Porous Metal-Organic Polyhedral Framework containing Cuboctahedron Cages as SBUs with High Affinity for H2 and CO2 Sorption: A Heterogeneous Catalyst for Chemical Fixation of CO2

Article abstract of DOI:10.1002/chem.201802829

Development of active porous materials that can efficiently adsorb H₂ and CO₂ is needed, due to their practical utilities. Here we present the design and synthesis of an interpenetrated Cu^II metal-organic framework (MOF) that is thermally stable, highly porous and can act as a heterogeneous catalyst. The Cu^II-MOF contains a highly symmetric polyhedral metal cluster (Cu₂₄) with cuboctahedron geometry as secondary building unit (SBU). The double interpenetration of such huge cluster-containing nets provides a high density of open metal sites, due to which it exhibits remarkable H₂ storage capacity (313 cm³g^?1 at 1 bar and 77 K) as well as high CO₂ capture ability (159 cm³g^?1 at 1 bar and 273 K). Further, its propensity towards CO₂ sorption can be utilized for the heterogeneous catalysis of the chemical conversion of CO₂ into the corresponding cyclic carbonates upon reaction with epoxides, with high turnover number and turnover frequency values.

Full text of DOI:10.1002/chem.201802829

A Journal of
Accepted Article
Title: Porous Metal Organic Polyhedral Framework Containing
Cuboctahedron Cages as SBUs with High Affinity for H2 and
CO2 Sorptions: A Heterogeneous Catalyst for Chemical Fixation
of CO2
Authors: Kumar Biradha, Kartik Maity, and Chandan Kumar Karan
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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published online in Early View as soon as possible and may be different
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201802829
Link to VoR: http://dx.doi.org/10.1002/chem.201802829
Supported by

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OMMUNICATION
Porous Metal Organic Polyhedral Framework Containing
Cuboctahedron Cages as SBUs with High Affinity for H and CO
Sorptions: A Heterogeneous Catalyst for Chemical Fixation of
CO
2
2
2
Kartik Maity, Chandan Kumar Karan and Kumar Biradha*[a]
Abstract: Development of active porous materials that can
efficiently adsorb H and CO are in need due to their practical
given their practical utility. The problems with the use of carbon
2
2
based fuel can be sorted out by employing H
2
gas as a dense
fuel as it does not produce any kind of carbon emission.2
6-28
It is
utilities. Here we present the design and synthesis of an
interpenetrated Cu(II)-MOF that is thermally stable, highly porous
and can act as a heterogeneous catalyst. The Cu(II)-MOF contains
highly symmetric polyhedral metal cluster (Cu24) with cuboctahedron
geometry as SBU. The double interpenetration of such huge cluster
containing nets provides high density of open metal sites due to
supposed to be the ideal fuel for the future generation with only
water as by-product.
In particular, the CO
gas and foremost culprit for global warming and subsequent
climate changes. For the last few decades the CO
2
is one of the primary anthropogenic
2
3
-1
which it exhibits remarkable H
and 77K) as well as high CO capture ability (159 cm g at 1bar and
73K). Further, its propensity towards the CO sorption utilized for
the heterogeneous catalysis of chemical conversion of CO into the
2
storage capacity (313 cm g at 1bar
concentration in the atmosphere increased over 380 ppm. and it
continues to mount. Due to the toxicity, corrosion and high
energy cost of conventional technologies involving amine based
3
-1
2
2
2
2
wet absorbents for CO
Therefore, it became essential for the researchers to develop
new solid materials for the efficient and selective capture of CO
and its sequestration.29-36 Further, the captured CO
can be
2
capture are becoming less important.
corresponding cyclic carbonates upon reaction with epoxides with
high TON and TOF values.
2
2
catalytically converted into commercially important value-added
chemicals which actually furnish non-toxic and low-cost resource
of carbon feedstock.37-47 This approach will help in diminishing
The phenomenal growth in the area of metal-organic
frameworks (MOFs) is emerging over the recent years due to
their diverse applications such as gas storage and separation,
heterogeneous catalysis, chemical sensing and many more.1-5
The main advantages of MOFs are considered to be their high
surface area, well defined pore sizes, exposed metal sites and
high thermal stabilities.6-8 The special feature of the MOFs
compared to traditional zeolites is that they can be tailor made
by introducing organic moieties for targeted absorption of gases.
The incorporation of secondary building units (SBUs) such as
the concerned greenhouse gas as well as generation of valuable
chemical commodities. Cycloaddition of CO
produce a five membered cyclic carbonates is being treated as
one of the beneficial strategy for CO fixation. The resulted cyclic
2
with epoxides to
2
carbonates can be used as valuable chemicals in various
applications such as intermediates in petroleum products,
electrolyte components, pharmaceuticals etc. Due to the
difficulties in catalyst separation in homogeneous catalysis for
2 4
well-known M (carboxylate) paddlewheel moiety was shown to
CO
2
fixation, the heterogeneous catalyst has been preferred.
Recently a number of MOFs have been shown to capture
produce variety of MOFs.9 Moreover the expansion of the pore
size and surface area of MOFs can be strategically achieved by
enlarging the ligand or by aggregating several of SBUs in to
bigger clusters, supramolecular building blocks (SBBs).11-15
However with the increasing size of the cavities or pores
increases probability of interpenetration of the frameworks which
reduces the cavity size but increases the stability.16-20
,10
CO
carbonates.
2
and catalyse its chemical conversion into the cyclic
37-47
However the design and synthesis of more
efficient and robust MOFs are very much necessary for the
effective fixation of CO with high yields and high turnover
frequencies. In pursuit of constructing high prolific CO storage
2
2
which can also efficiently catalyse its fixation reaction; we are
immensely fascinated in building of stable porous MOFs with the
use of elongated multidentate carboxylic acids as organic ligand
Several porous frameworks containing nitrogen rich
functional groups such as pyridine, amine, imidazole, acylamide
were shown to have a greater affinity towards the storing of
containing polar functional groups such as acylamide (H
Herein, we outline novel interpenetrated 3D-MOF,
[Cu24(DAIA)12(H O)24](solv.) (Cu-MOPF), which has been
synthesized using newly designed tetra carboxylic acid
DAIA (scheme 1). Due to the presence of exposed acylamide
group as well as open paddlewheel Cu(II) sites, Cu-MOPF found
to exhibit high CO uptake capacity along with efficient catalytic
activity in cycloaddition reaction between CO and various types
4
DAIA).
carbon dioxide (CO
can efficiently adsorb and store H
2
).21-25 Development of porous materials that
, and CO are in demand
a
2
2
{
2
x n
}
a
H
4
[
a]
Kartik Maity, Chandan Kumar Karan, Prof. Kumar Biradha
Department of Chemistry
Indian Institute of Technology
Kharagpur 721302, India
2
2
E-mail: kbiradha@chem.iitkgp.ernet.in
of epoxide. Further Cu-MOPF also displayed remarkable ability
for the storage of hydrogen gas.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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Chemistry - A European Journal
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OMMUNICATION
a)
b)
4
Scheme 1. Molecular structure of H DAIA.
The molecule
4
H DAIA was synthesized by the
c)
condensation of diacrylic acid with dimethyl ester of 5-amino-
isopthalic acid followed by hydrolysis and was characterized by
1H and 13C NMR (supporting information). Solvothermal reaction
by using a sealed tube or by simple refluxing of H
4
DAIA with
Cu(NO in DMF resulted in light blue coloured octahedral
3 2
)
shaped single crystals of Cu-MOPF. Single-crystal X-ray
diffraction analysis revealed that Cu-MOPF crystallised in
Fmmm space group and the asymmetric unit contains one and
half unit of DAIA, six Cu(II) ions and six coordinated water
molecules, both with half occupancy. All six Cu(II) ions exhibit
square pyramidal geometry as the Cu(II) ions are equatorially
coordinated by four carboxylates of four units of DAIA (Cu-O:
Supporting Information; Table S2) and the axial positions are
occupied by water molecules (Cu-O: Supporting Information;
Table S2). The combination of five coordinated two square
A
B
pyramidal Cu(II) centres leads to the formation
inorganic paddlewheel Cu (COO) SBUs with the Cu-Cu
separation of 2.6470(1), 2.6541(1) and 2.6487(1) Å.
Each bdc unit of DAIA connects to two Cu
a typical
2
4
2
paddlewheel
SBUs, overall twelve such SBUs were bridged by twenty four
bdc units of twenty four DAIA to produce a typical metal–organic
cuboctahedron containing a cavity (MOC, Cavity A). (Figure 1a)
The bent core nature of bdc exhibited the coordination mode at
an angle of 120˚ which produces an edge-directed corner-linked
MOC. The 24 bdc units represent the edges while the 12 SBUs
represent the corners of cuboctahedron similar to the MOC of
BDC and other BDC based MOFs.9,10 (Figure 1b) The
d)
C
coordinated water molecules in Cu
2
paddlewheel units are
decorated on inner and outer surfaces of MOCs and these can
be removed in order to have an activated material for porosity
and catalysis studies. There are total of eight triangular and six
square windows in each MOC which will allow the gases and
small molecules to enter into the interior cavities of the MOCs.
The MOCs are further connected to the vicinal MOCs
through the spacers of DAIA such that two more types of
cavities are formed: one type of cavity (B) is produced by the
linking of two paddlewheel SBUs by four DAIA units and other
2
Figure 1. a) Bridging of twelve Cu -paddlewheel SBUs to produce a typical
metal–organic cuboctahedron (MOC, cavity A); b) simplified representation of
MOC by reducing paddlewheel SBUs as nodes and BDC as edges; c) Linking
of MOCs in XY-plane by DAIA units; d) Linking of MOCs along Z-axis by the
DAIA units.
The interpenetrated networks interact via O−H---O and N-H---O
hydrogen bonding with water, DMF and amide functionalities.
Considering the MOCs as a six connected node, the Cu-MOPF
(
C) is produced by the linking of two clusters of four SBUs by the
four DAIA units. (Figure 1c & 1d) As a consequence each MOC
was found to be connected to the six neighbouring MOCs
through twenty four DAIA moieties, such connections resulted in
four and two cavities of type B and C, respectively, surrounding
each MOC (Supporting Information; Figure S3). Further, a
fourth cavity which is very big in size was observed in the middle
of eight MOCs of the 3D-framework which are filled through the
interpenetration of the networks (Figure 2b).48
represents a doubly interpenetrated network with PCU topology
3
(
33.6 x 33.6 x 32.3 Å ) (Figure 2c). In spite of having an
interpenetrated framework, the total accessible free volume in
completely desolvated Cu-MOPF was found to be 62% (44223.5
Å3 out of the 71343.0 Å3 unit cell volume) as calculated by
3
PLATON with the calculated density is 0.783 g cm , revealing
the highly porous nature of Cu-MOPF.
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Chemistry - A European Journal
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OMMUNICATION
600 ˚C. The completely activated sample was prepared by
exchanging the lattice solvent molecules in Cu-MOPF by
acetone followed by the degassing under high vacuum at 110˚C
for 10 hrs. A typical colour change of the materials was
observed from light blue to deep blue due to the generation of
open metal sites on removal of the coordinated water molecules
a)
(
Figure S9).
In order to investigate the permanent porosity of Cu-MOPF,
low pressure nitrogen sorption–desorption isotherms were
measured for the desolvated and activated phase of Cu-MOPF
at 77K and one bar pressure which exhibited type-I behavior
along with the reversibility. Cu-MOPF has the capacity to uptake
7
16 cm3g-1 of N
Emmett–Teller (BET) surface area was found to be 2091 m²/g
Figure 3b). All these characteristic of N sorption–desorption
isotherms demonstrated the micro porosity nature of Cu-MOPF.
2
at one bar pressure and the Brunauer–
(
2
Further Cu-MOPF was shown to absorb significant amount of H
and CO but not CH
The Cu-MOPF exhibited remarkable H
2
2
4
.
b)
2
uptake capacity of
13 cm3g-1 (2.8 wt%) at 77 k and one bar pressure without any
3
notable hysteresis of adsorption and desorption curves (Figure
c). We note here that the H uptake capacity of Cu-MOPF is
higher than several recently reported porous materials such as
3
2
4
0
49
Cu-based MOFs TMOF-1 , NOTT-103 and some of the well-
2
-1
known highly porous MOFs such as IRMOF-6 (2476 m g , 1.48
2
-1
2 -1
wt%), MOF-177 (4526 m g , 1.25 wt%) and PCN-68 (5109 m g ,
.87 wt%).27 A very few number of MOFs have been reported till
date with H uptake capacity of above 2.5 wt% at 77K and one
1
2
bar (Supporting Information; Table S3). The void spaces in the
interpenetrated framework of Cu-MOPF can be optimally used
as it contains more number of open metal sites which
consequently create the attractive electrostatic interactions
between adsorbate and adsorbent.50,51
c)
The presence of acylamide functionality and open metal
sites in Cu-MOPF encouraged us to investigate the CO
adsorption behavior of Cu-MOPF. The adsorption studies on Cu-
MOPF towards CO and CH at ambient conditions indicated the
higher affinity of Cu-MOPF towards CO compared to CH . At
73 K and one bar pressure, Cu-MOPF can uptake 159 cm g
31.3 wt%) of CO , maintaining the complete reversibility.
Whereas a very small amount of CH
observed by Cu-MOPF at 273 K and one bar pressure (Figure
d).
2
2
4
2
4
3
-1
2
(
2
3
-1
4
uptake (21 cm g ) was
3
2
The CO uptake capacity exhibited by Cu-MOPF is
comparable to the recently reported highly porous triazole-
containing Cu-MOFs25,41 and higher than many recently reported
Figure 2. a) Illustration for overall 3D-framework (red: 1,3-BDC unit; green:
diacrylamide spacer); b) 2-fold interpenetrated 3D-frameworks; c) PCU
network generated by denoting MOCs as six connected nodes and multiple
connections by DAIA in the same direction as one connection.
3 −1
Cu-based MOFs (eg: JUC-1000, 125; Cu-NTTA, 115.6 cm g ;
TMOF-1, 47.1 cm g )
Further, we note here CO
3
-1 43,39,40
(Table S4, Supporting Information).
2
adsorption ability of Cu-MOPF is also
comparable with well-known examples such as HKUST-1
Cu (BTC) ) and PCN-6 (Cu (TATB)
).33 The preferential uptake
of CO over CH by Cu-MOPF could be due to the presence of
polar functionality such as acylamide on the walls of channels
and also due to the exposed metal sites which accelerate the
(
3
2
3
2
2
4
The bulk purity of Cu-MOPF was confirmed by comparing
XRPD patterns of the as synthesized bulk material with that of
simulated pattern obtained from the crystal structure. Further
temperature variable XRPD patterns for Cu-MOPF revealed the
thermal stability of the material (Figure 3a). Thermogravimetric
analysis (TGA) of Cu-MOPF indicates the solvent loss takes
place up to 300 ˚C and the material is found to be stable beyond
attractive interactions with CO
Apart from these factors, the linear shape of CO
its passage into the
2
due to its quadrupolar moment.
2
also helps in
channels.
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Chemistry - A European Journal
10.1002/chem.201802829
OMMUNICATION
8
00
Adsorption
Desorption
a)
b)
o
2
50 C
700
600
o
2
1
1
00 C
o
50 C
o
00 C
500
400
300
200
100
0
o
5
0 C
o
2
5 C
10
20
30
40
50


0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P/P )
0
c)
d)
3
3
2
2
1
1
50
00
50
00
50
00
180
150
CO adsorption
Adsorption
Desorption
2
CO desorption
2
CH adsorption
4
CH desorption
4
120
90
60
30
0
5
0
0
0
100
200
300
400
500
600
700
800
0
200
400
600
800
Absolute Pressure (mmHg)
Absolute Pressure (mmHg)
Figure 3. a) Temperature variable XRPD patterns for Cu-MOPF; b) Nitrogen adsorption and desorption isotherm of Cu-MOPF at 77 K and one bar; c) Hydrogen
uptake isotherm of Cu-MOPF at 77 and one bar; d) CO and CH adsorption isotherms of Cu-MOPF at 273 and one bar.
K
2
4
K
The presence of Lewis acidic open metal sites in the
framework as well as high CO adsorption capability of Cu-
MOPF prompted us to investigate its catalytic ability in the
conversion of epoxides to cyclic carbonates by utilizing CO as a
renewable C1 building block. In a typical solvent free conditions,
.01 mmol of Cu-MOPF as a catalyst along with 2 mol%
tetrabutylammonium bromide (TBAB) as a co-catalyst were
immersed into the liquid epoxide (25 mmol) and CO purged at 1
atm pressure under reflux conditions (scheme 2). A facile
conversion of epoxides to cyclic carbonates was observed for as
many as five substrates with high TOF and TON values.
The epoxides considered are un-symmetric in nature and
have substitutions such as n-butyl, phenyl, phenyl ether and t-
butyl-ether on one side of the ring. The reactions were
monitored for 4h, and a good to excellent conversions were
achieved (Table 1). The TON and TOF values for Cu-MOPF
found to be higher than some of the recently reported similar
catalytic conversions by MOFs (Table S5, Supporting
Information). From the table 1, it can be seen that the TON as
well as TOF values are highest i.e 2500 and 625 h-1 for entry 4.
Further, the conversion found to be good (82%) for the substrate
containing n-butyl (entry 1) where as for the styrene oxide (entry
2) the conversion found to be moderate (69%). For entries 3 and
4, the conversions found to be excellent (94% & > 99%).
2
2
0
2
O
O
MOF catalyst
Reflux, 4 hrs
O
O
+ O C O
R
R
Scheme 2. Formation of cyclic carbonates by the addition of CO to epoxides.
2
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Chemistry - A European Journal
10.1002/chem.201802829
OMMUNICATION
catalytic cycle. The XRPD patterns of Cu-MOPF before and after
catalysis remained same revealing its structural integrity.
Table 1. Cycloaddition of various epoxides with CO a
.
2
Entry
1
Substrate
Conversionb
%)
TON
2050
TOF (h-1)
512.5
(
82
2
69
1725
431.2
Figure 4. Recyclability experiment of the catalyst (Cu-MOPF) for chemical
3
4
94
2350
2500
587.5
2
conversion of CO .
In conclusion, a newly designed acylamide functionalized
tetra carboxylic acid H DAIA has been employed for the
construction of a thermally stable interpenetrated microporous
D-MOF. The resultant 3D-MOF exhibited high porosity with the
incorporation of exposed metal sites and polar channels which
were found to be responsible for the high affinity towards CO
sorption. The CO uptake capacity was found to be promising in
4
>99
625
3
2
2
comparison to the some of the recently reported microporous
MOFs. Moreover, the Cu-MOPF also exhibited an excellent
5
40
1000
250
ability for H
the MOFs with highest reported values. Further, the superior
CO adsorption capacity, the presence of Lewis acidic open
2
gas sorption at low pressure which is comparable to
2
metal sites and confinement of the large pores in the framework,
make the Cu-MOPF as a perfect heterogeneous catalyst for the
chemical reaction of CO2 with various epoxides to form cyclic
carbonates. The Cu-MOPF exhibited very high TON and TOF
values with excellent recyclability.
[
a] Reaction conditions: epoxide (25 mmol), catalyst (0.01 mmol per copper
2
paddlewheel unit of Cu-MOPF), TBAB (0.16 g, 2 mol%) under CO (1 bar)
atmosphere, 373 K and 4 h. [b] From 1H NMR (Figure S11-S20, Supporting
Information)
These variations can be explained from
mechanism where the epoxide oxygen will bind to the Lewis
a tentative
Acknowledgements
acidic copper sites and the ring will be activated. Subsequently,
the Br− ion, generated from TBAB will attack upon the less
We acknowledge DST (SERB), New Delhi, India, for financial
support and DST-FIST for the single-crystal X-ray diffractometer.
K. M. thanks UGC for research fellowship and C. K. K. thanks
IIT Kharagpur for research fellowship.
hindered carbon atom of the activated epoxide ring to produce
the oxygen anion via ring opening. This oxygen anion will attack
on the carbon atom of CO to form an alkyl carbonate anion.
2
Finally the ring closure step leads to the desired cyclic
carbonates (Figure S10, Supporting Information). The yield of
cyclic carbonates found to reduce with the increasing bulkiness
of the side chain of the epoxides due to steric hindrance.
Keywords: metal organic polyhedral framework • stability •
hydrogen storage • carbon dioxide capture • carbon dioxide
fixation.
These reactions indicate that Cu-MOPF acts as very
promising and perfect heterogeneous catalyst given its stable
framework structure which is originated from cuboctahedron
building blocks and interpenetration of the networks. The
recyclability of Cu-MOPF was studied by reusing the catalyst
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Kartik Maity, Chandan Kumar Karan and
Kumar Biradha*
Page No. – Page No.
Porous Metal Organic Polyhedral
Framework
Cuboctahedron Cages as SBUs with
High Affinity for and CO
Sorptions: A Heterogeneous Catalyst
for Chemical Fixation of CO
Containing
H
2
2
2
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