3d-4f Heterometal-Organic Frameworks for Efficient Capture and Conversion of CO2

Article abstract of DOI:10.1021/acs.cgd.7b00063

Two novel three-dimensional 3d-4f heterometallic-organic frameworks {[TbZn(BPDC)₂(μ₂-H₂O)Cl(H₂O)₃]·5H₂O·0.5DMA}_n (1) and {[TbCo(BPDC)₂(μ₂-H₂O)Cl(H₂O)₃]·8H₂O·0.5DMA}_n (2) have been synthesized and structurally characterized. They are isostructural and exhibit irregular one-dimensional channels with a large potential pore volume. Importantly, both of them demonstrate excellent catalytic activity for the chemical fixation of CO₂ into cyclic carbonates under mild conditions. Moreover, the catalytic recycling of compound 1 as a representative example was explored; it can be easily separated and reused for at least four times without significant reduction in catalytic ability.

Full text of DOI:10.1021/acs.cgd.7b00063

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Article
3d-4f Heterometal-Organic Frameworks for
Efficient Capture and Conversion of CO2
Wan-Zhen Qiao, Hang Xu, Peng Cheng, and Bin Zhao
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00063 • Publication Date (Web): 17 Apr 2017
Downloaded from http://pubs.acs.org on April 25, 2017
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3dꢀ4f HeterometalꢀOrganic Frameworks for
Efficient Capture and Conversion of CO2
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WanꢀZhen Qiao, Hang Xu, Peng Cheng, Bin Zhao*
Department of Chemistry, Key Laboratory of Advanced Energy Material Chemistry (MOE), and
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai
University, Tianjin 300071, China
ABSTRACT: Two novel threeꢀdimensional 3dꢀ4f heterometallicꢀorganic frameworks
{[TbZn(BPDC)2(ꢁ2ꢀH2O)Cl(H2O)3]·5H2O·0.5DMA}n
(1)
and
{[TbCo(BPDC)2(ꢁ2ꢀ
H2O)Cl(H2O)3]·8H2O·0.5DMA}n (2) have been synthesized and structurally characterized. They
are isostructural and exhibit irregular oneꢀdimensional channels with large potential pore volume.
Importantly, both of them demonstrate excellent catalytic activity for the chemical fixation of
CO2 into cyclic carbonates under mild conditions. Moreover, the catalytic recycling of
compound 1 as a representative example was explored, it can be easily separated and reused for
at least four times without significant reduction in catalytic ability.
INTRODUCTION
Carbon dioxide (CO2), as the major greenhouse gas, has been considered to cause great
environmental concerns, such as ocean acidity, melting of glaciers.1,2 The CO2 emission mainly
originates from burning of fossil fuels and accumulates in the atmosphere at an alarming pace.3 It
is imperative to explore CO2 capture and sequestration (CCS) technologies to decrease CO2 from
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emission sources.4ꢀ6 Up to date, extensive efforts have been made to obtain new materials for
advanced CCS technologies.7ꢀ9 Additionally, as a renewable carbon feedstock, CO2 can be
utilized to transform into high value chemicals.10ꢀ16 Particularly, the cyclic carbonates formed by
the coupling of CO2 with epoxides have attracted significant attention owing to its 100% atom
economic nature.17,18 Besides, cyclic carbonates possess potential extensive application as
electrolytes in the lithiumꢀion batteries, precursors for polymeric materials, intermediates of fine
chemicals, organic solvents and so on.19ꢀ21 Impressively, various catalytic systems have been
developed for CO2 fixation into cyclic carbonates, including homogeneous catalysts and
heterogeneous catalysts, such as ionic liquids,22,23 alkali metal salts,24 metal oxides,25 and
functional polymers.26,27 Thus, it is more favorable to develop materials which can efficiently
capture CO2 and simultaneously catalyze CO2 conversion.
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Emerging as a new class of functional materials, metal organic frameworks (MOFs),28ꢀ33
which feature tailorable structures, exceptional properties,34ꢀ41 have been proposed to be
promising materials to meet the dual challenge of CO2 capture and conversion for the following
reasons: (a) the porous MOFs can significantly absorb CO2,42ꢀ45(b) the well ordered porous
structures can enrich substrates and facilitate the accessibility of substrates to active sites, (c) the
metal ions can serve as Lewis acid sites to efficiently activate epoxide,46ꢀ49 (d) stable MOFs, as
heterogeneous catalysts, remain excellent catalytic performance after being successively reused.
Thus, it is of vital importance to develop MOFꢀbased catalysts for efficient CO2 capture and
conversion.50ꢀ53
In this contribution, two 3dꢀ4f heterometallic MOFs {[TbZn(BPDC)2(ꢁ2ꢀ
H2O)Cl(H2O)3]·5H2O·0.5DMA}n (1) and {[TbCo(BPDC)2(ꢁ2ꢀH2O)Cl(H2O)3]·8H2O·0.5DMA}n
(2) were obtained based on 5,5′ꢀdicarboxylateꢀ2,2′ꢀdipyridine (H2BPDC) and structurally
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characterized. They are isostructural and exhibit oneꢀdimensional open channels with large
potential pore volume. Furthermore, both of them exhibit excellent catalytic performance for
CO2 conversion into cyclic carbonates in the absence of solvent under mild conditions and
compound 1 can be used as a recoverable heterogeneous catalyst with high activity.
EXPERIMENT SECTION
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Synthesis of {[TbZn(BPDC)2(µ2ꢀH2O)Cl(H2O)3]·5H2O·0.5DMA}n (1)
A mixture of Tb(ClO4)3·6H2O (28.5 mg, 0.05 mmol), H2BPDC (24.4 mg, 0.1 mmol), ZnCl2
(6.8 mg, 0.05 mmol), H2O (1 mL) and DMA (4 mL) were added into a 8 mL glass vial. The glass
vessel was heated at 80 °C for three days under autogenous pressure and then cooled to room
temperature at 2 °C/h under ambient conditions. The colorless block crystals were obtained and
washed with DMA. Yield: 50%, based on Tb(ClO4)3·6H2O. Elemental analysis (%) Calcd for
compound 1 (TbZnC26H34.5N4.5O17.5Cl): C 32.86, H 3.63, N 6.64. Found: C 32.89, H 3.69, N
6.68.
Synthesis of {[TbCo(BPDC)2(µ2ꢀH2O)Cl(H2O)3]·8H2O·0.5DMA}n (2)
A mixture of Tb(ClO4)3·6H2O (28.5 mg, 0.05 mmol), H2BPDC(24.4 mg, 0.1 mmol),
CoCl2·6H2O (11.9 mg, 0.05 mmol), H2O (1 mL) and DMA (4 mL) were added to a 8 mL glass
vial. The glass vessel was heated at 80 °C for three days under autogenous pressure and then
cooled to room temperature at 2 °C/h under ambient conditions. The colorless block crystals
were obtained and washed with DMA. Yield: 50%, based on Tb(ClO4)3·6H2O. Elemental
analysis (%) Calcd for compound 2 (TbCoC26H40.5N4.5O20.5Cl): C 31.31, H 4.06, N 6.32. Found:
C 31.36, H 4.10, N 6.34.
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Catalytic Performance Evaluation
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In each individual reaction, 2 mmol epoxide substrate and 20 mg compound 1 catalyst (1 mol %
based on Tb metal center) together with 32 mg tetrabutylammonium bromide (TBAB, 5 mol %)
were added into a 10 mL reaction tube. The tube was purged with CO2 at 1 atm under solvent
free environment and then was stirred (600 rpm) for 12h to complete the reaction. After the
catalytic reaction, the catalyst was separated by centrifugation and the product yields were
determined by 1H NMR. To explore the recyclability, the catalyst was isolated from the reaction
solution, washed with CH2Cl2 for three times, dried at ambient temperature, and then reused in
the next run of the reaction.
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RESULTS AND DISCUSSION
Structure
The Xꢀray singleꢀcrystal diffraction analysis reveals that 1 and 2 are isostructural. They both
crystallize in the monoclinic system with space group C2/c. Thus compound 1 as a representative
example is selected to describe the crystal structures in details. The asymmetric unit in 1 consists
of one Tb3+ ion, one Zn2+ion, one ꢁ2ꢀH2O molecule and two BPDC2ꢀ anions. Eightꢀcoordinated
Tb3+ has an triangular dodecahedron geometry, which is achieved by four carboxylic oxygen
atoms, two water molecules and two ꢁ2ꢀH2O molecules (Figure 1). The framework is composed
of two distinct building blocks [Tb2(ꢁ2ꢀH2O)2(COO)8(H2O)4] (abbr. as [Tb2] unit) and
[Zn(BPDC)2(H2O)Cl] (abbr. as [Zn(BPDC)2] unit) (Figure S2). Two Tb3+ ions are bridged into a
binuclear [Tb2] unit by two ꢁ2ꢀ H2O molecules. Four nitrogen atoms from two BPDC2ꢀ ions, one
water molecule and one chloride ion complete the sixꢀcoordinated environment of Zn2+ anions
(Figure 1a), forming a [Zn(BPDC)2(H2O)Cl] motif, which connects the [Tb2] unit into a 3D
neutral framework (Figure 1b). The framework possesses oneꢀdimensional irregular channels
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along c direction with a diameter of about 6 Å (Figure 1b). Additionally, the potential pore
volume of 1 is as high as 46%, calculated by the PLATON program.
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In order to simplify the complicated framework, each [Tb2] unit is considered as an 8ꢀ
connected node which links with eight [Zn(BPDC)2] units and each [Zn(BPDC)2] unit is
regarded as a 4ꢀconnected node which bridges four [Tb2] units. Thus the framework can be
simplified into a (4,8)ꢀconnected topological structure with topology symbol of flu54 (Figure 1c,
Figure S2). Thermogravimetric (TGA) analysis and elemental microanalyses (EA) indicate that
five water molecules and half of one N,Nꢀdimethyl acetamide (DMA) molecule are in the
asymmetric unit.
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Figure 1. (a) the coordinated environments of Tb3+, Zn2+ and BPDC2ꢀ ligand in compound 1.
(b) 3D framework of 1 along c direction. (c) Simplified flu topology of 1.
Powder Xꢀray diffraction Analyses (PXRD) and Thermogravimetric Analysis (TGA)
PXRD analyses were carried out at ambient conditions. The PXRD patterns of asꢀ
synthesized samples are in conformity with the simulated ones from the singleꢀcrystal data
suggesting the high phase purity of the sample (Figure S3). As shown in the Figure S4, TGA
curve of compound 1 exhibits two steps of weight loss. The first weight loss of 20.3% between
36 °C and 190 °C corresponds to the loss of five free water molecules, half of one free DMA
molecule and three coordinated water molecules (calcd: 19.9%). Subsequently, TGA curve
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mainly stays in a plateau, indicating the high thermal stability of the framework 1. Then, the
second weight loss above 350 °C stems from the decomposition of 3D framework. As to
compound 2, TGA curve also exhibits two steps of weight loss. The first weight loss of 24.4%
between 46 °C and 220 °C corresponds to the loss of eight free water molecules, half of one free
DMA molecule and three coordinated water molecules (calcd: 24.2%). Subsequently, TGA curve
mainly stays in a plateau, indicating the high thermal stability of the framework 2. Then, the
second weight loss above 350 °C stems from the decomposition of 3D framework.
Gas Adsorption
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Inspired by its large void volume, the gas adsorption property of 1 as a representative
example was studied. Before the measurement, about 100 mg crystals of compound 1 was
immersed in CH2Cl2 for six days during which the supernatant was exchanged once every eight
hours. Then the crystals were outgassed under dynamic vacuum at 25 °C for 12 hours to afford
1a. At 298 K, the CO2 adsorption property was studied in a relative pressure ranging from 10ꢀ3
to 1 atm. As shown in Figure S5, the adsorption measurement shows linear increase with a
maximum adsorption CO2 capacity of 25 cm3/g at point P/P0 = 1.0, which is relatively low
compared to other MOFs materials.58 It is interesting that the desorption isotherm of 1a does not
retrace the adsorption one, showing a large hysteresis and an abrupt drop at point P/P0 = 0.1. It is
very difficult to desorb all of the included CO2, possibly suggesting the strong chemisorption
interaction occurs between CO2 and the framework 1a.45,55.
Catalytic Properties
The moderate CO2 uptake properties of compound 1 motivated us to investigate its
heterogeneous catalytic ability for cycloaddition of CO2 with epoxides to generate cyclic
carbonates. The styrene oxide was chosen as the model substrate to explore the optimized
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reaction condition. During our investigations of various reports, we chose relatively mild
conditions in the presence of 2.5 mol % TBAB to study the catalytic ability of compound 1, the
results were summarized in Table 1. It can be seen that the yield gradually increased when the
temperature was increased, but the yield was only 77% at 70 °C (Table 1, entries 1ꢀ3). In order to
avoid much energy consume from higher temperature, the TBAB amount was increased to 5
mol % (Table 1, entries 4ꢀ6). The results revealed that the optimized condition should be 20 mg
compound 1 and 5 mol % TBAB at 70 °C (Table 1, entry 6). Under the optimized conditions, the
conversion reached over 99%. Comparably, the yield was less than 1% when TBAB was absent
in the system and the yield was only 57% when compound 1 was absent in the system under the
employed reaction conditions. (Table 1, entries 7 and 8). Thus, both compound 1 and TBAB
performed indispensable roles in the reaction. It is proposed that metal ions serve as Lewis acid
sites to efficiently activate epoxide and TBAB is employed as a cocatalyst in the experiment in
the previous reports.50,51 The synergistic effect of compound 1 and TBAB is the main reason of
high catalytic activity of the catalyst system under mild conditions.
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Generally, Lewis acid sites are widely considered to be responsible for CO2 conversion with
epoxides. The oxyphilic and highly Lewis acidic nature make rare metals potentially good
catalysts for the activation of epoxides and the subsequent coupling with CO2.56,57 Furthermore,
one isostructural MOF (compound 2) was synthesized and investigated on its catalytic ability in
the catalytic system.
As shown in Table 2, compound 2 was investigated on its catalytic ability in the catalytic
system. In the presence of 2.5 mol % TBAB, the yield was only 77% at 70 °C (Table 2, entry 1).
In order to avoid much energy consume from higher temperature, the TBAB amount was
increased to 5 mol % (Table 2, entries 2ꢀ5). The results revealed that the optimized condition
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should be 20 mg compound 2 and 5 mol % TBAB at 80 °C (Table 2, entry 5). Under the
optimized conditions, the conversion reached over 99%. Comparably, the yield was less than 1%
when TBAB was absent in the system and the yield was only 69% when compound 2 was absent
in the system under the employed reaction conditions. (Table 2, entries 6 and 7). In comparison,
the optimized temperature for compound 1 was 70 °C. These results demonstrated that Zn and
Co metal centers also activated the epoxides. Thus the excellent catalytic performance can be
ascribed to significant synergistic effects between the Tb centers and transition metal (Zn, Co)
centers.
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Table 1. Cycloaddition reaction of CO2 and Styrene Oxide under various conditionsa.
Entry
Catalyst 1 (mg)
TBAB (mol %)
T (°C)
50
Yield (%)b
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0
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>99
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a Reaction conditions: styrene oxide (240.3 mg, 2.0 mmol), solvent free, 20 mg catalyst 1 loading
(based on Tb metal center, 1 mol %), CO2 (0.1 MPa), 12h
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b Determined by 1H NMR spectroscopy using 1,3,5ꢀtrimethoxybenzene as an internal standard.
Table 2. Cycloaddition reaction of CO2 and Styrene Oxide under various conditionsa with
compound 2.
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Entry
Catalyst 2 (mg)
TBAB (mol %)
T (°C)
Yield (%)b
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>99
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a Reaction conditions: styrene oxide (240.3 mg, 2.0 mmol), solvent free, 20 mg catalyst 2 loading
(based on Tb metal center, 1 mol %), CO2 (0.1 MPa), 12h.
b Determined by 1H NMR spectroscopy using 1,3,5ꢀtrimethoxybenzene as an internal standard.
In order to verify the potential generality of the catalyst system, compound 1 was selected
as representative example and the scope of the reaction was further extended to other epoxides.
As shown in Table 3, compound 1 revealed excellent catalytic performance toward the
conversion of CO2 with various epoxides in high yields (92-99%, Table 3). It can be inferred that
compound 1 has the potential application in catalytic synthesis of cyclic carbonates from CO2
and epoxides.
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Table 3. Cycloaddition reaction of CO2 and various epoxides with catalyst 1a.
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Entry
1
Epoxides
Products
Yield (%)b
95
2
3
>99
>99
4
92
a
Reaction conditions: epoxides (2.0 mmol), solvent free, catalyst 1 loading (based on Zn metal
center, 1 mmol %), CO2 (0.1 MPa), 70 °C, 12h, TBAB (32.4 mg, 0.1 mmol, 5 mol %).
b Determined by 1H NMR spectroscopy using 1,3,5ꢀtrimethoxybenzene as an internal standard.
To test its recyclability, taking the CO2 cycloaddition with styrene epoxide as an example,
catalyst 1 (as a representative example) was successively reused for four runs without any
significant decrease in the catalytic efficiency (Figure 2). Additionally, the structure integrity of
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compound 1 after catalysis was proved by TGA analysis (Figure S6). Inductively coupled plasma
(ICP) studies revealed that only trace amounts of leakage from the robust framework occurred,
demonstrating its high recoverable performance (Table 4). Overall, the high efficiency and good
recyclability make compound 1 appealing among heterogeneous catalysts for chemical fixation
of CO2 into cyclic carbonates.
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Figure 2. Recycling efficiency of compound 1 for CO2 cycloaddition with styrene oxide.
Compound
Tb3+ (ppm)
Zn2+ (ppm)
1 after catalytic recyclings (filter liquor)
0.1106
0.1901
Mass loss percent (%)
0.16
0.79
Table 4. The ICP results of compound 1 after catalytic recyclings and mass loss percent.
On the basis of some previous reports,51 a tentative mechanism was proposed for the
cycloaddition of CO2 and epoxides into cyclic carbonates catalyzed by the strong Lewis acid
based catalyst 1 (as a representative example), as illustrated in Figure 3.
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Figure 3. A representation of possible mechanism of cycloaddition of epoxide with CO2.
First, the framework enriched CO2 and substrates. Then the reaction was initiated by
binding the epoxide with Lewis acid metal sites through the oxygen atom of epoxide to activate
the epoxy ring. Thus the CꢀO bond of the epoxide is weakened, partly due to electron transfer
from oxygen atom to metal center. Subsequently, the Brꢀ from TBAB attacked the lessꢀhindered
carbon atom of the coordinated epoxide to open the epoxide ring, due to its lower steric effect
and higher positive charge. Then the carbon atom of CO2 interacted with the oxygen anion of the
opened epoxide ring and positively charged carbon of the epoxide interacted with one oxygen
atom from CO2, forming an alkylcarbonate anion. Finally, the corresponding cyclic carbonate
was obtained through the intramolecular ring closure. It could be deduced that the synergistic
effect of the Lewis acid metal sites and the moderate uptake of CO2 promote the cycloaddition
reaction, leading to high catalytic activity of compound 1 for CO2 conversion into cyclic
carbonates.
CONCLUSIONS
In summary, two microporous 3dꢀ4f heterometallic MOFs were obtained under
solvothermal condition. They are isostructural and feature large potential pore volume.
Furthermore, both of them exhibit excellent performance as catalysts for chemical fixation of
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CO2 into cyclic carbonates under mild conditions. Significantly, compound 1 could be easily
separated and remain its high catalytic activity after at least four runs of recyclings.
ASSOCIATED CONTENT
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Supporting Information
The supporting information is available free of charge on the ACS Publications website.
PXRD, TGA and other experimental details (PDF).
Accession codes
CCDC 1520461 and 1533607 contain the supplementary crystallographic data for this paper.
These data can be obtained freely from the Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
AUTHOR INFORMATION
Corresponding Author
*Email: zhaobin@nankai.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supporting by the NSFC (21625103, 21571107 and 21421001), SFC of Tianjin
(15JCZDJC37700), and 111 Project (B12015).
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3dꢀ4f HeterometalꢀOrganic Frameworks for Efficient Capture and
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Conversion of CO2
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WanꢀZhen Qiao, Hang Xu, Peng Cheng, Bin Zhao*
Two threeꢀdimensional 3dꢀ4f heterometallic MOFs demonstrate excellent catalytic ability
for CO2 conversion into cyclic carbonates with high yield, and compound 1 can be used as a
recoverable heterogeneous catalyst with high activity.
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