A Triazole-Containing Metal-Organic Framework as a Highly Effective and Substrate Size-Dependent Catalyst for CO2 Conversion

Article abstract of DOI:10.1021/jacs.5b13335

A highly porous metal-organic framework (MOF) incorporating both exposed metal sites and nitrogen-rich triazole groups was successfully constructed via solvothermal assembly of a clicked octcarboxylate ligand and Cu(II) ions, which presents a high affinit

Full text of DOI:10.1021/jacs.5b13335

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Communication
A Triazole-Containing Metal-Organic Framework as a Highly
Effective and Substrate Size-Dependent Catalyst for CO2 Conversion
Pei-Zhou Li, Xiao-Jun Wang, Jia Liu, Jie Sheng Lim, Ruqiang Zou, and Yanli Zhao
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b13335 • Publication Date (Web): 05 Feb 2016
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A Triazole-Containing Metal-Organic Framework as a Highly
Effective and Substrate Size-Dependent Catalyst for CO2
Conversion
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†
,¶,§
†,¶,§
‡,¶,§
†
,‡,¶
,†,¶,
#
PeiꢀZhou Li,
XiaoꢀJun Wang,
Jia Liu,
Jie Sheng Lim, Ruqiang Zou,* and Yanli Zhao*
†
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological
University, 21 Nanyang Link, Singapore 637371
‡
Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, Department of Materials Science and
Engineering, College of Engineering, Peking University, Beijing 100871, China
¶
Singapore Peking University Research Centre for a Sustainable LowꢀCarbon Future, 1 Create Way, Singapore 138602
#
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798, Singapore
Supporting Information Placeholder
ous catalysts have been developed for the CO chemical converꢀ
sion.
ABSTRACT: A highly porous metalꢀorganic framework (MOF)
incorporating both exposed metal sites and nitrogenꢀrich triazole
groups was successfully constructed via solvothermal assembly of
a clicked octcarboxylate ligand and Cu(II) ions, which presents a
2
3
high affinity toward CO molecule clearly verified by gas adsorpꢀ
2
tion and Raman spectral detection. The constructed MOF featurꢀ
ing CO ꢀadsorbing property and exposed Lewisꢀacid metal sites
2
could serve as an excellent catalyst for CO based chemical fixaꢀ
2
tion. Catalytic activity of the MOF was confirmed by remarkably
high efficiency on CO cycloaddition with small epoxides. When
2
extending the substrates to larger ones, its activity showed a sharp
decrease. These observations reveal that MOFꢀcatalyzed CO2
cycloaddition of small substrates was carried out within the
framework, while large ones cannot easily enter into the porous
framework for catalytic reactions. Thus, the synthesized MOF
exhibits high catalytic selectivity to different substrates on acꢀ
count of the confinement of the pore diameter. The high efficienꢀ
cy and sizeꢀdependent selectivity toward small epoxides on cataꢀ
lytic CO cycloaddition make this MOF a promising heterogeneꢀ
2
ous catalyst for carbon fixation.
Figure 1. (a) Perspective view of threeꢀdimensional porous
framework of 1 showing the incorporation of unsaturated Cu2
sites and accessible nitrogenꢀrich triazole groups with two kinds
of pores (yellow and blue balls). (b) Coordination of clicked ocꢀ
Carbon dioxide (CO ) as the primary anthropogenic gas has
been cited as the leading culprit in inducing average temperature
2
tcarboxylate ligand L1 and unsaturated paddlewheel Cu units. (c)
2
increase of the global surface as well as subsequent climate
Lamellar framework with regularly located Cu sites connected by
2
1
changes. The CO emitted from the power plants actually can be
isophthalate moieties from L1. (d) Illustration of the (4,3,4)ꢀ
connected network of 1.
2
taken as an abundant carbon source. Besides the physical adsorpꢀ
tion and permanent underground deposition of CO , an alternative
2
Owing to high porosity, adjustable compositions and decorative
pore surface, metal–organic frameworks (MOFs) have emerged as
highly promising materials for wide applications, including the
and more attractive strategy for addressing anthropogenic CO2
emission issues should be catalytically chemical conversion of
CO into valueꢀadded chemicals and materials, so that the emitted
2
4
2,3
adsorption and separation of small molecules such as H , CH
2 4
CO can be reused in the carbon recycling on the earth. This
2
5
,6
1
and other hydrocarbons as well as CO . Recently, MOFs have
approach not only reduces the anthropogenic greenhouse gas
emission, but also generates valuable chemical commodity to
decrease our dependence on petrochemicals. Therefore, it should
be a reliable way toward a sustainable lowꢀcarbon future. Taking
account of the issues of the product purifications and catalyst
recycling in homogeneous catalytic processes, some heterogeneꢀ
2
also been demonstrated as efficient catalysts in heterogeneous
7
catalytic reactions. Although some MOFs have been considered
8
as catalysts for CO chemical conversion, it is still necessary to
2
construct more effective MOFs for such reaction especially under
mild reaction conditions in order to lower the energy consumption
and production costs. Moreover, the factors such as the frameꢀ
1
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work affinity toward CO and the poreꢀsize effect to the substrates
still need to be well investigated during the processes of MOFꢀ
accessible volume of 1 was estimated to be 63.3% and the density
2
ꢀ
3
1
2
3
4
5
6
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8
9
1
1
1
1
1
1
1
1
1
1
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5
5
6
of the desolvated framework was calculated to be 0.762 g cm ,
further indicating that 1 possesses a high porosity. The structural
analysis and calculations clearly reveal that 1 has a highly porous
framework incorporated with both exposed metal sites and coorꢀ
dinationꢀfree nitrogenꢀrich triazole units.
based CO2 catalytic conversion. Herein, we present successful
fabrication of a highly porous MOF, {Cu [(C H N )(COO) ]}
n
4
57 32 12
8
9
(
1), that incorporates both unsaturated Cu sites and accessible
nitrogenꢀrich triazole units exhibiting a high affinity to CO2,
which shows remarkably high efficiency on catalytic CO2 cyꢀ
cloaddition with small epoxides at 1 atm and room temperature.
The MOF showed a sharp decrease of its activity to larger subꢀ
strates at the same conditions, indicating its high selectivity toꢀ
ward the size of the substrates.
N adsorption measurements were carried out to confirm the
2
porosity. The MOF was degassed under vacuum after being thorꢀ
oughly soaked by dichloromethane. The powder Xꢀray diffraction
(PXRD) pattern of the activated sample presents a good agreeꢀ
ment with calculated PXRD pattern from its crystal data (Figure
S3 in the SI), indicating that the framework was retained after the
activation. Then, the activated sample of 1 was subjected to nitroꢀ
gen sorption at 77 K. As illustrated in Figure 2a, 1 exhibits reꢀ
versible type I sorption isotherms with a quickly increased step
prior to the plateau, demonstrating that it possesses a microporous
0
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0
An inherent structural feature of MOFs distinct from other inꢀ
organic porous materials is that they have decorative organic moiꢀ
eties that endow them with chemical tunability by introducing
functional groups. Theoretical and experimental investigations
have demonstrated that accessible nitrogenꢀdonor groups, such as
amine, pyridine, imidazole, triazole and tetrazole, in the porous
17
3
ꢀ1
feature. The overall N uptake of 1 is 655 cm g at 1 atm, and
2
1
0ꢀ12
materials have a high affinity to CO2 molecule.
click chemistry” can easily afford the formation of nitrogenꢀrich
triazole rings with high yield under mild conditions, with which
Versatile
its BrunauerꢀEmmettꢀTeller (BET) surface area was calculated to
2
ꢀ1
“
be 2436 m g (Figure S5 in the SI), which is comparable with
12b
reported MOFs having similar structures such as NTUꢀ111 and
1
2,13
14b
various functional materials have been fabricated.
these advantages into account, a nitrogenꢀrich octcarboxylate
ligand, 5,5',5'',5'''ꢀ((methanetetrayltetrakisꢀ(benzeneꢀ4,1ꢀdiyl))
Taking
ZJUꢀ5. The calculations based on the N sorption isotherm at 77
2
K with the nonꢀlocal density functional theory were also carried
out to reveal that its pore size distribution ranges from 0.75 to
1.11 Å (Figure 2a). The pore size distribution is consistent well
tetrakis (1Hꢀ1,2,3ꢀtriazoleꢀ4,1ꢀdiyl)) tetraisoꢀphthalic acid (H L1),
8
was successfully synthesized via the “click” reaction and subseꢀ
quent deprotection (see the Supporting Information (SI) for deꢀ
tails). Some studies have also revealed that unsaturated metal sites
with the observation from its crystal structure. N sorption invesꢀ
tigation further confirms that 1 is a highly porous MOF.
2
incorporated into MOFs not only dramatically increase the affiniꢀ
8dꢀg,i
1377
ty to CO , but also act as Lewis acid catalytic centers.
On
2
account of easy generation of unsaturated paddlewheel Cu units,
2
Cu(II) ion was selected for the MOF construction with H L1, and
8
o
-
80
60
C
C
high quality blue crystals of 1 (Figure S1 in the SI) were successꢀ
fully obtained after solvothermal reaction.
o
-
(a) 700
(b) 160
CO , 273K
2
CO
, 298K
o
6
5
4
3
2
1
00
00
00
00
00
00
0
N2 adsorption
N2 desorption
140
2
-40
C
C
120
o
-20
0
100
o
8
0
C
Pore size distribution
60
40
20
0
o
20
C
1
2
3
4
5
Vacuum
Pore Width / nm
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure P/P
0
Relative Pressure P/P0
1200
1400
1600
Figure 2. (a) N adsorption/desorption isotherms of 1 at 77 K and
-1
2
Raman shift (cm )
its pore size distribution calculated from the isotherms. (b) CO2
adsorption isotherms at 273 K and 298 K, respectively.
Figure 3. Temperature dependent Raman spectra of 1 (Vacuum)
o
Singleꢀcrystal Xꢀray diffraction analysis reveals that 1 is a
threeꢀdimensional porous network with a framework formula of
and CO ꢀadsorbed 1 (20 to –80 C) showing obvious spectroscopꢀ
2
ic changes before and after the CO adsorption of 1.
2
[
Cu (L1)] (Figure 1a and Figure S2 in the SI). As illustrated in
4 n
High porosity together with the incorporation of exposed metal
sites and nitrogenꢀrich triazole units within the framework of 1
inspired us to investigate its affinity toward CO . Firstly, the CO
Figure 1b, two neighboring Cu(II) ions are bridged by four disꢀ
tributed carboxylate groups from four different L1 ligands to form
1
2,14
2
2
an paddlewheel Cu cluster.
Two neighboring Cu clusters are
2
2
sorption capability of 1 was evaluated. As shown in Figure 2b, 1
then bridged by the short linker, isophthalate moiety of L1, giving
3
ꢀ1
shows a CO ꢀuptake value of 160.8 cm g at 273 K and 1 atm,
2
the formation of a Cu clusterꢀpair that connects with each other
2
which is higher than reported MOFs possessing similar surface
areas and even comparable with some highly porous MOFs. For
example, SNUꢀ50', 77H, NTUꢀ111, NTUꢀ112, and NTUꢀ113
to construct twoꢀdimensional (2D) parallel layers with the padꢀ
dlewheel Cu clusters arranged regularly in quadrilateral geomeꢀ
2
tries (Figure 1c). Finally, each L1 connecting four pairs of
showed CO ꢀuptake values of 120.0, 41.8, 124.6, 158.5, and 166.8
2
isophthalate bridged Cu clusterꢀpairs from the 2D layers makes 1
2
3
ꢀ1
cm g under the same conditions, having their BET surface areas
into a (4,3,4)ꢀconnected network with "clicked" nitrogenꢀrich
2
ꢀ1
12b,18
of 2300, 3670, 2450, 2992, and 3095 m g , respectively.
triazole rings uniformly located between paddlewheel Cu conꢀ
2
1
5
The high CO uptake should be attributed to the successful introꢀ
2
structed layers. The regular combination of the paddlewheel Cu2
clusters and nitrogenꢀrich triazoleꢀcontaining L1 endows 1 with a
high porosity, having two kinds of pores in diameters of 7.9 Å and
duction of exposed metal sites and nitrogenꢀrich triazole units into
12
the framework of 1. Then, the isosteric heat of adsorption (Qst)
for CO capture was calculated based on the adsorption isotherms
2
1
2.6 Å, respectively. After removing the discrete and coordinated
at 273 and 298 K (Figure 2b and Figure S6 in the SI) through the
solvent molecules in the framework, the MOF structure was calꢀ
1c
16
ClausiusꢀClapeyron equation. It was found that the Q value of
st
culated using PLATON/VOID program. The total solventꢀ
2
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ꢀ
1
1
for CO sorption is ~32.2 kJ mol at low loading range, folꢀ
MOF with the same embedded Lewis acid metal sites (exposed
2
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
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2
2
2
2
2
2
2
2
3
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6
lowed by the convergence into a pseudoꢀplateau at Q of ~25.8 kJ
paddlewheel Cu clusters), HKUSTꢀ1 was also taken as a catalyst
in these heterogeneous reactions as control experiments.
st
2
ꢀ
1
14a
mol with relatively high uptake. The Qst is also comparable to
ꢀ
some reported nitrogenꢀrich MOFs such as NTUꢀ105 (~35 kJ mol
Yields of the obtained cyclic carbonates produced from CO2
with related epoxides catalyzed by 1 and HKUSTꢀ1 were deterꢀ
1
ꢀ1
at low loading range and ~24 kJ mol at relatively high upꢀ
take), confirming that the constructed MOF 1 has a high affiniꢀ
12a
mined under 1 atm CO pressure at room temperature for 48 h. As
2
ty to CO2.
shown in Figure 4 and Table 1, the reaction yields catalyzed by 1
from related epoxides are 96% for 2ꢀmethyloxirane, 83% for 2ꢀ
ethyloxirane, 85% for 2ꢀ(chloromethyl)oxirane, and 88% for 2ꢀ
Scheme 1. Catalytic cycloaddition of CO with epoxides to proꢀ
2
(
bromomethyl)oxirane with corresponding turnover frequency
duce cyclic carbonates.
ꢀ1
(TOF) values of 200.0, 172.9, 177, and 183.3 h per paddlewheel
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
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0
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2
3
4
5
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7
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9
0
1
2
3
4
5
6
7
8
9
0
O
Cu cluster. For comparison, the yields are 65%, 54%, 56%, and
2
57% catalyzed by HKUSTꢀ1 with TOF values of 135.4, 112.5,
O
MOF Catalyst
ꢀ
1
+ CO2
O
O
116.7, and 118.8 h per Cu cluster, respectively. The comparison
2
Room Temperature
of the yields for all four products clearly reveals that the triazoleꢀ
containing 1 shows remarkably higher performance than HKUSTꢀ
R
R
1
for catalytic CO cycloaddition with epoxides at the same condiꢀ
2
Raman spectroscopy has recently been employed to study MOF
tions. Given similar pore size and the same embedded Lewis acid
metal sites in both 1 and HKUSTꢀ1, the high catalytic activity of 1
properties via spectroscopic changes before and after gas adsorpꢀ
19
tion. Therefore, in-situ Raman spectral measurements were imꢀ
plemented to 1 in order to monitor its affinity toward CO moleꢀ
should be ascribed to the increase of the CO affinity via the inꢀ
2
2
troduction of the nitrogenꢀrich triazole groups into the framework.
ꢀ
1
cule. As shown in Figure 3, a new peak for 1 appears at 1377 cm
Taking the catalytic CO cycloaddition with propylene oxide to
2
after adsorbing CO . While this peak is weaker and broader at
2
produce propylene carbonate as an example, the recyclability was
tested by using recycled catalyst 1 collected by centrifugation. No
significant decrease in catalytic activity was observed even after 5
runs of the same reactions (Figure S9 in the SI). The stability of 1
was also proven by the PXRD measurements, showing that the
PXRD patterns of the recycled 1 are a good agreement with calcuꢀ
lated pattern from its crystal data (Figure S10 in the SI). The
PXRD results indicate that the framework was retained very well
room temperature, it becomes much clearer and sharper at lower
temperatures. The generated peak should correspond to CO adꢀ
2
sorbed in the framework by showing the symmetric C=O stretch
19
mode of CO based on the literature description. The peak posiꢀ
2
ꢀ
1
tion is redꢀshifted for ~11 cm as compared with the reported
value for gaseous CO at 1388 cm . The peak shift should be due
ꢀ
1
2
to the interaction between adsorbed CO and the framework of 1.
2
8
Thus, the framework affinity to CO is indisputably evidenced by
2
after the catalytic reactions. Based on previous reports, possible
Raman spectroscopic investigations.
MOFꢀbased catalytic mechanism was discussed in the SI (Figure
S11). The high activity and recyclability make MOF 1 an excelꢀ
O
O
O
O
O
O
O
lent heterogeneous catalyst for carbon fixation via CO chemical
O
O
2
O
O
O
Cl
conversion reactions.
100
96%
Br
88%
Table 1. Yields of various cyclic carbonates prepared from the
8
5%
83%
cycloaddition of CO with small/bigꢀsize epoxides catalyzed by 1.
8
0
0
2
65%
Entry
Epoxides
Products
Yields
6
56%
57%
54%
Small substrates
1
O
96
O
O
O
40
20
0
O
2
O
83
O
O
O
O
3
O
85
88
Cl
1
2
3
4
O
Cl
Reactions
O
O
4
O
Br
O
Figure 4. Yields of various cyclic carbonates prepared from the
Br
cycloaddition of CO with related epoxides catalyzed by MOF 1
2
Large substrates
5
(black) and HKUSTꢀ1 (gray) under 1 atm CO pressure at room
2
temperature for 48 h. The reaction was conducted in a Schlenk
O
O
O
8
6
O
tube using epoxide (20 mmol) with CO purged at 1 atm under
2
solventꢀfree environment at room temperature, catalyzed by 0.2
mol% per copper paddlewheel unit of MOF with a coꢀcatalyst of
tetraꢀnꢀtertbutylammonium bromide (TBAB, 0.65 g, 10 mol%).
6
7
O
O
O
O
O
O
The inherent CO ꢀadsorbing property and embedded Lewis acid
5
2
O
O
O
O
metal sites in the framework suggest that MOF 1 should be a
highly promising heterogeneous catalyst for CO related reactions.
2
Then, we extended this work to larger epoxide substrates in orꢀ
Among CO chemical conversion reactions, catalyzed CO cyꢀ
2
2
der to check the generality for such CO cycloaddition reactions.
cloaddition with epoxides has been intensively investigated due to
wide applications of the produced carbonates in pharmaceutical
2
Since the experiments were conducted under solventꢀfree condiꢀ
tions, three large liquid substrates were selected (Table 1). When
8,20
and electrochemical industries.
Therefore, catalytic perforꢀ
1
,2ꢀepoxyoctane (5), 1,2ꢀepoxydodecane (6) and 2ꢀethylhexyl
mance of 1 in the cycloaddition of CO with epoxides to produce
2
glycidyl ether (7) were employed, the product yields showed
various carbonates (Scheme 1) was explored. As a benchmark
3
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sharp decreases in the same conditions. They were just 8%, 6%
and 5% (entries 5ꢀ7 in Table 1) respectively, suggesting that large
substrates cannot enter into the porous framework of 1 for cataꢀ
lyzed reactions. These observations also indicate that the former
reactions of small substrates (entries 1ꢀ4 in Table 1) were carried
out within the framework of 1, and the MOF exhibits the size
selectivity to small and large substrates in the reactions. Thus,
remarkably high efficiency and the size selectivity to small epoxꢀ
(3) (a) Iizuka, K.; Wato, T.; Miseki, Y.; Saito, K.; Kudo, A. J. Am.
Chem. Soc. 2011, 133, 20863−20868. (b) Xie, Y.; Wang, T.ꢀT.; Liu, X.ꢀH.;
Zou, K.; Deng, W.ꢀQ. Nat. Commun. 2013, 4, 1960. (c) Tu, W.; Zhou, Y.;
Zou, Z. Adv. Mater. 2014, 26, 4607–4626. (d) Lin, S.; Diercks, C. S.;
Zhang, Y.ꢀB.; Kornienko, N.; Nichols, E. M.; Zhao, Y.; Paris, A. R.; Kim,
D.; Yang, P.; Yaghi, O. M.; Chang, C. J. Science 2015, 349, 1208ꢀ1213.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
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5
5
5
5
5
5
5
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(4) (a) Sculley, J.; Yuan, D.; Zhou, H.ꢀC. Energy Environ. Sci. 2011, 4,
2721–2735. (b) Suh, M. P.; Park, H. J.; Prasad T. K.; Lim, D.ꢀW. Chem.
Rev. 2012, 112, 782ꢀ835.
ides on catalytic CO cycloaddition confirm that MOF 1 is a suitꢀ
able heterogeneous catalyst for carbon fixation.
(5) (a) He, Y.; Zhou, W.; Yildirim, T. Chen, B. Energy Environ. Sci.
2013, 6, 2735ꢀ2744. (b) He, Y.; Zhou, W.; Qiand, G.; Chen, B. Chem. Soc.
Rev. 2014, 43, 5657ꢀ5678.
2
In summary, we have synthesized a triazoleꢀcontaining ocꢀ
tcarboxylate linker by versatile “click chemistry”, and subseꢀ
quently it has been utilized for the construction of a highly porous
MOF with Cu ions. The constructed MOF incorporating both
exposed metal sites and nitrogenꢀrich triazole groups presents a
(6) (a) Xiang, S.ꢀC.; Zhang, Z.; Zhao, C.ꢀG.; Hong, K.; Zhao, X.; Ding,
0
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2
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2
search sheds light on how the framework affinity of MOFs to CO2
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the efficiency of CO chemical conversion during the process of
2
the carbon fixation.
ASSOCIATED CONTENT
Supporting Information
Experimental details. CCDC 1436567. This material is available
free of charge via the Internet at http://pubs.acs.org.
(9) MOF 1 in the main text can be cited as NTU-180.
(10) (a) Vogiatzis, K. D.; Mavrandonakis, A.; Klopper, W.; Froudakis,
AUTHOR INFORMATION
G. E. ChemPhysChem 2009, 10, 374–383. (b) Li, P.ꢀZ.; Zhao, Y. Chem.
Asian J. 2013, 8, 1680ꢀ1691.
Corresponding Author
(11) (a) Vaidhyanathan, R.; Iremonger, S. S.; Shimizu, G. K. H.; Boyd,
zhaoyanli@ntu.edu.sg; rzou@pku.edu.cn
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S.Y.; Ang, C.Y.; Chen, H.ꢀZ. Liu, J.; Zou, R.ꢀQ.; Zhao, Y. Angew. Chem.
Int. Ed. 2015, 54, 12748ꢀ12752.
Author Contributions
§
P.ꢀZ. Li, X.ꢀJ. Wang and J. Liu contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This research was financially supported by the National Research
Foundation (NRF), Prime Minister’s Office, Singapore through its
Campus for Research Excellence and Technological Enterprise
(14) (a) Chui, S. S.ꢀY.; Lo, S. M.ꢀF.; Charmant, J. P. H.; Orpen, A. G.;
Williams, I. D. Science, 1999, 283, 1148ꢀ1150. (b) Rao, X.; Cai, J.; Yu, J.;
He, Y.; Wu, C.; Zhou, W.; Yildirim, T.; Chen, B.; Qian, G. Chem. Com-
mun. 2013, 49, 6719ꢀ6721.
(CREATE) Program—Singapore Peking University Research
Centre for a Sustainable LowꢀCarbon Future, and the NTUꢀ
A*Star Silicon Technologies Centre of Excellence under grant
No. 11235100003. R. Z. thanks the National Natural Science
Foundation of China (no. 51322205, 21371014, and 11175006)
for the financial support.
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