Salen-Co(III) insertion in multivariate cationic metal-organic frameworks for the enhanced cycloaddition reaction of carbon dioxide

Article abstract of DOI:10.1039/c8cc10268f

The salen-Co(iii) motif was inserted into imidazolium-functionalized multivariate cationic zirconium metal-organic frameworks (MOFs). The salen-Co(iii), as a Lewis acid site, and the Br^- of imidazolium, as a nucleophile, are synergistically catalytic for the enhanced cycloaddition reaction of carbon dioxide with epoxides.

Full text of DOI:10.1039/c8cc10268f

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Salen-Co(III) insertion in multivariate cationic metal-organic
frameworks for the enhanced cycloaddition reaction of carbon
dioxide
Received 00th January 20xx,
Accepted 00th January 20xx
Tao-Tao Liu,a,b Jun Liang, Rui-Xu, Yuan-Biao Huang,*a,b and Rong Cao*a,b
a
a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Salen-Co(III) motif was inserted into imidazolium-functionalized MOFs with different length of ligands has been achieved due
multivariate cationic zirconium metal-organic frameworks (MOFs). to the versatile connectivity and the easy formation of defect
-
7
8
6
The salen-Co(III) as Lewis acid site while Br of imidazolium as of the Zr cluster. The successful incorporation of porphyrin
nucleophile is synergistically catalytic for the enhanced or 1,2-bis(5-(4- carbonxyphenyl)-2-methylthien-3-yl)cyclopent-
9
cycloaddition reaction of carbon dioxide with epoxides.
1-ene (BCDTE) into UiO-66 make it possible to insert salen-M
into the framework of Zr-based MOF. However, to the best of
our knowledge, very rare salen-M based MTV-MOFs were
2
As the major by-product of fossil fuel combustion, CO is one
of the culprits of the greenhouse effect that causes
environmental problems including global warming, glacier
retreat and frozen soil. Therefore, it is an urgent need to
10
reported
and there was no report on the salen-M
incorporated into imidazolium-functionalized multivariate
cationic MOF.
Herein, salen-Co(III) motif was incorporated into the
framework of the imidazolium-functionalized UiO-66 via a
sequential mixed-ligands synthesis and post-synthetic
ionization strategy (Scheme 1). The salen-Co(III) motif as Lewis
reduce the content of CO
2
in air. Compared with the
adsorption method, the conversion of the adsorbed CO
2
into
2
1
highly value-added chemicals, such as cyclic carbonate, is
one of the most promising approaches that has the effect of
two birds with one stone.
-
acid center and Br of imidazolium part as nucleophile in the
As we know, the combination of salen-Co(III) complex and
co-catalyst, such as nucleophilic anion-contain imidazolium salt,
has been verified to be a very effective catalytic system for
cationic MTV-MOF can serve as heterogeneous catalyst for the
2
synergistically enhanced catalysis of CO cycloaddition reaction
with epoxides.
promotion of cycloaddition reaction of CO
2
with olefin
Initially, the imidazole-functionalized MTV-MOFs were
synthesized from the reaction of 2-(imidazol-1-yl)terephthalic
3
epoxides. However, it is difficult to separate the product from
the homogeneous catalytic system and the catalyst can’t be
easily recovered and reused. To circumvent these drawbacks,
the incorporation of salen-Co(III) motif into porous
heterogeneous catalyst containing co-catalyst is highly desired.
acid
(Im-BDC),
N,N'-Bis(3-carboxyl-salicylidene)-1,2-
cyclohexanediamino cobalt(III) acetate (salen-Co(III)) with
o
4
ratios of 6/4 or 9/1 and ZrCl in DMF at 120 C for 12 h (Schem-
e 1). Then, the imidazolium-functionalized cationic MTV-MOFs
were obtained by the reaction of the imidazole-functionalized
MTV-MOF with bromoethane. According to the inductive
coupled plasma emission spectroscopy (ICP) results (Table S1),
the molar ratio of the incorporated salen-Co(III) motif in all the
ligands of the two cationic MTV-MOFs are 23% and 12%,
respectively. So, the obtained imidazole-functionalized MTV-
4
Porous metal-organic frameworks (MOFs) constructed by
metal nodes and organic linkers have shown great potential in
CO
2
capture and heterogeneous catalysis due to their high
5
surface area, tunable chemical and pore structures.
Particularly, multivariate MOFs (MTV-MOFs) containing
multifunctional active sites have emerged as promising
candidates for synergistic catalysis and tandem reactions.6
Recently, the breakthrough for the synthesis of Zr-based MTV-
MOFs are denoted as Salen-Co(23%)⊂Im-UiO-66, Salen-
Co(12%) Im-UiO-66, while the corresponding cationic MTV-
⊂
-
MOFs are named as Salen-Co(23%)⊂(Br )Etim-UiO-66 and
-
Salen-Co(12%)⊂(Br )Etim-UiO-66, respectively. For comparison,
a.State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences Fujian, Fuzhou, 350002, P.R.
China. E-mail: rcao@fjirsm.ac.cn, ybhuang@fjirsm.ac.cn;
imidazolium-functionalized cationic UiO-66 (denoted as (Br-
)Etim-UiO-66) was also prepared according to our previously
b.
University of the Chinese Academy of Sciences, Beijing, China.
2k
reported method (Fig. S2). Notably, we tried to synthesize
†
Footnotes relating to the title and/or authors should appear here.
salen-Co(III) based Zr-MOF by direct synthesis method under
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See DOI: the same conditions, however, only low crystallinity powder
1
0.1039/x0xx00000x
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Scheme 1 Synthesis of salen-Co(III) inserted imidazolium-functionalized MTV-MOFs by mixed-ligands synthesis and post-synthetic
ionization.
was obtained (Fig. S3).
promoting catalysis. According to energy dispersive spectrom-
As shown in Fig. 1, the powder X-ray diffraction (PXRD) eter (EDS) results (Table S2), the atomic content of Br in Salen-
-
-
patterns of the four MTV-MOFs are consistent with those of Co(23%)⊂(Br )Etim-UiO-66 and Salen-Co(12%)⊂(Br )Etim-UiO-
the phase-pure UiO-66, indicating that the introduction of 66 are 0.44% and 1.44%, respectively, indicating that
salen-Co(III) ligands and postsynthesis procedure did not imidazolium was successfully formed. The energy-dispersive X-
change their topology of UiO-66. It is worth mentioning that ray spectroscopy (EDX) mapping analysis image of Salen-
-
the low crystallinity of Salen-Co(23%)
⊂
Im-UiO-66 and Salen- Co(23%)
⊂
(Br )Etim-UiO-66 reveals that N, Br and Co elements
-
Co(23%)
⊂
(Br )Etim-UiO-66 revealed by the broad PXRD are homogeneously distributed in the frameworks (Fig. 2c)
reflections was caused by their nanosized crystallites as shown suggesting that salen-Co(III) and imidazolium were uniformly
11
in SEM images (Fig. 2a and Fig. S10a). In the infrared grafted into the MTV-MOF.
-
1
spectroscopy (IR) curves (Fig. S4), the two peaks at 2939 cm
To further confirm that whether the salen-Co(III) ligand was
and 2860 cm- that attributed to the methylene in 1,2- coordinated to the Zr
aminocyclohexane motif were observed in the IR of the Salen- the cage of the (Br )Etim-UiO-66, N,N'-Bis(3-Br-salicylidene)-
Co(23%)⊂(Br )Etim-UiO-66, indicating that salen-Co(III) has 1,2-cyclohexanediamino cobalt(III) acetate (salen(Br)-Co(III))
1
clusters framework or encapsulated in
6
-
-
been successfully incorporated into these MTV-MOFs. The that has the similar size with salen-Co(III) but without
scanning electron microscopy (SEM) images show that Salen- carboxylic acid groups, was used to replace salen-Co(III) to
-
-
Co(23%)⊂(Br )Etim-UiO-66 (Fig. 2a) and Salen-Co(12%)⊂(Br conduct control experiments under the same conditions.
-
)
Etim-UiO-66 nanocrystals (Fig. 2b) have uniform small size of Different from light green color of salen-Co(12%)
⊂
(Br )Etim-
about 30 nm and 100-200 nm, respectively. Such nanoscale UiO-66 (Fig. 2d), white powders were obtained (Fig. 2e),
MTV-MOFs are favorable for contacting with substrate and
indicating that the ligand salen(Br)-Co(III) was not incorporated
-
Fig. 2 SEM images of a) Salen-Co(23%)
⊂
(Br )Etim-UiO-66 and
-
b) Salen-Co(12%)
⊂
(Br )Etim-UiO-66 (scale bar = 100 nm), c)
HAADF-STEM image and EDX elemental-mapping image (scale
Fig. 1 PXRD patterns of the simulated UiO-66 (black line),
-
-
bar = 50nm) of Salen-Co(23%)
⊂
(Br )Etim-UiO-66, photographs
Salen-Co(12%)
⊂
Im-UiO-66 (purple line), Salen-Co(12%)
⊂(Br
-
-
of d) Salen-Co(12%)
⊂
(Br )Etim-UiO-66 and e) (Br )Etim-UiO-66
)
Etim-UiO-66 (wine red line), Salen-Co(23%)
⊂
Im-UiO-66 (red
-
obtained from the reaction of salen(Br)-Co(III) and Im-BDC.
line) and Salen-Co(23%)
⊂(Br )Etim-UiO-66 (blue line).
2
| J. Name., 2012, 00, 1-3
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Table 1 Synthesis of cyclic carbonates from epoxides and
View Article Online
a
DOI: 10.1039/C8CC10268F
-
2
CO catalyzed by Salen-Co(23%)⊂(Br )Etim-UiO-66.
Entry
Substrate
Conv / %b
Selec / %b
O
O
1
2
3
92
84
79
96
93
96
O
O
O
4
84
87
2
Fig. 3 a) Nitrogen sorption curves at 77 K and b) CO sorption curves
at 298 K of the four MOFs (filled symbols for adsorption, open
symbols for desorption).
O
O
5
86
＞99
a
b
2
Reaction conditions: epoxide (5 mmol), 30 mg catalyst, CO (0.1 MPa), 393 K, 12 hours.
-
in (Br )Etim-UiO-66 and highlights the importance of the carbo- Determined by GC.
9
6
xylic acid group, which could coordinate to the Zr clusters.
-
More importantly, the color of the low crystallinity powder MTV-MOFs, Salen-Co(12%)⊂(Br )Etim-UiO-66 and Salen-
-
obtained from the reaction of salen-Co(III) and ZrCl
4
is brown Co(23%)⊂(Br )Etim-UiO-66, showed decreased N
2
adsorption
-
(
(
Fig. S10c) and the mixture of the low crystallinity powder and uptakes compared with (Br )Etim-UiO-66 (Fig. S11) and their
Br )Etim-UiO-66 is light brown (Fig. S10d), proving salen-Co(III) corresponding parent imidazole-functionalized MTV-MOFs,
-
2
-1
were inserted in MTV-MOFs rather than the mixture of the low both of them have moderate BET surface areas of 369 m g
-
2 -1
crystallinity powder and (Br )Etim-UiO-66.
and 208 m g , respectively. Moreover, Salen-Co(12%)
⊂
3
Im-
-1
Furthermore, X-ray photoelectron spectroscopy (XPS) (Fig. UiO-66 showed the highest CO
2
adsorption uptake (21 cm g )
S6 for Co) analysis revealed that the binding energy of Co 2p1/2 among the four MTV-MOFs, which was attributed to its high
and Co 2p3/2 in both salen-Co(III) ligand and Salen- BET surface area. Interestingly, although the cationic MTV-
-
Co(23%)⊂(Br )Etim-UiO-66 were 796 eV and 781 eV, MOFs have smaller BET surface areas compared with their
corresponding MOF parents, both of Salen-Co(12%)⊂(Br-
respectively, indicating that the valence state of cobalt eleme-
1
2
-
nt is +3. Furthermore, compared with the binding energy of )Etim-UiO-66 and Salen-Co(23%)
⊂
(Br )Etim-UiO-66 have large
N-Co (399.5 eV, Fig. S7) in salen-Co(III) ligand, the same peak in CO
2
adsorption uptakes of 19 and 14 cm3g-1 (Fig. 3b),
-
Salen-Co(23%)
⊂
(Br )Etim-UiO-66 was also observed. The respectively, which is ascribed to the high CO
2
affinity of the
results suggested that the salen-Co(III) motif was stable during imidazolium in the cationic MTV-MOFs. The high CO
the synthesis procedures. Such high valence state of Co(III) is adsorption of the MTV-MOFs could enhance the CO
2
2
favorable for activating the C-O bond of epoxides, thus could cycloaddition reaction.
3
promote the cycloaddition reaction of CO
2
. Moreover, the Co-
Such highly porous cationic MTV-MOFs containing salen-
-1
O peak (736 cm , Fig. S8) of the IR of salen(Br)-Co(III) still Co(III) Lewis acid site and imidazolium could make them as
exists under the same synthesis conditions further confirmed promising heterogeneous catalysts for CO cycloaddition
2
that Co atom could not leach from the salen-Co(III) ligand reactions with epoxides at 0.1 MPa without using any co-
-
during the synthesis of MTV-MOFs. In addition, the peak at catalyst. Firstly, Salen-Co(23%)⊂(Br )Etim-UiO-66 was used as
-
4
01.5 eV of N1s in the XPS of Salen-Co(23%)
⊂
(Br )Etim-UiO-66 catalyst and 5 mmol allyl glycidyl ether was chosen as
o
(
Fig. S7b) confirmed that the successfully formation of substrate to screen the optimized reaction conditions. At 60 C,
imidazolium in the cationic MTV-MOF.
although only 8% allyl glycidyl ether was transferred, very high
The pore features of these MTV-MOFs were tested by N
2
selectivity for 4-allyloxymethyl-1,3-dioxolan-2-one was
adsorption isotherms at 77 K (Fig. 3a). The curves for Salen- observed (98%, Table S3, entry 1). With the temperature
o
Co(12%)
⊂
Im-UiO-66 present
a
typical type-I behavior, increasing to 90 C, the conversion of allyl glycidyl ether
indicating it is microporous material with pore sizes of 0.7 nm, increased to 44% (Table S3, entry 2). Interestingly, 92% allyl
1
.2 nm and 1.5 nm (Fig. S9a). Interestingly, compared with glycidyl ether can be transferred into the corresponding cyclic
o
Salen-Co(12%)
curve in the range of P/P = 0.85-1 for Salen-Co(23%)
6 is observed, indicating that macropores were formed by the temperature for the following catalysis. It is necessary to
⊂
Im-UiO-66, an obvious hysteresis desorption carbonate with 96% selectivity at 120 C within 12 h (Table S3,
0
o
⊂
Im-UiO- entry 3). Therefore, 120 C was chosen as the optimal
6
interspaces of the small nanospheres. This phenomenon was mention that Co cannot be detected by ICP after hot-filtration
coincident with the SEM image (Fig. S10a). Compared with test, suggesting that the salen-Co(III) in the MOF is stable
o
Salen-Co(12%)
Teller (BET) surface area of 670 m g , Salen-Co(23%)
6
⊂
Im-UiO-66 with high Brunauer
–
Emmett
–
during the reaction at 120 C.
2
-1
⊂
Im-UiO-
It should be noted that the reaction could not proceed
6 has a decreased BET surface area of 340 m g , which was without any catalyst (Table S3, entry 4). Compared with Salen-
ascribed to that more pores were occupied by larger amount Co(23%)⊂(Br )Etim-UiO-66 with 92% selectivity, only 72%
of salen-Co(III) motifs. The results also indicated that salen- conversion was obtained when using Salen-Co(12%)⊂(Br-
Co(III) has been inserted in Im-UiO-66. After postsynthesis with )Etim-UiO-66 containing less amounts of salen-Co(III) sites
2
-1
-
ionization, although the imidazolium-functionalized cationic
under the same conditions (Table S3, entry 5). Furthermore,
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-
Tan, Y. Liu, W. Gong, Y. Cui, J. Am. Chem. SocV.i,ew2A0r1tic7le, O1n3lin9e
,
the cationic MOF, (Br )Etim-UiO-66 containing no salen-Co(III)
site exhibited only 70% conversion and 82% selectivity (Table
S3, entry 6). These control experiments indicated that the
incorporation of Lewis acid site salen-Co(III) in cationic MOFs
indeed significantly enhanced the activity and selectivity.
8
259; d) H. Xu, J.Hu, D. Wang, Z. Li, Q. Zhang, Y. Luo, S. Yu, H.
DOI: 10.1039/C8CC10268F
Jiang, J. Am. Chem. Soc., 2015, 137, 13440; e) C. Gao, Q.
Meng, K. Zhao, H. Yin, D. Wang, J. Guo, S. Zhao, L. Chang, M.
He, Q. Li, H. Zhao, X. Huang, Y. Gao, Z. Tang, Adv. Mater.,
2016, 28, 6485; f) X. Wang, Y. Zhou, Z. Guo, G. Chen, J. Li, Y.
-
Shi, Y. Liu and J. Wang, Chem. Sci., 2015,
Z. Chen, J. Tong, M. Yang, Z. Jiang and C. Li, ACS Catal., 2016,
, 1172; h) Z. Yang, H. Zhang, B. Yu, Y. Zhao, Z. Ma, G. Ji, B.
6, 6916; g) Q. Jiang,
Besides the Lewis acid site salen-Co(III), the counterion Br of
imidaolium part also plays important role in the catalysis.
Notably, the metalloligand salen-Co(III) (64% conversion and
3% selectivity, Table S3, entry 7) and Salen-Co(23%)
6 (65% conversion and 90% selectivity, Table S3, entry 8)
could catalyze the reaction due to the presence of the
nucleophilic acetate ion and imidazole nitrogen atoms,
respectively. However, compared with the bifunctional catalyst
6
Han and Z. Liu, Chem. Commun., 2015, 51, 11576; i) K. Wu, T.
Su, D. Hao, W. Liao, Y. Zhao, W. Ren, C. Denga and H. Lü,
Chem. Commun., 2018, 54, 9579; j) T. Liu, J. Liang, Y. Huang
and R. Cao, Chem. Commun., 2016, 52, 13288; k) J. Liang, R.
Chen, X. Wang, T. Liu, X. Wang, Y. Huang and R. Cao, Chem.
9
6
⊂Im-UiO-
1
3
14
Sci., 2017, 8, 1570; l) J. Liang, Y. Huang and R. Cao, Coordin.
Chem. Rev., 2019, 378, 32.
-
Salen-Co(23%)
⊂
(Br )Etim-UiO-66, both of them containing no
counterion Br of imidaolium nucleophile groups showed much
lower conversions and selectivities. Moreover, the physical
3
4
a) F. Song, C. Wang, J. Falkowski, L. Ma, and W Lin, J. Am.
Chem. Soc., 2010, 132, 15390; b) H. Yang, L. Zhang, W. Su, Q.
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Furukawa, K. Cordova, M. Keeffe and O. Yaghi, Science.,
-
-
mixture of (Br )Etim-UiO-66 and salen-Co(III) (Table S3, entry 9)
showed lower catalytic activity (62% conversion and 89%
selectivity), highlighting the importance of the salen-Co(III)
insertion in the frameworks for the synergistically enhanced
cycloaddition reaction. In addition, the bifunctional catalyst
could promote transformation of a variety of long-chain and
aromatic substituted epoxides, including 1,2-Epoxyhexane,
2
013, 341, 1230444; c) G. Yuan, H. Jiang, L. Zhang, Y. Liu and
Y. Cui, Coordin. Chem. Rev., 2019, 378, 483; d) J. Jiao, C. Tan,
Z. Li, Y. Liu, X. Han, and Y. Cui, J. Am. Chem. Soc., 2018, 140
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,
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Soc., 2018, 140, 16229; f) G. Yuan, Q. Zhang, Z. Wang, K.
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1
,2-Epoxyoctane, styrene oxide, and allyl phenyl ether with
satisfactory activities and selectivities (Table 1).
5
,
-
1605446; c) Y. Liu, A. Howarth, N. Vermeulen, S. Moon, J.
Hupp and O. Farha, Coordin. Chem. Rev., 2017, 346, 101; d) K.
Manna, P. Ji, Z. Lin, F. Greene, A. Urban, Nathan. Thacker and
More importantly, the catalyst Salen-Co(23%)⊂(Br )Etim-
UiO-66 possesses high stability and can be easily recovered
from reaction mixture by centrifugation and reused for at least
five runs without significant reduction in catalytic activity (90%
conversion and 96% selectivity, Fig. S12). After recycled five
runs, the PXRD revealed that Salen-Co(23%)⊂(Br )Etim-UiO-66
still remains UiO-66 topology (Fig. S13), although it shows
reduced BET surface area (Fig. S14).
In summary, we have successfully synthesized bifunctional
cationic Zr-based MTV-MOFs containing salen-Co(III) motif and
imidazolium by a sequential mixed-ligands synthesis and post-
synthetic ionization strategy. The amount of installed salen-
Co(III) can be controllable. The cationic MTV-MOF Salen-
W. Lin, Nat. Commun., 2016, 7, 12610.
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2
016, 55, 6471; b) J. Liang, Y. Xie, Q. Wu, X. Wang, T. Liu, H. Li,
-
Co(23%)⊂(Br )Etim-UiO-66 was demonstrated to be highly
Y. Huang and R. Cao, Inorg. Chem., 2018, 57, 2584.
active for the CO
2
cycloaddition reaction with epoxide.
9
1
1
J. Park, Q. Jiang, D. Feng and H. Zhou, Angew. Chem. Int. Ed.,
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016, 55, 7188.
Moreover, it has high stability and can be recovered easily and
reused at least five times without significant loss of activity.
We acknowledge the financial support from the National
Key Research and Development Program of China
2018YFA0208600, 2017YFA0700100), Key Research Program 12 T. Akitsu and Y. Einaga, Polyhedron., 2005, 25, 2655.
of Frontier Science, CAS (QYZDJ-SSW-SLH045), Strategic
Priority Research Program of the Chinese Academy of Sciences
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Notes and references
1
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a) A. Decortes, A. Castilla, A. Kleij, Angew. Chem. Int. Ed.,
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Cui, J. Am. Chem. Soc., 2016, 138, 12332; c) Q. Xia, Z. Li, C.
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| J. Name., 2012, 00, 1-3
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