A novel metalloporphyrin-based conjugated microporous polymer for capture and conversion of CO2

Article abstract of DOI:10.1039/c4ra16675b

A novel conjugated microporous polymer was solvothermally synthesized using an aluminum porphyrin as a main building block, which had a high Brunauer-Emmett-Teller specific surface area up to 839 m² g^-1 and a pore volume of 2.14 cm³ g^-1. The polymer displayed excellent capacity to capture carbon dioxide (4.3 wt%) at 273 K and 1 bar, and good catalytic activity for cyclic carbonate synthesis with TOF up to 364 h^-1.

Full text of DOI:10.1039/c4ra16675b

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PAPER
A novel metalloporphyrin-based conjugated
microporous polymer for capture and conversion
of CO2
Cite this: RSC Adv., 2015, 5, 31664
a
a
a
Xingfeng Sheng,ab Hongchen Guo, Yusheng Qin, Xianhong Wang
*
*
and Fosong Wanga
A novel conjugated microporous polymer was solvothermally synthesized using an aluminum porphyrin as
a main building block, which had a high Brunauer–Emmett–Teller specific surface area up to 839 m2 gꢀ1
Received 19th December 2014
Accepted 27th March 2015
and a pore volume of 2.14 cm3
(4.3 wt%) at 273 K and 1 bar, and good catalytic activity for cyclic carbonate synthesis with TOF up to
364 hꢀ1
g
ꢀ1. The polymer displayed excellent capacity to capture carbon dioxide
DOI: 10.1039/c4ra16675b
www.rsc.org/advances
.
because the porphyrin framework can be carefully designed,
which may provide an opportunity to further enhance catalytic
activity. However, these homogeneous catalysts still have diffi-
culty in industrial applications because they are expensive and
difficult to be recovered or reused. Thus, it is necessary to
develop highly efficient heterogeneous catalysts for synthe-
sizing cyclic carbonates.
Induction
There is much environmental concern about the increasing
levels of atmospheric carbon dioxide (CO2) which is suspected
to be a primary factor in global climate change.1 Thus, CO2
capture and sequestration (CCS) technologies have been
developed to effectively reduce its accumulation in the atmo-
sphere during the past decade.2 Due to the drawbacks of high
energy demands for the chemical sorption method of CO2 in
industry, researchers pay much attention to developing alter-
native approaches for CCS. Numerous porous materials, such as
zeolites,3 activated carbons4 and metal–organic frameworks
(MOFs),5 have been found to effectively capture CO2, which
exhibit great potential in industrial applications.
On the other hand, chemical conversion of captured CO2 to
large scale chemicals is attractive since it is an abundant,
inexpensive and nontoxic C1 resource. One of the chemicals is
cyclic carbonate formed from cycloaddition of CO2 and
epoxide,6 which are widely used as polar aprotic solvent, elec-
trolyte in lithium-ion battery, fuel additive and intermediate for
polycarbonate.7 Because of high thermodynamic stability of
CO2,8 numerous catalyst systems for cyclic carbonate synthesis
have been reported,9 especially some homogeneous catalyst
systems, such as salen metal complexes10 and metal-
loporphyrins,11 which show higher catalytic activities under
mild conditions compared with heterogeneous catalysts.
Recently, Ema's group12 developed bifunctional porphyrin
catalysts, which showed high turnover number numbers (TON
¼ 103 000) for the synthesis of cyclic carbonates. Furthermore,
metalloporphyrins are considered to be promising catalysts
Currently, conjugated microporous polymers (CMPs) are of
great interest because of their extraordinarily high surface area,
well-dened pore structure and extended p-conjugation effect.13
A series of CMPs have been developed for applications in areas
such as gas sorption,14 conducting material,15 molecular sepa-
ration16 and catalysis.17 For example, metallosalen-based CMPs
have been reported, which had high surface area and ability to
catalyze the coupling of CO2 and epoxides in mild reaction
conditions.18 Chen's group prepared a metalloporphyrin-based
CMP with high catalytic activity for the oxidation of thiols.19
Furthermore, Liu et al. reported metalloporphyrin based CMPs
which displayed excellent CO2 uptake capacity (up to 13.9 wt%)
at 273 K and 1 bar.20 Subsequently, Echegoyen and coworkers
developed a new metalloporphyrin based CMP which exhibited
very good selectivity for CO2/CH4 adsorption.21 CMP has the
physical backbone and structure of the conjugated framework
in addition to the chemical properties of the incorporated
metal–organic moieties, which may have capability of not only
CO2 capture but also its simultaneous conversion. CMPs based
on metalloporphyrin units have shown good potential for CO2
capture,22 however, to the best of our knowledge, the catalytic
performance of metalloporphyrin-based CMPs for the coupling
of CO2 and epoxides have rarely been explored. It is interesting
to develop metalloporphyrin-based CMP for both CO2 capture
and its simultaneous conversion, which also could be recovered
from the product easily.
aKey Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, People's Republic of China.
E-mail: ysqin@ciac.ac.cn; xhwang@ciac.ac.cn
In this study, aluminum porphyrin-based conjugated
microporous polymer (Al-CMP) has been solvothermally
bUniversity of Chinese Academy of Sciences, Beijing 100039, People's Republic of China
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synthesized. As expected, it is insoluble in common organic solution was stirred for another 1 h. Aer ltration, the ltrate
solvents and water, and can be recovered from the reaction was concentrated using a rotary evaporator to produce a residue
system easily. The Al-CMP exhibits high surface area, and is which was puried by column chromatography (silica, petro-
capable of capturing and transforming CO2 to cyclic carbonates leum ether/dichloromethane v/v ¼ 1 : 1) to obtain a purple solid
in mild reaction conditions.
in 22% yield.
1H NMR (300 MHz, CDCl3, d): 8.84 (s, 8H), 8.05 (d, 8H), 7.88
(d, 8H), ꢀ2.86 (s, 2H; NH). 13C NMR (75 MHz, CDCl3, d): 141.00,
135.98, 131.33, 130.15, 122.81, 119.15.
Experimental
MS (MALDI-TOF): m/z ¼ 926.9 [M + H]+ (calcd 926.9).
Compound 2. A solution of compound 1 (1.0 mmol) in 20 mL
dry dichloromethane was degassed with a stream of argon for
5 min in an ice-bath. Aer 1.3 mmol Et2AlCl was added slowly,
the reaction solution was heated to room temperature and
stirred for 1 h. The mixture was concentrated using a rotary
evaporator to produce a residue which was puried by column
chromatography (neutral alumina, dichloromethane/methanol
v/v ¼ 10 : 1) and obtained as a purple solid in 97% yield.
1H NMR (300 MHz, DMSO-d6, d): 9.03 (s, 8H), 8.13 (d, 8H),
8.04 (d, 8H). 13C NMR (75 MHz, DMSO-d6, d): 146.48, 140.03,
135.85, 132.29, 130.07, 122.25, 119.03.
General procedures and methods
All reactions of air- and/or moisture-sensitive complexes and
product manipulations were performed under inert atmosphere
using standard Schlenk technique or in a glove box. Dichloro-
methane (CH2Cl2), chloroform (CHCl3), acetonitrile (CH3CN),
pyrrole, propylene oxide (PO) were distilled over CaH2 under
inert atmosphere. The CO2 gas (99.999%) was purchased and
used without further purication. Other chemicals were
obtained from Aldrich or Acros, and used as received without
further purication unless otherwise stated.
Solution nuclear magnetic resonance (NMR) spectra were
recorded at ambient atmosphere using a Bruker ARX-300
spectrometer at room temperature in deuterated chloroform
(CDCl3) or dimethyl sulfoxide (DMSO-d6), tetramethylsilane
(TMS) was used as internal reference. Matrix-assisted laser
desorption/ionization time-of-ight mass spectroscopy
(MALDI-TOF/MS) was performed on a Bruker autoex III mass
spectrometer. Fourier transform infrared (FTIR) spectrum was
recorded on Bruker Optics Tensor 27 spectrometer. The spec-
tral resolution is 2 cmꢀ1. UV-Visible spectra for complex 2 was
recorded on HITACHI U-4100 spectrophotometer using CHCl3
as the solvent. UV-Visible diffuse-reection spectra for Al-CMP
was recorded on SHIMADZU UV-2550 spectrophotometer.
1H–13C CP/MAS solid-state NMR spectra were obtained by a
Bruker AVANCE III 400 WB spectrometer. Scanning electron
microscopy (SEM) image was obtained on a XL30 ESEM FEG.
High-resolution transmission electron microscope (HR-TEM)
image was obtained on a Tecnai G2 F20 S-TWIN. Thermog-
ravimetry analysis (TGA) was performed on a Perkim-Elmer
Pyris 1 TGA thermal analyzer under a N2 atmosphere at a
heating rate of 10 ꢁC minꢀ1 from ambient temperature to
800 ꢁC. Inductively coupled plasma (ICP)-optical emission
spectroscopy (OES) was performed using a ThermoScientic
iCAP6300 instrument. Nitrogen adsorption isotherms at 77 K
were measured in liquid nitrogen bath with an Autosorb-IQ2
instrument (Quantachrome). CO2 adsorption isotherms were
measured by a Micromeritic ASAP 2000 instrument at 273 K
and 298 K.
UV (CHCl3) lmax 419, 518, 549, 589, 631 nm. Elemental
analysis for C44H24AlBr4ClN4 (990.74): calcd C 53.34, H 2.44, Al
2.72, Cl 3.58, N 5.66; found C 53.29, H 2.42, Al 2.75, Cl 3.55,
N 5.68.
MS (MALDI-TOF): m/z ¼ 950.8 [M ꢀ Cl]+ (calcd 950.8).
Al-CMP. Al-CMP was obtained as reported.18b Compound 2
(0.57 mmol), 1,3,5-triethynylbenzene (180 mg, 1.2 mmol), CuI
(50 mg) and tetrakis-(triphenylphosphine) palladium(0)
(100 mg) were dissolved in a mixture of toluene (15 mL) and
triethylamine (6 mL). The reaction mixture was heated to 40 ꢁC
and stirred for 1 h under an argon atmosphere (to exclude
oxygen and prevent any homocoupling of the alkyne mono-
mers). Next, the reaction mixture was heated to 80 ꢁC, stirred for
72 h and then cooled to room temperature. The insoluble
precipitated polymer was ltered and washed four times with
dichloromethane, methanol, water and acetone to remove any
unreacted monomers or catalyst residues. Further purication
of the polymer was carried out by Soxhlet extraction with
methanol and dichloromethane (volume ratio ¼ 1 : 1) for 48 h.
The product was dried in a vacuum for 24 h at 70 ꢁC and isolated
as a brown powder.
UV lmax 421, 550, 601, 641 nm. Elemental analysis for
Al-CMP [(C60H28AlClN4)n]: calcd C 83.09, H 3.25, Al 3.11, Cl 4.09,
N 6.46; found C 83.15, H 3.79, Al 2.81, Cl 3.63, N 6.52.
Cycloaddition reaction
Synthetic procedure for Al-CMP
Propylene oxide, Al-CMP and cocatalyst were added to a
stainless-steel autoclave with a magnetic stirrer in a glove
box. CO2 was pressurized to this mixture and the reaction was
operated under determined conditions. Aer reaction, the
The synthesis of Al-CMP is illustrated in Scheme 1.
The detailed synthesis process is listed in the following.
Compound 1. Compound 1 was obtained as reported.23
A
solution of 4-bromobenzaldehyde (1.9 mmol) and pyrrole autoclave was cooled to room temperature, and the CO2
(1.9 mmol) in 380 mL dry dichloromethane was degassed with a pressure was released by opening the outlet valve. Then the
stream of argon for 10 min. The solution was stirred for 1 h aer crude reaction mixture was obtained to calculate the
triuoroacetic acid (0.37 mL) was added, then 2,3-dichloro- conversion by 1H NMR spectroscopy in deuterated
5,6-dicyano-p-benzoquinone (DDQ) (0.9 g) was added and the chloroform.
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Scheme 1 Synthesis of Al-CMP.
aromatic rings in the polymer. Therefore, these results clearly
Results and discussion
Al-CMP Characterization
indicated that the cross-coupling of compound
1,3,5-triethynylbenzene formed a conjugated polymer.
2 and
The morphological structure of Al-CMP was investigated by
SEM and HR-TEM, as shown in Fig. 3. The SEM image of
Al-CMP showed very small granules with an average size of 47
nm. According to the HR-TEM image, nanometer-sized pores
were presented in the bulk of the polymer.
Al-CMP was synthesized from the reaction of compound 2 with
1,3,5-triethynylbenzene in the presence of a Pd(0) catalyst in
toluene. The resultant brown powdery compound had a low
density, and was not soluble in any common organic solvents or
water. The polymerization process was monitored via IR spec-
troscopy. Fig. 1 displayed the IR spectra before and aer poly-
merization. The disappearance of the C–Br vibrations (n ¼ 483
cmꢀ1) of the starting material indicated both the complete
consumption of monomer (compound 2) and the success of
phenyl-alkynyl coupling.
The molecular structure of Al-CMP was investigated by
1H–13C CP/MAS solid-state nuclear magnetic resonance (NMR).
As shown in Fig. 2, the peaks at 91.0 and 82.0 ppm were
assigned to sp-hybridized –C^C– sites. The peaks at approxi-
mately 115.0–150 ppm were ascribed to the carbon atoms of the
The porous properties of Al-CMP were investigated by
nitrogen adsorption analyses at 77 K. According to IUPAC
classication, Al-CMP showed type I nitrogen adsorption
isotherms as shown in Fig. 4a. The high uptake at very low
pressures (0–0.1 bar) indicates the material was microporous.
With increase of pressure, the nitrogen uptake increased
slightly, indicating the existence of a little external surface area
due to the presence of very small particles. Therefore, Al-CMP
has a predominantly microporous structure in its framework.
The sharp increase in the nitrogen uptake at high relative
pressure may be attributed in part to interparticulate porosity
associated with the meso- and macrostructures of the sample. A
surface area of 839 m2 gꢀ1 was obtained by applying the
Fig. 2 Solid-state 1H–13C CP/MAS NMR spectra of Al-CMP recorded
Fig. 1 IR spectra of monomer (compound 2) and polymer (Al-CMP).
31666 | RSC Adv., 2015, 5, 31664–31669
at a spinning speed of 8 kHz.
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The content of Al in polymer was found to be 2.81 wt%, revealed
1.04 mmol gꢀ1 metal-porphyrin species for Al-CMP, which was
slightly less than the theoretical value of 3.11 wt%, indicating
that a small portion of porphyrin ligands in the Al-CMP was not
coordinated to metal atoms. Furthermore, Al-CMP was stable at
a high temperature up to ꢂ400 ꢁC, displaying good thermal
stability (Fig. 4c).
Because of its high surface area and pore volume, abundant
nitrogen atoms and coordinated metal sites, Al-CMP exhibited a
good CO2 uptake capacity as shown in Fig. 4d. When the pres-
sure P (actual pressure) approached 760 mm Hg (that is, P/P0
approached 1), the CO2 uptake reached 27.43 mg gꢀ1 at 298 K
and 43.12 mg gꢀ1 at 273 K. Its adsorption curves gradually
increased with increasing pressure, suggesting further high
adsorption capacity for carbon dioxide at elevated pressure.
Fig. 3 SEM (a) and HR-TEM (b) of Al-CMP.
Catalytic performance of Al-CMP
Considering the porosity of Al-CMP and the existence of metal-
porphyrin species, Al-CMP was used as a solid catalyst for the
coupling of carbon dioxide and propylene oxide (PO). The
results were summarized in Table 2.
Generally, a cocatalyst, such as amine, phosphine or
quaternary onium salt, played a signicant role in the coupling
of CO2 and PO.27 In the absence of any cocatalyst, the coupling
reaction by Al-CMP yielded only 1.5% PC at 70 ꢁC (Entry 1). Once
the cocatalyst was used, the catalytic activity of Al-CMP
increased notably (Entries 2–5). With PPNCl as cocatalyst,
Al-CMP exhibited high catalytic activity and 74% PO conversion
ꢁ
was obtained at 70 C and 3 MPa for 5 h, while PO conversion
Fig. 4 (a) N2 adsorption–desorption isotherms of Al-CMP (77 K), (b)
pore size distribution diagrams (based on DFT method) of Al-CMP, (c)
TGA curve of Al-CMP, and (d) CO2 sorption isotherms for Al-CMP at
273 and 298 K, respectively.
was low (27%) with PPNCl alone (Entry 11). In addition, no
other by-products were observed in the conversion to propylene
carbonate (PC) by Al-CMP. When PPNCl was replaced by TBAB,
the catalyst system gave a relatively low catalytic activity and the
PO conversion was only 28%. When amines (DMAP, MeIm) were
employed as cocatalysts, the PO conversions decreased signi-
cantly to below 10%. Therefore, PPNCl was the best cocatalyst in
this catalyst system. Furthermore, the molar ratio of catalyst
(Al-CMP) to co-catalyst (PPNCl) was also a major factor for the
catalytic activity (Entries 2 and 6). When the molar ratio of
Al-CMP to PPNCl was changed from 1 : 10 to 1 : 1, the PO
conversion decreased from 74% to 22%.
As observed, temperature also had a strong inuence on the
catalytic activity. As shown in Table 2, a rise of temperature from
25 to 100 ꢁC favored PO conversion. At 25 ꢁC, PO conversion was
only 3%. With temperature raising, PO conversion increased
exponentially, and reached to 91% at 100 ꢁC. Generally, CO2
Brunauer–Emmett–Teller (BET) model and a surface area of
1278 m2 gꢀ1 was obtained by applying the Langmuir model
within the pressure range of P/P0 ¼ 0–1 bar (Table 1). The pore-
size distribution diagram based on the density functional
theory (DFT) method in Fig. 4b also showed a typical micro-
porous nature of the material, and the pore size was estimated
as 1.42 nm. According to Table 1, the total pore volume of
Al-CMP was 2.14 cm3 gꢀ1, which was substantially larger than
the volume of many porphyrin-based CMPs, including MMPF-2
(0.61 cm3 gꢀ1),24 CoP-CMP (0.36 cm3 gꢀ1),25 PCPF-1
(0.86 cm3 gꢀ1).26 Metal (Al) was detected in polymer by induc-
tively coupled plasma-optical emission spectroscopy (ICP-OES).
Table 1 Physical properties of Al-CMP
Polymer SBETa (m2 gꢀ1
)
SLang (m2 gꢀ1
)
Smicrob (m2 gꢀ1
)
Vtot (cm3 gꢀ1
)
Vmicrod (cm3 gꢀ1
)
Mcalce (wt%) MICP (wt%) CO2 uptakeg (mg gꢀ1
)
c
f
Al-CMP 839
1278
229
2.14
0.103
3.11
2.81
27.43
a
b
Specic surface area calculated from the nitrogen adsorption isotherm using the BET method. Micropore surface area calculated from the
c
d
nitrogen adsorption isotherm using the t-pot method. Total pore volume at P/P0 ¼ 0.99. Micropore volume calculated using the t-pot
e
f
method. Data calculated based on each monomer unit. Data obtained with inductively coupled plasma-optical emission spectroscopy (ICP-
OES). g Volumetric CO2 adsorption–desorption isotherms measured for Al-CMP at 298 K.
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Table 2 Coupling reaction of CO2 and PO catalyzed by Al-CMPa
Entry
Cocatalyst
Temperature (ꢁC)
Pressure (MPa)
Conversionb (%)
TONc
TOFd (hꢀ1
)
1
2
3
4
—
70
70
70
70
70
70
25
50
100
70
70
3
3
3
3
3
3
3
3
3
1
3
1.5
74
28
6.1
9.2
22f
3.0
43
30
1480
560
122
180
440
60
860
1820
1460
540
6
296
112
24
37
55
PPNCl
TBAB
DMAP
MeIm
PPNCl
PPNCl
PPNCl
PPNCl
PPNCl
PPNCl
5
6e
7
12
8
9
172
364
292
—
91
73
27
10
11g
a
b
c
Reaction conditions: PO (10 mL), [PO]/[Al]/cocatalyst ¼ 2000 : 1 : 10, 5 h. Determined by 1H NMR spectroscopy. Turnover number of PO to
d
e
f
products. Turnover frequency of PO to products. Reaction conditions: PO (10 mL), [PO]/[Al]/cocatalyst ¼ 2000 : 1 : 1, 8 h. Polycarbonates
1
g
(4.6%) were observed by H NMR spectroscopy. Reaction conditions: PO (10 mL), [PO]/[PPNCl] ¼ 2000 : 10, 5 h.
pressure was also a major factor on coupling of CO2 and PO. Following each cycle, Al-CMP was simply recovered by ltration
However, when CO2 pressure decreased from 3 to 1 MPa, the PO aer reaction and reused for next run aer being dried. The PO
conversion varied insignicantly, indicating that the rate of conversion and TOF gradually decreased with increase of reused
coupling reaction was almost independent of CO2 pressure in times, but they still kept above 50% and 200 hꢀ1 aer 5 runs
this range.
respectively. The aluminum content in Al-CMP aer 5 runs was
Recently, metallosalen-based CMPs have been used as solid determined to be 0.78 wt% by ICP-OES, which was much lower
catalytic systems to catalyze the coupling of PO and CO2.18 These than the original value (2.81 wt%). This indicated that the metal
solid systems showed TOFs of 109–224 hꢀ1 at 100 ꢁC18a,b and 40– aluminum was partially dissociated from the porphyrin ligand of
157 hꢀ1 at 60 ꢁC.18c By contrast, Al-CMP in this work showed Al-CMP during the reaction and dissolved in the reaction system,
TOFs up to 364 hꢀ1 at 100 ꢁC and 296 hꢀ1 at 70 ꢁC, which which may be the main reason for the decrease in catalytic activity.
indicated this metalloporphyrin-based CMP was an efficient
solid catalyst for CO2 conversion to cyclic carbonates.
Conclusions
An important additional feature for any catalyst having
potential practicability is its reusability without signicant loss in
catalytic activity. As shown in Fig. 5, the catalyst was recycled for
ve runs under the same reaction conditions (70 ꢁC, 3 MPa, 5 h).
A new metalloporphyrin-based conjugated microporous poly-
mer (Al-CMP) was solvothermally synthesized using a metal-
loporphyrin as a main building block, which had high BET
surface area and good capacity of carbon dioxide capture. When
PPNCl was used as co-catalyst, Al-CMP displayed good catalytic
activity for cyclic carbonate synthesis with 364 hꢀ1 TOF.
Furthermore, Al-CMP had relatively good stability, and the PO
conversion and TOF still kept above 50% and 200 hꢀ1 respec-
tively aer it was reused 5 times.
Acknowledgements
The authors thank nancial support from the National Natural
Science Foundation of China (Grant no. 51321062, 51273197
and 21134002).
Notes and references
1 (a) M. Aresta and A. Dibenedetto, Dalton Trans., 2007, 2975;
(b) M. Mikkelsen, M. Jorgensen and F. C. Krebs, Energy
Environ. Sci., 2010, 3, 43.
Fig. 5 Recycle experiment with Al-CMP. Standard reaction condi-
tions: 0.05 mol% Al-CMP, 0.5 mol% PPNCl, 70 ꢁC, 3 MPa, 5 h.
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2 (a) D. Y. C. Leung, G. Caramanna and M. M. Maroto-Valer,
Renewable Sustainable Energy Rev., 2014, 39, 426; (b)
J. Shimonishi, C. Maeda and J.-Y. Hasegawa, J. Am. Chem.
Soc., 2014, 136, 15270.
S. L. O. Seigo, S. Dohle and M. Siegrist, Renewable 13 (a) J.-X. Jiang, F. Su, A. Trewin, C. D. Wood, N. L. Campbell,
Sustainable Energy Rev., 2014, 38, 848.
H. Niu, C. Dickinson, A. Y. Ganin, M. J. Rosseinsky,
Y. Z. Khimyak and A. I. Cooper, Angew. Chem., Int. Ed.,
2007, 46, 8574; (b) J.-X. Jiang and A. I. Cooper, in
Functional Metal–Organic Frameworks: Gas Storage,
Separation and Catalysis, ed. M. Schroder, Springer, 2010,
vol. 293, pp. 1–33; (c) N. B. McKeown and P. M. Budd,
Macromolecules, 2010, 43, 5163; (d) Y. Zhang and
S. N. Riduan, Chem. Soc. Rev., 2012, 41, 2083; (e) P. Kaur,
J. T. Hupp and S. T. Nguyen, ACS Catal., 2011, 1, 819; (f)
Z. Xiang and D. Cao, J. Mater. Chem. A, 2013, 1, 2691; (g)
Y. Kou, Y. Xu, Z. Guo and D. Jiang, Angew. Chem., Int. Ed.,
2011, 50, 8753.
3 (a) C. Lu, H. Bai, B. Wu, F. Su and J. Fen-Hwang, Energy Fuels,
2008, 22, 3050; (b) A. Zukal, I. Dominguez, J. Mayerova and
J. Cejka, Langmuir, 2009, 25, 10314; (c) M. R. Hudson,
W. L. Queen, J. A. Mason, D. W. Fickel, R. F. Lobo and
C. M. Brown, J. Am. Chem. Soc., 2012, 134, 1970.
4 (a) M. S. Shafeeyan, W. M. A. W. Daud, A. Houshmand and
A. Shamiri, J. Anal. Appl. Pyrolysis, 2010, 89, 143; (b)
T. C. Drage, J. M. Blackman, C. Pevida and C. E. Snape,
Energy Fuels, 2009, 23, 2790; (c) N. A. Rashidi, S. Yusup,
A. Borhan and L. H. Loong, Clean Technol. Environ. Policy,
2014, 16, 1353.
5 (a) H. Y. Cho, D.-A. Yang, J. Kim, S. Y. Jeong and W.-S. Ahn, 14 A. Li, R.-F. Lu, Y. Wang, X. Wang, K.-L. Han and W.-Q. Deng,
Catal. Today, 2012, 185, 35; (b) D. A. Yang, H. Y. Cho, J. Kim, Angew. Chem., Int. Ed., 2010, 49, 3330.
S. T. Yang and W. S. Ahn, Energy Environ. Sci., 2012, 5, 6465; 15 L. Chen, Y. Honsho, S. Seki and D. Jiang, J. Am. Chem. Soc.,
(c) Y. Liu, Y. Yang, Q. Sun, Z. Wang, B. Huang, Y. Dai, X. Qin
and X. Zhang, ACS Appl. Mater. Interfaces, 2013, 5, 7654.
6 (a) D. J. Darensbourg and M. W. Holtcamp, Coord. Chem.
Rev., 1996, 153, 155; (b) T. Sakakura and K. Kohno, Chem.
Commun., 2009, 1312.
2010, 132, 6742.
16 A. Li, H. X. Sun, D. Z. Tan, W. J. Fan, S. H. Wen, X. J. Qing,
G. X. Li, S. Y. Li and W. Q. Deng, Energy Environ. Sci., 2011,
4, 2062.
17 J. X. Jiang, C. Wang, A. Laybourn, T. Hasell, R. Clowes,
Y. Z. Khimyak, J. Xiao, S. J. Higgins, D. J. Adams and
A. I. Cooper, Angew. Chem., Int. Ed., 2011, 50, 1072.
7 (a) G. Rokicki, Prog. Polym. Sci., 2000, 25, 259; (b)
J. H. Clements, Ind. Eng. Chem. Res., 2003, 42, 663; (c)
A. A. G. Shaikh and S. Sivaram, Chem. Rev., 1996, 96, 951; 18 (a) Y. Xie, R. X. Yang, N. Y. Huang, H. J. Luo and W. Q. Deng,
(d) B. Schaeffner, F. Schaeffner, S. P. Verevkin and
A. Boerner, Chem. Rev., 2010, 110, 4554.
8 A. Taheri Najafabadi, Int. J. Energy Res., 2013, 37, 485.
9 (a) M. North, R. Pasquale and C. Young, Green Chem., 2010,
J. Energy Chem., 2014, 23, 22; (b) Y. Xie, T. T. Wang, X. H. Liu,
K. Zou and W. Q. Deng, Nat. commun., 2013, 4, 1960; (c)
S. U. Son, J. Chun, S. Kang, N. Kang, S. M. Lee and
H. J. Kim, J. Mater. Chem. A, 2013, 1, 5517.
12, 1514; (b) Y. Zhang, S. Yin, S. Luo and C. T. Au, Ind. Eng. 19 L. Chen, Y. Yang and D. Jiang, J. Am. Chem. Soc., 2010, 132,
Chem. Res., 2012, 51, 3951; (c) P. P. Pescarmona and 9138.
M. Taherimehr, Catal. Sci. Technol., 2012, 2, 2169; (d) 20 X. Liu, H. Li, Y. Zhang, B. Xu, S. A, H. Xia and Y. Mu, Polym.
A. Decortes, A. M. Castilla and A. W. Kleij, Angew. Chem., Chem., 2013, 4, 2445.
Int. Ed., 2010, 49, 9822; (e) X.-B. Lu and D. J. Darensbourg, 21 V. S. P. K. Neti, X. Wu, S. Deng and L. Echegoyen, Polym.
Chem. Soc. Rev., 2012, 41, 1462; (f) C. Maeda, Y. Miyazaki
and T. Ema, Catal. Sci. Technol., 2014, 4, 1482.
10 (a) Z. Q. Qin, C. M. Thomas, S. Lee and G. W. Coates, Angew.
Chem., 2013, 4, 4566.
22 W.-Y. Gao, M. Chrzanowski and S. Ma, Chem. Soc. Rev., 2014,
43, 5841.
Chem., Int. Ed., 2003, 42, 5484; (b) D. J. Darensbourg, Chem. 23 W. Wu, Y. Qin, X. Wang and F. Wang, J. Polym. Sci., Part A:
Rev., 2007, 107, 2388; (c) X. B. Lu, B. Liang, Y. J. Zhang, Polym. Chem., 2013, 51, 493.
Y. Z. Tian, Y. M. Wang, C. X. Bai, H. Wang and R. Zhang, J. 24 X.-S. Wang, M. Chrzanowski, C. Kim, W. Y. Gao, L. Wojtas,
Am. Chem. Soc., 2004, 126, 3732; (d) D. Tian, B. Liu,
Q. Gan, H. Li and D. J. Darensbourg, ACS Catal., 2012, 2,
2029.
Y.-S. Chen, X. P. Zhang and S. Ma, Chem. Commun., 2012,
48, 7173.
25 Z. S. Wu, L. Chen, J. Liu, K. Parvez, H. Liang, J. Shu,
H. Sachdev, R. Graf, X. Feng and K. Muellen, Adv. Mater.,
2014, 26, 1450.
11 (a) T. Aida and S. Inoue, J. Am. Chem. Soc., 1985, 107, 1358;
(b) T. Aida, M. Ishikawa and S. Inoue, Macromolecules,
1986, 19, 8; (c) C. Chatterjee and M. H. Chisholm, Inorg. 26 X. S. Wang, J. Liu, J. M. Bonefont, D. Q. Yuan,
Chem., 2011, 50, 4481; (d) C. Chatterjee and P. K. Thallapally and S. Ma, Chem. Commun., 2013, 49, 1533.
M. H. Chisholm, Inorg. Chem., 2012, 51, 12041; (e) 27 (a) L. N. Saunders, N. Ikpo, C. F. Petten, U. K. Das,
C. Chatterjee, M. H. Chisholm, A. El-Khaldy,
R. D. McIntosh, J. T. Miller and T. Wu, Inorg. Chem., 2013,
52, 4547; (f) N. Ikpo, J. C. Flogeras and F. M. Kerton,
Dalton Trans., 2013.
L. N. Dawe, C. M. Kozak and F. M. Kerton, Catal.
Commun., 2012, 18, 165; (b) R. L. Paddock and
S. T. Nguyen, Chem. Commun., 2004, 1622; (c) T. Chang,
H. Jing, L. Jin and W. Qiu, J. Mol. Catal. A: Chem., 2007,
264, 241; (d) X. B. Lu, X. J. Feng and R. He, Appl. Catal., A,
2002, 234, 25; (e) X. Jiang, F. Gou and H. Jing, J. Catal.,
2014, 313, 159.
12 (a) T. Ema, Y. Miyazaki, S. Koyama, Y. Yano and T. Sakai,
Chem. Commun., 2012, 48, 4489; (b) T. Ema, Y. Miyazaki,
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