to store hydrogen and other fuel the severe corrosion problems and high energy consumption
gases is also one of the effective ways to solve the above problems. during the treating processes. While the CO
storage relying on physical adsorption on MOPs is a promising
method to deal with the problem of excess CO emissions,
2
capture and
a
2
CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and
Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China.
E-mail: yangrq@qibebt.ac.cn; Fax: +86 532 80662778; Tel: +86 532 80662700
University of Chinese Academy of Sciences, Beijing 100049, China
Department of Chemistry, National Central University, 300 Jhong-Da Road,
Chung-Li 32001, Taiwan
because of the physicochemical stability and lower regeneration
energy penalty of MOPs. Meanwhile, MOPs also exhibit great
potential in the storage of small gas molecules such as hydrogen,
methane and acetylene.
Conjugated microporous polymers (CMPs) as a sub-family of
MOPs have attracted extensive attention not only because they
can be prepared by different synthetic methods, but also they
b
c
†
Electronic supplementary information (ESI) available: Experimental details for
the synthesis of m-1 to m-3. See DOI: 10.1039/c4nj01477d
These authors contributed equally to this work.
‡
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3
combine the porosity with the extended p-conjugation skeleton. (m-3) were synthesized according to the literature method.
The adsorption ability of small gases of CMPs relies greatly on The details of synthesis are shown in the ESI.†
the BET surface areas, the pore size and the isosteric enthalpy
Synthesis of TEPO polymers
of materials. In order to enhance the CO2 capture ability of
CMPs, several strategies have been employed, for example The TEPO-1 polymer was prepared by palladium-catalyzed
1
4
generating the constricted pores, opening metal-sites, post- homo-coupling of tris(4-ethynylphenyl)phosphine oxide (m-1).
synthetic modification, and introducing CO -philic functional And TEPO-2 and TEPO-3 were prepared using Sonogashira–
groups such as N-rich and O-rich groups into the polymer.
2
2
8
Hagihara coupling condensation reactions between tris(4-ethynyl-
These novel materials have exhibited a high CO
2
uptake capa- phenyl)phosphine oxide (m-1) and tris(4-bromophenyl)phosphine
2
À1
À1
city, such as APOP-1 (SBET = 1298 m g , 4.26 mmol g at oxide (m-2) and tris(5-bromothiophen-2-yl)phosphine oxide (m-3),
2
9
2
À1
À1
2
2
2
73 K/1.31 bar), CPOP-1 (SBET = 2220 m
g
, 21.2 wt% at respectively. The molar ratio of ethynyl to bromine functionalities
3
0
2
À1
73 K/1.0 bar) and Co-CMP (SBET = 965 m g , 79.3 mg g at in the monomer feed was set at 1.5 : 1 as the reports of CMPs
98 K/1.0 bar). In the past few years, CMPs were constructed synthesized by the Cooper group and our previous work.
1
4
33,38
The
from carbon–carbon bonds or carbon–heteroatoms through details of the preparation of TEPOs are as follows.
transition-metal-mediated cross coupling. Different main group TEPO-1. m-1 (200 mg, 0.57 mmol), tetrakis(triphenylphosphine)-
elements of C, N and Si as the nodes of the CMP frameworks palladium(0) (20.2 mg, 0.017 mmol) and copper(I) iodide (6.5 mg,
have been reported owning their excellent performance in CO 0.034 mmol) were added into the solvent of DMF (4 mL) and TEA
2
capture and sequestration. Phosphorus which is a light element (4 mL), and the mixture was degassed by the freeze–pump–thaw
with facile chemical modification properties, however, has not cycles under an Ar atmosphere to rigorously exclude oxygen. The
3
1–33
received enough attention as the node of CMPs so far.
It is resulting mixture was slowly heated to 80 1C and stirred for 72 h.
an attractive work to intercalate the phosphorus group into the After cooling to room temperature, the brown precipitate was
skeleton and modify it to functionalize the CMPs. In our filtered and washed with chloroform, water, acetone and methanol
previous work, we have succeeded in synthesizing two new to remove any unreacted monomers or catalyst residues. Further
functional thienyl-phosphine microporous polymers containing purification of the polymer was carried out by Soxhlet extraction
the phosphorus group which had exhibited great carbon dioxide with methanol for 24 h and THF for another 24 h. The product was
3
3
capture. And the polymer containing PQO groups show higher then dried under vacuum for 24 h at 80 1C to give 188 mg dark
CO capture capacity than the one with PQS groups under the brown stiff solid (94%). Anal. calcd. for TEPO-1: C, 80.63; H, 4.35.
2
same conditions. Along these lines, here three kinds of CMPs Found: C, 79.96; H, 4.37.
based on the phosphine-oxide unit were designed and synthe-
sized in expectation of excellent performance.
TEPO-2. m-1 (105 mg, 0.3 mmol), m-2 (103 mg, 0.2 mmol),
tetrakis(triphenylphosphine)palladium(0) (10.5 mg, 0.009 mmol)
In order to get different morphologies and a high uptake and copper(I) iodide (3.6 mg, 0.018 mmol) were added into the
capacity of carbon dioxide and other gases, two methods were solvent of DMF (2.5 mL) and TEA (2.5 mL), and the mixture was
employed to optimize the polymer structures. In this paper, we degassed by the freeze–pump–thaw cycles under an Ar atmo-
take TEPO-2 as the reference. Firstly, we design TEPO-1 which sphere and following the same steps as TEPO-1. The final
has one more triple bond in the monomer structure compared product went through the same workup procedure to give
to TEPO-2, which can help us understand the relationship of 191 mg light brown powder (92%). Anal. calcd. for TEPO-2: C,
performance of CMPs with the length of the rigid skeleton. And 79.45; H, 4.62. Found: C, 79.04, H, 4.46.
in attempting to functionalize TEPO-2, TEPO-3 was designed by
TEPO-3. This polymer was synthesized following the method
utilizing the thienyl functional group instead of the benzene mentioned above through coupling condensation reaction
ring in TEPO-2. The electron-rich thiophene group is chosen between m-1 (105 mg, 0.3 mmol) and m-3 (160 mg, 0.2 mmol).
because it is a Lewis base which may have strong interaction The final product followed the same workup procedure and
3
4
with electron-deficient CO
2
molecules. Finally, the effects of gave light brown powder (251.75 mg, 95%). Anal. calcd. for
the rigid length and functionalization of the monomer skeleton TEPO-3: C, 58.43; H, 2.94; S, 23.40. Found: C, 58.72; H,
on the performance of porous materials are investigated.
2.78; S, 22.94.
Characterization
1
13
H and C NMR spectra were recorded on a Bruker AV 600 MHz
spectrometer with tetramethylsilane (TMS) as the internal
reference. Solid-state C CP/MAS NMR measurements were
carried out using a Bruker Avance III model 400 MHz NMR
Experimental section
Materials
1
3
All reagents and solvents, unless otherwise specified, were pur- spectrometer at a MAS rate of 5 kHz. FT-IR spectra were
chased from J&K, Aldrich and Acros Chemical Co. and used as collected in attenuated total reflection (ATR) mode on a
received. Tetrahydrofurane (THF), dimethyl formamide (DMF) and Thermo Nicolet 6700 FT-IR spectrometer. Scanning electron
triethylamine (TEA) were distilled prior to use. Tris(4-ethynyl- microscopy (SEM) was recorded using a Hitachi S-4800 with
3
5,36
phenyl)phosphane oxide (m-1),
tris(4-bromophenyl)phosphine acceleration voltage 3 kV and working different distances.
3
7
oxide (m-2) and tris(5-bromothiophen-2-yl)phosphine oxide Samples were coated by a thin layer of Au before investigation.
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Gas sorption analysis
The three polymers were degassed at 120 1C for 10 h under
vacuum before analysis. BET surface areas and pore size dis-
tributions of TEPOs were measured by N
at 77 K. H uptake was tested at 77 K up to the pressure of
and CH isotherms were measured at 273 K and
98 K up to 1.1 bar. All the samples were tested using an
2
adsorption–desorption
2
1
2
.1 bar. CO
2
4
Autosorb-iQ-MP-VP volumetric adsorption analyzer after the
same degassing procedure.
Results and discussion
Structural characterization
The three phosphine-containing microporous polymers were
synthesized via Sonogashira–Hagihara coupling condensation
reaction, and the structures of TEPOs are shown in Scheme 1.
The molecular levels of the TEPOs were investigated by
1
3
31
C solid NMR and P solid NMR spectra as shown in Fig. 1.
The –CRC– linkages have been confirmed by the character-
istic resonance of triple-bonded carbon with a corresponding
peak at around 93 ppm (Fig. 1a). In addition, the signals of the
carbon chemical shift in the range of 120–140 ppm are related
to the aromatic carbon atoms of building blocks. The reso-
2
nance at 128 ppm is assigned to the sp benzene connected
with the alkynylene (CAr–CR). The observed appearance of
2
resonance at 133 ppm belongs to the sp carbons in the
3
1
benzene rings (CAr–H). P-NMR measurements were carried
out to confirm the presence of the –PQO bond. It is showed Fig. 1 (a) C CP-MAS NMR. (b) P CP-MAS NMR of the TEPOs.
in Fig. 1b that the TEPOs have a signal at 29 ppm corre-
13
31
sponding to the –PQO stretch. Paying special attention to
TEPO-3, there are two obvious peaks which correspond to the
In the FR-IR spectra (Fig. 2), a strong stretch is observed at
À1
different situations of the –PQO bond in the structure, and the 1186 cm , which confirms the presence of –PQO in the
À1
peak around 4 ppm is assigned to –PQO connecting with polymers. Meanwhile the band of –CRC– stretch at 2202 cm
1
3
31
thiophene groups. The results of C NMR and P NMR is found in the spectra of TEPOs. SEM images (Fig. 3) for TEPOs
confirm the structure of TEPOs and also indicate that this show that the polymers have similar amorphous aggregation
cross-coupling reaction is effective in the synthesis of conju- morphologies as the reported CMPs. The images here are
gated organic polymers.
observed from different distances so that one can see the
Scheme 1 Structures of TEPOs.
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Fig. 2 FT-IR spectra of the TEPOs.
Fig. 3 Scanning electron microscopy (SEM) images at different distances
for (a) TEPO-1 at 8.2 mm, (b) TEPO-2 at 8.1 mm and (c) TEPO-3 at 6.7 mm
with magnification of 30k.
structure clearly. It’s easy to recognize that the morphologies of
TEPOs are spherular.
Fig. 4 (a) Nitrogen adsorption–desorption isotherms of the TEPOs mea-
sured at 77 K. (b) Pore size distribution curves; the curves of TEPO-2 and
3
À1
3
À1
TEPO-3 were shifted vertically by 2.0 cm
g
and 4.0 cm
g for clarity.
Porosity measurements
The BET surfaces and pore structures of the TEPOs were
characterized by nitrogen adsorption–desorption isotherms of around 1.30 nm, while the pores of TEPO-2 and TEPO-3 are
samples at 77 K. Samples were degassed at 120 1C for 10 h centered at two main sizes 1.08 nm and 1.31 nm. It should be
under vacuum before analysis. The corresponding nitrogen pointed out that there are some mesopores in the TEPO-1 (pore
2
adsorption isotherms and pore size distributions are shown width 42 nm), which is corresponding to its N adsorption
in Fig. 4. According to the IUPAC classification, all of the TEPOs isotherm (Fig. 4a). The pore size distribution gives us strong
are typical microporous materials, and the full reversible proof that the pore structure of materials is highly dependent on
adsorption–desorption of nitrogen with rapid uptake occurred the length of the rigid skeleton which can explain why the
0
at a low relative pressure (P/P = 0–0.1), indicating the perma- dominant pore size and pore volume of TEPO-1 are larger than
nent microporous nature of all the TEPOs. The BET specific the other two analogues and the TEPO-2 shares a similar pore
2
À1
2
À1
2
À1
surface areas are 485 m g , 543 m g and 592 m g for size distribution as TEPO-3.
TEPO-1, TEPO-2 and TEPO-3, respectively. These surfaces are
3
3
Gas uptake studies
comparable to previous reported phosphine-containing CMPs.
The upturn in the isotherm of TEPO-1 at relative higher pres-
CO adsorption. To investigate the CO uptake of the TEPOs,
2
2
sures indicates that the TEPO-1 possessed mesopores or macro- the isotherms of the TEPOs were measured up to 1.1 bar at
pores, which can result in the condensation of nitrogen in the 273 K and 298 K, respectively. As shown in Fig. 5a, at 273 K and
3
9–42
macropores and interparticle voids.
TEPO-1 and TEPO-2 can be explained as the general trend, when 8.40 wt% for TEPO-1, TEPO-2 and TEPO-3, respectively. It is
similar monomers were used, polymers prepared from the larger obvious that all the TEPOs show significant uptake of CO
2
The difference between 1.0 bar, the CO uptake of TEPOs is 6.52 wt%, 7.62 wt%,
2
monomers showed lower surface areas, as the reported CMPs although their surfaces are moderate and no saturation is
constructed with longer connecting struts have lower BET sur- observed in the measured range of pressures and temperatures.
3
8
face areas. As the dynamic effective diameter of the thiophene It means that the CO storage of TEPOs can be enhanced with
2
group is smaller than the benzene ring, TEPO-3 shows a higher the pressure increasing or temperature decreasing. To provide
BET surface than TEPO-2. This result coincides with our expecta- a better understanding of the CO uptake properties, the CO2
2
tion. Analysis on the pore size distribution of the TEPOs (Fig. 4b) isosteric enthalpies of adsorption (Qst) were calculated from the
2
shows that all the samples are micropores mainly, as the pore CO sorption isotherms measured at 273 K and 298 K in terms
width is less than 2 nm. The pore center for TEPO-1 is located of the Clausius–Clapeyron equation and the curves are shown
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demonstrate ultrahigh hydrogen storage properties under the
same condition compared to other microporous polymers whose
2
À1
BET surface areas are less than 600 m g
.
The CO in the natural gas would reduce the net heat of fuel
2
combustion and corrode pipelines. Therefore, the separation of
CO
CO
2
over CH
4
is important for the industry. The selectivity of
2
/CH is calculated from the initial slopes of adsorption
4
isotherms at low pressure (Fig. 6b), and the separation cap-
abilities of these polymers are outstanding. The selectivity of
TEPO-1 to TEPO-3 is 12.6, 14.1 and 15.5 at 273 K, which is
higher than some reported materials, for example the selectivity
Fig. 5 (a) CO
2
adsorption properties at 273 K and 298 K. (b) The isosteric
heats of CO
2
adsorption for the TEPOs.
4
3
10
of ZIF-78 is 10, P-1 is 4, and 2-D MOF is 13 which is with open
4
4
in Fig. 5b. It can be observed that the isosteric heat of TEPO-1 to sites. Such good selectivity of the TEPOs is expected to arise
À1
À1
À1
TEPO-3 is about 26.88 kJ mol , 26.34 kJ mol and 27.60 kJ mol
at the near zero coverage, respectively. Then, the heat values of able phosphine-oxide units and CO
from the strong interactions between the polymers with polariz-
2
molecules. The excellent
À1
TEPO-1 and TEPO-2 dropped to about 24 kJ mol with the performance of TEPO-3 may be ascribed to the electron-rich
loading increasing; however, the Qst of TEPO-3 remained stable, thiophene group which is a Lewis base having strong interaction
À1
À1
2
decreasing from 27.60 kJ mol to 27.49 kJ mol , with only with electron-deficient CO molecules. The detailed porosity
À1
negligible (0.11 kJ mol ) variation, this may be attributed to the structural parameters and gas uptake capacities of TEPOs are
electron-rich thiophene functional groups in the molecule. As the shown in Table 1.
heats of adsorption remain below the energy of the chemical bond
but are large enough to uptake CO , the TEPOs are perfect
2
candidates for CO adsorption and facile release which is mean- Conclusions
2
ingful for the reutilization of materials in practical applications.
We have successfully synthesized three tris(4-ethynylphenyl)-
It is well known that materials with low-density and high-
phosphine oxide (TEPO) based microporous polymers named
porosity are promising materials for gas storage applications.
TEPO-1, TEPO-2 and TEPO-3 through Sonogashira–Hagihara
Conjugated microporous polymers (CMPs) are good candidates
coupling condensation reaction. Although the BET surface area
of the polymers is less than 600 m g , the materials show
relatively high sorption abilities for carbon dioxide (6.52 wt% to
for gas adsorption and storage due to their high specific surface
2
À1
area, narrow pore distribution and low framework density.
Hydrogen and methane storage capacities of the TEPOs were
explored, as both gases have attractive cleaning energy. The
hydrogen uptake for TEPOs at 77 K/1.0 bar is 0.89 wt%, 0.97 wt%
and 1.02 wt%, respectively (shown in Fig. 6a). Considering that
the surface areas of the TEPOs are moderate, the three materials
8
1
.40 wt% at 273 K/1.0 bar) and hydrogen uptake (0.89 wt% to
.02 wt% at 77 K/1.0 bar) compared to materials with similar
Brunauer–Emmett–Teller (BET) surface areas. Interestingly, the
polymers obtained exhibit remarkable performance in separat-
ing CO over CH as the selectivity of CO /CH is as high as
2
4
2
4
12.6, 14.1 and 15.5 at 273 K, respectively. From the comparison
of TEPO-1 and TEPO-2, when monomers with the same
chemical component were used, polymers prepared from the
larger building blocks showed lower surface areas as they went
against to build the stiff porous structure. Compared with
TEPO-2, TEPO-3 shows higher gas uptake capacity which can
be attributed to the electron-rich thiophene group having a
stronger interaction with small gas molecules and a shorter
rigid length than the benzene ring. This work clearly reveals
that the gas uptake capacity of materials is highly dependent on
Fig. 6 (a) H
2
adsorption properties at 77 K. (b) Initial CO
2
and CH
4
uptake the length of the rigid skeleton and the modification of func-
slopes of the TEPOs at 273 K.
tional groups in the monomer structure.
Table 1 Surface properties and gas uptake for the TEPOs
CO
2
uptake [wt%]
H
2
uptake [wt%]
2 4
CO /CH selectivity
a
2
À1
b
3
À1
c
3
À1
Polymer
S
BET [m g
]
V
Micro [cm g
]
V
Total [cm g
]
VMicro/VTotal
273 K
298 K
77 K
273 K
TEPO-1
TEPO-2
TEPO-3
485
543
592
0.11
0.21
0.22
0.82
0.30
0.30
0.13
0.69
0.72
6.52
7.62
8.40
3.65
3.93
5.33
0.89
0.97
1.02
12.6
14.1
15.5
a
b
c
Surface area calculated from the N
2
isotherm. The micropore volume derived using the t-plot method. Total pore volume at P/P
0
= 0.99.
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Acknowledgements
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Technology of China (2010DFA52310), Shandong Provincial
Natural Science Foundation (ZR2011BZ007), and Qingdao
Municipal Science and Technology Program (11-2-4-22-hz).
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