A Porphyrin-Based Porous rtl Metal–Organic Framework as an Efficient Catalyst for the Cycloaddition of CO2to Epoxides

Article abstract of DOI:10.1002/chem.201603465

A porous rtl metal–organic framework (MOF) [Mn₅L(H₂O)₆?(DMA)₂]?5DMA?4C₂H₅OH (1?Mn) (H₁₀L=5,10,15,20-tetra(4-(3,5-dicarboxylphenoxy)phenyl)porphyrin; DMA=N,N′-dimethylacetamide) was synthesized by employing a new porphyrin-based octacarboxylic acid ligand. 1?Mn exhibits high Mn^IIdensity in the porous framework, providing it great Lewis-acid heterogeneous catalytic capability for the cycloaddition of CO₂with epoxides. Strikingly, 1?Mn features excellent catalytic activity to the cycloaddition of CO₂to epoxides, with a remarkable initial turnover frequency 400 per mole of catalyst per hour at 20 atm. As-synthesized 1?Mn also exhibits size selectivity to different epoxide substrates on account of their steric hindrance. The high catalytic activity, size selectivity, and stability toward the epoxides on catalytic cycloaddition of CO₂make 1?Mn a promising heterogeneous catalyst for fixation and utilization of CO₂.

Full text of DOI:10.1002/chem.201603465

DOI: 10.1002/chem.201603465
Full Paper
&
Metal–Organic Frameworks
A Porphyrin-Based Porous rtl Metal–Organic Framework as an
Efficient Catalyst for the Cycloaddition of CO to Epoxides
2
[a]
[a]
[a]
[b]
[a]
Wei Jiang, Jin Yang,* Ying-Ying Liu, Shu-Yan Song,* and Jian-Fang Ma*
Abstract: A porous rtl metal–organic framework (MOF)
tures excellent catalytic activity to the cycloaddition of CO2
to epoxides, with a remarkable initial turnover frequency
400 per mole of catalyst per hour at 20 atm. As-synthesized
1·Mn also exhibits size selectivity to different epoxide sub-
strates on account of their steric hindrance. The high catalyt-
ic activity, size selectivity, and stability toward the epoxides
[
Mn L(H O) ·(DMA) ]·5DMA·4C H OH
(1·Mn)
(H L=
10
5
2
6
2
2
5
5,10,15,20-tetra(4-(3,5-dicarboxylphenoxy)phenyl)porphyrin;
DMA=N,N’-dimethylacetamide) was synthesized by employ-
ing a new porphyrin-based octacarboxylic acid ligand. 1·Mn
II
exhibits high Mn density in the porous framework, provid-
ing it great Lewis-acid heterogeneous catalytic capability for
on catalytic cycloaddition of CO make 1·Mn a promising
2
the cycloaddition of CO with epoxides. Strikingly, 1·Mn fea-
heterogeneous catalyst for fixation and utilization of CO2.
2
Introduction
separation of the catalysts from the products is greatly difficult,
[7]
restricting their wide application.
Carbon dioxide (CO ) as the primary greenhouse gas has raised
In recent years, metal–organic frameworks (MOFs), as a spe-
cial class of crystalline porous materials, have received exten-
sive attention for their applications in heterogeneous catalysis
2
a great deal of concern owing to its resulting linkage effect on
[
1]
global warming and climate change. Thereby, the develop-
[8]
ment of efficient CO capture technologies has received global
as well as gas storage. The modular nature and facile tunabil-
ity of MOFs make them ideal heterogeneous catalysts with uni-
2
[
2]
attention. In this regard, CO activation and efficient transfor-
2
[9]
mation into valuable chemicals by chemical fixation are highly
attractive because it is a nontoxic, cheap, and renewable
form active sites through wisely chosen building blocks. In
this regard, porphyrin-based porous MOFs have captured
widespread research interest because of their excellent catalyt-
[
3]
carbon resource for making carbohydrates. In terms of chem-
[10]
ical fixation of CO , one of the most green approaches is the
ic and biomimetic properties very recently. During the cata-
lytic process, porphyrin-based MOFs always function as mild
2
synthesis of cyclic carbonates from CO and epoxides by 100%
2
[
4]
[11]
atom-economical reaction. In particular, the promising target
cyclic carbonates could be widely utilized as precursors for
producing polycarbonates as well as a large number of fine
Lewis acids. More importantly, the inclusion of porphyrin or
metalloporphyrin in MOFs may lead to improving the stability
and enriching the Lewis acid sites, which supports a high yield
[
5]
[12]
chemicals. Thus far, numerous heterogeneous and homoge-
of the catalytic products.
neous catalysts have been developed for CO cycloaddition to
In the early reports, rigid porphyrin linkers have been stud-
ied and they played a significant role in targeting porous
2
epoxides, in which homogeneous catalysts, such as quaternary
ammonium and phosphonium salts, ionic liquids, metal com-
[13]
MOFs exhibiting superior catalytic performance. In contrast,
flexible porphyrin-based porous frameworks with fascinating
structural motifs have been received less attention as the
[6]
plexes, and alkali metal salts, have been extensively studied.
These homogeneous catalysts are effective, and some metal
complexes are very active in the presence of co-catalysts, but
[14]
promising catalysts. Taking inspiration from the above con-
sideration, for the first time, we explored the flexible octacar-
boxylate-based
5,10,15,20-tetra(4-(3,5-dicarboxylphenoxy)-
[
a] Dr. W. Jiang, Prof. J. Yang, Dr. Y.-Y. Liu, Prof. J.-F. Ma
Key Lab of Polyoxometalate Science, Department of Chemistry
Northeast Normal University
Changchun 130024 (P. R. China)
E-mail: yangj808@nenu.edu.cn
phenyl)porphyrin (H L; Scheme 1), and present the successful
10
fabrication
of
a
porous
rtl
MOF
[
Mn L(H O) ·(DMA) ]·5DMA·4C H OH (1·Mn; DMA=N,N’-dime-
5
2
6
2
2
5
II
thylacetamide). Remarkably, 1·Mn exhibits high Mn density in
majf247@yahoo.com
the porous framework, providing it great Lewis acid heteroge-
[b] Dr. S.-Y. Song
State Key Laboratory of Rare Earth Resource Utilization
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences
Changchun 130022 (P. R. China)
neous catalytic capability for the cycloaddition of CO with ep-
2
oxides. More importantly, catalyst 1·Mn is stable, very active,
and could be easily separated and reused.
E-mail: songsy@ciac.ac.cn
Supporting information for this article (crystallographic data in CIF format,
1
H NMR spectra, GC spectra, tables, TG curve, and PXRD patterns) is avail-
able on the WWW under: http://dx.doi.org/10.1002/chem.201603465.
Chem. Eur. J. 2016, 22, 1 – 8
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Scheme 1. The porphyrin-based octacarboxylic acid ligand used herein.
Results and Discussion
Structural description of 1·Mn
Crystals of 1·Mn were synthesized with H L and MnCl ·4H O
10
2
2
under solvothermal conditions. During the refinement of 1·Mn,
the disordered solvents were removed by applying the
[
15]
SQUEEZE routine in PLATON. Thermal gravimetric (TG) analy-
sis (Supporting Information, Figure S1), elemental analysis, and
diffuse electron density in the void suggest the presence of
five lattice DMA and four free ethanol molecules per formula
unit. 1·Mn crystallizes in the monoclinic space group P2 /c. The
1
asymmetric unit of 1·Mn is composed of half an L anion, two
II
and a half Mn atoms, one coordinated DMA molecule, and
II
three coordinated water molecules. Three Mn atoms (Mn1,
Mn2, and Mn3) exhibit the same octahedral coordination
sphere but different coordination environments. Mn1 is coordi-
nated with four pyrrolyl nitrogen atoms of porphyrin core, and
two DMA oxygen atoms lying at the axial positions. The bond
distances of Mn1ÀN1 and Mn2ÀN2 are 2.021 and 2.009 ꢁ, re-
II
spectively, which are located in the range of known Mn ÀN
[
16]
bonds. Mn2 is coordinated by six carboxylate oxygen atoms
of three different porphyrin-based L anions, whereas the coor-
dination geometry of Mn3 is completed by three water oxygen
atoms and three carboxylate oxygen atoms from two porphy-
rin-based L anions. Three carboxylate groups bridge Mn2 and
Mn3 atoms to afford a paddlewheel-like Mn (COO) (H O) sec-
2
4
2
3
ondary building unit (SBU), as illustrated in Figure 1a. The
backbone of each L anion bridges six paddlewheel-like SBUs,
and each SBU is linked by three L anions (Figure 1a), then re-
sulting in a remarkable 3D framework with an open channel
2
along the a axis (16ꢂ7 ꢁ ) (Figure 1b–d). Topologically, the 6-
connected L anion and 3-connected Mn (COO) (H O) SBU cor-
2
4
2
3
respond to the six-coordinated Ti atom and three-coordinated
O atom in the rutile (rtl) net, respectively. Thus, the structure of
Figure 1. a) View of coordination mode of L anion in 1·Mn. Symmetry codes:
#1 Àx, y+1/2, ÀzÀ1/2; #2 Àx+1, y+1/2, ÀzÀ1/2; #3 xÀ1, y, z; #4 x+1, y,
z. b) View of 3D framework of 1·Mn. c) Representation of the 3D (3,6)-con-
nected rtl net. d) Natural tiling for the rtl structure of 1·Mn. The picture is
drawn with the 3dt program using an input generated with ToposPro.
1
·Mn will be simplified as a rtl net with a point symbol of
2
2
10
3
(4·6 ) (4 ·6 ·8 ). The total accessible volume of the unit cell was
2
3
estimated to be 4260.1 ꢁ by using PLATON, which accommo-
dates approximately 55.8% of the unit cell volume
3
[15]
(7633.0 ꢁ ).
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Gas adsorption of 1·Mn
2
Table 1. Different substituted epoxides coupled with CO catalyzed by
[
a]
1
·Mn at 1 atm.
The gas adsorption properties of activated 1·Mn were studied
[
b]
Entry
Epoxides
Products
Time [h]
4
Yields [%]
by CO adsorption at 298 K and N adsorption at 77 K. For
2
2
1
·Mn, there is nearly no N adsorption at 77 K (Supporting In-
2
formation, Figure S2). 1·Mn exhibits selective uptake for N and
1
2
>99
>99
2
CO . When the pressure is equal to the atmospheric pressure,
2
3
À1
CO uptake reaches to 25.51 cm g at 298 K. It can be found
2
4
4
that about 4.24 CO molecules in each unit cell of 1·Mn is ad-
2
sorbed at 1 bar when the adsorption amount is converted to
the numbers of CO . The selective adsorption of CO over N
2
3
30
2
2
makes 1·Mn a possible catalyst candidate in capturing and
[
17]
converting CO2. Noticeably, TG analysis combined with FTIR
analysis of activated 1·Mn indicates that the DMA molecules
still remain coordinated after desolvation (Supporting Informa-
tion, Figures S1,S3), which reduces the amount of space avail-
able for CO and then leads to the low uptake of CO . More-
4
5
4
4
41
43
2
2
[
a] Reaction conditions: expoxide (1 mmol), 1·Mn (0.005 mmol) and
over, the PXRD pattern after the gas adsorption showed no
change in the peak position (Supporting Information, Fig-
ure S4), demonstrating that the structure of 1·Mn was main-
tained.
nBu NBr (1 mmol), CO (1 atm). [b] Yield of isolated product was calculat-
ed by GC and H NMR spectroscopy.
4
2
1
(
Table 1, entry 1). The results indicate the excellent synergistic
Catalytic cycloaddition of CO to epoxides
2
effect of 1·Mn and nBu NBr on the catalysis of CO cycloaddi-
4
2
[19]
Recently, MOFs have been shown to serve as heterogeneous
tion.
To check the generality for such a cycloaddition reaction of
CO , a family of epoxides with variable dimensions were select-
Lewis acid catalysts for chemical conversion of CO into cyclic
2
[
18]
carbonates.
Given the high affinity toward CO molecules
2
2
II
and the high density of Mn ions confined in 1·Mn, detailed
ed as substrates in following catalytic reactions (Supporting In-
formation, Table S2). As shown in Table 1, the small substrate
1,2-epoxyhexane was fully converted into the 4-butyl-1,3-diox-
olan-2-one after 4 h of the reaction (entry 2). This observation
suggests that the small substrate was easily carried out within
the porous framework of 1·Mn for the catalytic reaction. Never-
theless, when the large substrates 1,2-epoxyethylbenzene, gly-
cidyl phenyl ether, and benzyl glycidyl ether were utilized, the
corresponding product yields revealed sharp decreases under
the same conditions (entries 3–5); they were just 30%, 41%,
and 43%, respectively. This lower activity mainly accounts for
the high steric hindrance of the substrates during the catalytic
reaction, which influenced the transport of the substrates and
catalytic performance of CO fixation was evaluated for 1·Mn
2
at both 1 atm and 20 atm, respectively. The catalytic experi-
ments were conducted at 808C for 4 h with 1·Mn and nBu NBr
as co-catalysts. The reaction of epichlorohydrin with CO2 at
4
1
atm was utilized as the model reaction to investigate the
effect of various parameters on the catalytic performance
Scheme 2). The product carbonates were confirmed by
(
[20]
products through the channels of 1·Mn. These results mani-
fest that 1·Mn exhibits the size selectivity to small and large
2
Scheme 2. Representation of the cycloaddition of CO to epichlorohydrin.
[21]
substrates in the catalytic process. To achieve high conver-
sion rates, we have tried to extend the catalytic reaction time.
As illustrated in Figure 2, the product yields were enhanced
after 12 h of the catalytic reaction.
1
H NMR studies (Supporting Information, Figures S5–S9) and
the yields of the cyclic carbonates were calculated by gas chro-
matography (GC; Supporting Information, Figures S10–S13).
When only 1·Mn was used as catalyst at atmospheric pressure
To further understand the catalytic activities of 1·Mn, a de-
tailed kinetic study was also conducted in the presence of
of CO , the product 4-chloromethyl-1,3-dioxolan-2-one was
2
achieved in a 45% yield with heating at 808C after 4 h (Sup-
nBu NBr as co-catalyst. The catalytic reaction was performed at
4
porting Information, Table S1, entry 1), demonstrating that
different time intervals from 1 to 4 h. As depicted in Figure 3,
just 40% of the epichlorohydrin was transformed to the 4-
chloromethyl-1,3-dioxolan-2-one after 1 hour of the reaction,
and the total conversion (>99%) of the epichlorohydrin was
accomplished after 4 h.
1·Mn could activate CO2 in this reaction. Once only the
nBu NBr was chosen as catalyst, just 31% yield of the 4-chloro-
4
methyl-1,3-dioxolan-2-one was obtained for the cycloaddition
of CO to epichlorohydrin (Supporting Information, Table S1,
2
entry 2). Particularly, when 1·Mn was combined with the
Moreover, to verify the heterogeneous nature of the reac-
tion, catalyst 1·Mn was removed after 1 hour of the catalytic
reaction, and then the reaction was further performed under
nBu NBr as binary catalytic system, the substrates were com-
4
pletely converted to the carbonates after 4 h of reaction
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Figure 4. Recycling experiments for catalyst 1·Mn at 1 atm.
Figure 2. Yields of carbonates catalyzed by 1·Mn after 4 h (light gray) and
2 h (dark gray) of reactions at 1 atm.
ered 1·Mn after 4 runs during the cycloaddition reaction was
determined. All of the characteristic peaks of 1·Mn are well re-
peated, demonstrating a good structural integrity in successive
runs of catalysis (Supporting Information, Figure S4).
1
In industrial applications, high pressure is always employed
[22]
in CO coupling reactions. Thereby, the cycloaddition of CO2
2
by 1·Mn was also investigated at 20 atm (Supporting Informa-
tion, Figure S14). In a typical experiment, the catalytic reaction
was conducted in a high-pressure microreactor using epoxides
(
20 mmol) as substrate with CO2 pressurized to 20 atm at
08C. As shown in Table 2, among various epoxides, the epi-
8
chlorohydrin is the most active in producing the cyclic carbon-
À1
ate with a high turnover frequency (TOF) of 400 h (entry 1).
The substrate 1,2-epoxyhexane was almost completely con-
verted into the product carbonate within 4 h with a TOF of
À1
200 h
(entry 2). The glycidyl phenyl ether (entry 4) and
benzyl glycidyl ether (entry 5) were catalyzed by 1·Mn in con-
Table 2. Different substituted epoxides coupled with CO
2
catalyzed by
Figure 3. Curves of CO
at 1 atm (black ) and by the filtrate of 1·Mn after 1 hour of the reaction
gray *).
2
cycloaddition to epichlorohydrin catalyzed by 1·Mn
[
a]
1
·Mn at 20 atm.
&
(
[
b]
[c]
À1 [d]
Entry
Epoxides
Time [h] Yields [%]
TON
TOF [h
]
1
2
2
4
>99
>99
800
800
400
the same condition as listed in entry 1. As shown in Figure 3,
no obvious increase in the formation of the product carbonate
was observed. Furthermore, inductively coupled plasma (ICP)
analysis was employed to detect the reaction mixture filtrate
200
3
4
44
352
88
II
at the end of the reaction. The ICP data suggested no Mn
leaching, demonstrating the catalytic reaction is heterogene-
ous.
4
5
4
4
91
92
728
736
182
184
Further experiments were also conducted to examine the re-
usability of catalyst 1·Mn using the epichlorohydrin as the sub-
strate. During the cycloaddition of CO , catalyst 1·Mn can be
2
[
a] Reaction conditions: expoxide (20 mmol), 1·Mn (0.005 mmol) and
easily separated in successive runs by filtrating and drying. As
shown in Figure 4, 1·Mn keeps very high catalytic activity after
four runs, indicating the good reusability of catalyst 1·Mn. The
comparative PXRD patterns of as-synthesized 1·Mn and recov-
nBu NBr (30 mmol), CO (20 atm). [b] Yield of isolated product was calcu-
lated by GC and H NMR spectroscopy. [c] Moles of cyclic carbonate per
mole of catalyst 1·Mn. [d] Moles of cyclic carbonate per mole of catalyst
4
2
1
1
·Mn per hour.
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version rates of 91% and 92%, respectively, after 4 h. Never-
theless, when the 1,2-epoxyethylbenzene was employed as the
substrate, only 44% of the cyclic carbonate was achieved after
4
h of the reaction. The results indicate that the catalytic activi-
ty and selectivity of 1·Mn at 20 atm are in accordance with
those as demonstrated under ambient pressure.
Moreover, 1,2-epoxyethylbenzene was selected as the model
reaction during the coupling reaction of CO , as shown in
2
Figure 5. The catalytic performance was detected at different
Figure 6. Recycling experiments for catalyst 1·Mn at 20 atm.
Figure 5. The yields (black
&
2
) and TON values (gray bars) of CO cycloaddi-
tion to 1,2-epoxyethylbenzene at 20 atm.
time intervals. In the presence of 0.3 mmol of nBu NBr, the
4
loading of 0.125 mol% ratio of 1·Mn (based on Mn) afforded
a 44% conversion of the 1,2-epoxyethylbenzene with a turn-
over number (TON) 352 after 4 h of the reaction. Finally, 94%
of the 1,2-epoxyethylbenzene was converted to the product 4-
phenyl-1,3-dioxolan-2-one and the TON value was 752 per
mole of catalyst 1·Mn after 10 h. Remarkably, in comparison
Scheme 3. Proposed mechanism of the cycloaddition of CO to epoxides
2
with the cycloaddition of CO taken at ambient pressure (Sup-
4
with 1·Mn and nBu NBr as co-catalysts.
2
porting Information, Table S1), approximately 20 times of the
TON value of 1,2-epoxyethylbenzene were achieved with the
same mole catalyst 1·Mn at 20 atm, indicating that the conver-
the epoxide, producing the intermediate species (A) via a ring-
opening reaction. Subsequently, the oxygen atom of the inter-
sion rate was improved markedly with the increasing CO pres-
2
sure.
mediate (A) combined with CO to form a new intermediate
2
Furthermore, the stability and recyclability of catalyst 1·Mn
were also examined at 20 atm. The PXRD patterns show that
the structural integrity of 1·Mn was well maintained after catal-
ysis at 20 atm (Supporting Information, Figure S4). After 5 runs,
the yields of the product 4-phenyl-1,3-dioxolan-2-one slightly
decreased and a total TON value of 3536 was achieved, dem-
onstrating that the catalytic activity of 1·Mn was still retained
(B). Oxygen atom of the intermediate (B) further attacks its
À
inner carbon atom to release the Br anion, forming the cyclic
carbonate and regenerating the nBu NBr. Obviously, the syner-
4
II
gistic effect of the high density of Lewis acid Mn sites in 1·Mn
and nBu NBr as the co-catalysts make the reaction proceed
4
smoothly.
during the cycloaddition of CO under high pressure (Figure 6).
2
Conclusion
On the basis of previous mechanistic studies as well as cur-
rent catalytic results, a plausible synergistic catalytic mecha-
In summary, we have synthesized a unique porous rtl MOF cat-
alyst 1·Mn by employing a new flexible porphyrin-based octa-
carboxylic acid ligand. Remarkably, the constructed MOF 1·Mn,
[
23]
nism is proposed in Scheme 3. At the beginning, the Lewis
II
acidic Mn sites confined in 1·Mn interact with the oxygen
II
atom of the epoxide, which then activate the epoxide ring.
featuring selective CO2 adsorption and rich Lewis-acid Mn
À
Meanwhile, the Br anion from the nBu NBr makes a nucleo-
sites, could serve as an excellent heterogeneous catalyst for
4
philic attack on the less sterically hindered b-carbon atom of
CO -based chemical fixation, which has been clearly verified by
2
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the highly efficient catalytic cycloaddition of CO to epoxides
technique. The structure was solved by direct methods with
2
2
SHELXS-97 and refined on F by full-matrix least-squares using the
at both 1 atm and 20 atm. 1·Mn also exhibits the highest cata-
lytic activity with a TON of 800 per mole of catalyst 1·Mn in
the first cycle at 20 atm. Importantly, 1·Mn shows the size se-
lectivity to small and large epoxides in the catalytic process.
The excellent catalytic activity, size selectivity, and good stabili-
ty suggest that porphyrin-based porous MOF 1·Mn is an effi-
cient heterogeneous catalyst for the cycloaddition reaction of
[24]
SHELXTL-97 program within WINGX. Non-hydrogen atoms were
refined anisotropically. Hydrogen atoms on carbon were generated
geometrically.
CCDC 1493789 contains the supplementary crystallographic data
for this paper. These data are provided free of charge by The Cam-
bridge Crystallographic Data Centre.
ubiquitous CO to epichlorohydrin and is quite promising for
2
potential applications.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 21277022, 21371030,
Experimental Section
21301026, and 21471029).
Materials and methods: All reagents and solvents were purchased
from commercial sources. The FTIR spectrum was measured in
À1
4
000–400 cm range on a Mattson Alpha-Centauri spectrometer.
Keywords: carbon dioxide · cycloaddition · epoxides · metal–
organic frameworks · porphyrins
Elemental analysis was determined on a PerkinElmer 240 CHN ele-
mental analyzer. PXRD patterns were recorded on a Rigaku Dmax
2
000 X-ray diffractometer with graphite monochromatized CuKa
1
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Cycloaddition of CO to epoxides at 1 atm: In a typical proce-
2
[
[
dure, epoxide (1 mmol), nBu NBr (32 mg, 0.1 mmol), and activated
4
1
1
·Mn (13 mg, 0.005 mmol) were placed in a 10 mL reactor. The re-
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1
product structure was confirmed by H NMR and the yields were
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73–379.
Cycloaddition of CO to epoxides at 20 atm: Typically, epoxide
2
[
[
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The product structure was also confirmed by H NMR and the
yields were calculated by GC.
Synthesis of [Mn L(H O) ·(DMA) ]·5DMA·4C H OH: A mixture of
5
2
6
2
2
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H L (20 mg, 0.015 mmol), MnCl ·4H O (20 mg, 0.10 mmol), DMA
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0
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[
obtained in
a 39% yield based on H L. Anal. calcd for
10
C112H126Mn N O : C 53.66, H 5.06, N 2.23; found: C 53.45, H 5.11,
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4
44
À1
N 2.15. IR (KBr pellet, cm ): 3732 (w), 3433 (m), 2927 (w), 1658 (s),
614 (s), 1565 (s), 1498 (s), 1448 (s), 1376 (s), 1246 (m), 1208 (m),
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1
1
7
[
[
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Received: July 21, 2016
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Published online on && &&, 0000
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Full Paper
FULL PAPER
The porphyrin-based porous rtl metal–
organic framework 1·Mn features high
catalytic activity, size selectivity, and sta-
bility toward the cycloaddition of CO2
to epoxides. These features make 1·Mn
a promising heterogeneous catalyst for
fixation and utilization of CO2.
&
Metal–Organic Frameworks
W. Jiang, J. Yang,* Y.-Y. Liu, S.-Y. Song,*
J.-F. Ma*
&
& – &&
A Porphyrin-Based Porous rtl Metal–
Organic Framework as an Efficient
Catalyst for the Cycloaddition of CO2
to Epoxides
&
&
Chem. Eur. J. 2016, 22, 1 – 8
www.chemeurj.org
8
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!