A highly augmented, (12,3)-connected Zr-MOF containing hydrated coordination sites for the catalytic transformation of gaseous CO2 to cyclic carbonates

Article abstract of DOI:10.1039/c9dt02117e

A porous Zr-based MOF, [Zr₆(BTEB)₄(μ₃-O)₄(μ₃-OH)₄(H₂O)₄], which contains partially hydrated, 12-connected {Zr₆} nodes and extended carboxylate ligands (BTEB^3-), was synthesized and physicochemically characterised. The resulting (12,3)-connected, 3D framework adopts an uncommon llj topology with a large, solvent accessible void volume of ca. 79% of the unit cell volume. The porous structure facilitates the uptake of N₂ and activated samples give rise to BET surface areas of >1000 m² g^-1. Furthermore, the porosity and accessibility of Lewis acidic Zr(iv) sites promote the catalytic transformation of gaseous CO₂ to cyclic carbonates via cycloaddition reactions using epoxide reactants, whereby solvated MOFs exhibit higher catalytic performance than thermally treated samples.

Full text of DOI:10.1039/c9dt02117e

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DOI: 10.1039/C9DT02117E
Dalton Transactions
ARTICLE
Highly augmented, (12,3)-connected Zr-MOF containing hydrated
coordination sites for the catalytic transformation of gaseous CO2
to cyclic carbonates
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a
a
a
a
Guanghua Jin,‡ Debobroto Sensharma,‡ Nianyong Zhu, Sebastien Vaesen and Wolfgang
Schmitt
www.rsc.org/
a
A porous Zr-based MOF, [Zr
Zr
6
(BTEB)
4
(μ
3
-O)
4
(μ
3
-OH)
4
3
(H
2 4
O) ], that contains partially hydrated, 12-connected
-
{
6
} nodes and extended carboxylate ligands (BTEB ) was synthesized and physicochemically characterisied.
The resulting (12,3)-connected, 3D framework adopts an uncommon llj topology has a large, solvent
accessible void volume of ca. 79 % of the unit cell volume. The porous structure facilitates the uptake of N
and activated samples give rise to BET surface areas of > 1000 m /g. Furthermore, the porosity and
2
2
2
accessibility of Lewis acidic Zr(IV) sites, promote the catalytic transformation of gaseous CO to cyclic
carbonates via cycloaddition reactions using epoxide reactants whereby solvated MOFs reveal higher
catalytic performance than thermally treated samples.
Introduction
Zirconium-based metal-organic frameworks (MOFs) represent
a highly desired class of compound, due to their tunable and
stable nature, providing porous materials for targeted
applications.1 In Zr-based reaction systems, the formation of
oligonuclear oxo-clusters that can serve as secondary building
units (SBUs), is favoured by condensation reactions involving
Zr(IV) ions. The reaction system generally promotes the
formation of highly connected nodes that impart stability to
–6
Zr-MOFs.7 The d outer electronic configuration of Zr ions,
and the consequent absence of ligand field stabilisation, allows
a degree of structural diversity in SBU formation and results in
kinetics, amenable to ligand substitution despite the hardness
and oxophilicity of the metal ions. Connectivities varying from
–9
0
4+
6
to 12 for Zr SBUs and a relatively high tolerance to variation
4
,5,10–13
in the Zr coordination environment are reported.
Zr
nodes have been used to great effect for a variety of
applications when combined with extended carboxylate-based
1
4–19
ligands to form MOFs.
In addition, the use of acetylene
spacers to provide linear extension to ligands is a reliable and
frequently used strategy to create large, highly accessible
framework voids.2
0–24
Porous MOFs based on Zr SBUs are
Fig. 1 a) and b) Structure of the {Zr
in TCM-16 showing the carboxylate binding modes that result in the
overall 12-connnected {Zr } SBUs, as well as coordinated water
molecules. Colour code: Zr teal, C grey; O red; O-donor atoms of
coordination H O molecules are shown in a darker shade of red; c)
Tritopic 4, 4’, 4’’-[1,3,5-benzenetriyltris(ethyne-2,1-diyl)]tribenzoic acid
BTEB) ligand used for the preparation of in TCM-16.
6 3 4 3 4 2 4
(μ -O) (μ -OH) (H O) } oxo-cluster
6
a. School of Chemistry and SFI AMBER centre, Trinity College Dublin, College Green,
Dublin 2, Ireland; ‡ Authors contributed equally
Electronic Supplementary Information (ESI) available: Crystallographic details,
supplementary characterisation, and additional images. See
DOI: 10.1039/x0xx00000x
2
(H
3
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
4
+
known for their remarkable gas sorption behaviour (e.g. NU- hexanuclear Zr units that are linked by fully deprotonated
View Article Online
DOI: 10.1039/C9DT02117E
3
-
1
10, PCN-229, NU-1103), and increasingly for the catalysis of BTEB ligands (Fig. 1). The overall formula for the framework is
1
3,25–35
several organic reactions yielding high-value products.
6 4
[Zr (BTEB) (μ
3
-O)
4
(μ
3
-OH)
4
(H
2
O)
4
]. The inorganic SBU is based
4
+
The use of gaseous chemical feedstocks of naturally abundant on the well-characterised {Zr
compounds, i.e. atmospheric CO
of sustainable approaches for the synthesis of value-added and μ
chemical products.36 Chemical means to CO
fixation and of the polygon. However, while the typical SBU as seen in
heterogeneous catalytic approaches involving porous MOFs, such as UiO-66, NU-1000 or the structurally related
6
} oxo-cluster, in which six Zr
, may allow the development ions are arranged at the vertices of an octahedron, and μ
3
-O2-
2
-
3
-OH moieties occupy the centres of the triangular faces
2
3
-
materials to transform CO
research, whereby CO
epoxides are of particular importance due the wide range of by monodentate carboxylate binding modes at four positions,
2
are particularly intriguing areas of BTEB stabilised MOF-1004, consists uniformly of bidentate
2
conversions to carbonates using carboxylate binding modes, the SBU in TCM-16 is characterised
4
+
product applications in pharmaceutical, medical, polymer and whereby the 8-coordination of the Zr centre is completed by
chemical industries.3
7–39
However, many catalytic approaches coordinating H
O ligands.
1,44,45
This type of coordination
2
4
+
to carbonates suffer from demanding reaction conditions environment can allow access to Lewis acidic Zr sites when
operating at high temperatures, pressures, or requiring long the water ligands are displaced during
a
chemical
reaction times.4
0–42
MOFs can represent attractive potential transformation. Hence, one of the three carboxylate groups on
3
-
catalysts for the single-step CO
2
transformations to carbonates each BTEB ligand binds in a monodentate fashion while the
} SBU is connected to 12
number of active Lewis acidic sites (e.g. Zr sites) per volume separate BTEB ligands, and each organic ligand is connected
as the augmented, porous frameworks can provide a high other two are bidentate. Each {Zr
6
4
+
3-
3
7
which are accessible to substrates at high diffusion rates.
6
to three {Zr } SBUs to form a 3D framework (Fig. 2). The
We have a strong interest in metal-organic materials that give resultant (12,3)-connected net adopts a rather uncommon llj
rise to porosity43 and here, we report the synthesis and topology with the point symbol {4 .6 .8 }{4 }
20
28 18
3
4
, and
characterisation of a new Zr-based MOF that is stabilised by structurally relates to a corresponding hafnium-based MOF
4
6–48
extended tritopic 4,4’,4’’-[1,3,5-benzenetriyltris(ethyne-2,1- (Fig. 3) .
3
-
diyl)]tribenzoate ligands (BTEB ). The applied synthetic The structure of TCM-16 was solved in the tetragonal space
approach results in a porous, (12,3)-connected net with group I4/m, adopting unit cell dimensions of a = 33.102(3) Å, b
uncommon llj topology containing labile coordination sites. = 33.102(3) Å, and c = 21.711(2) Å. The framework as shown in
These structural attributes prompted us to investigate its Fig. 2, is highly augmented, with cuboidal channels extending
utility as a heterogeneous co-catalyst for the synthesis of cyclic in the direction of the crystallographic c-axis and whose square
3
-
carbonates from CO
2
and epoxides.
cross-sections are bounded by four BTEB ligands and four
Zr } SBUs. The channel diameter is 16.8 Å and the coordinated
O ligands are highly accessible through these channels. The
{
H
6
2
Results and Discussion
maximum void diameter is ca. 18 Å, and the void volume of
the framework structure was determined to be ca. 79 % of the
unit cell volume. This is in good agreement with the
The MOF, [Zr
Trinity College Materials), was synthesised using a highly
saturated solution of benzoic acid in DMF, and heating ZrCl
with H BTEB under autogenous pressure at 120 °C for 96
6 4 3 4 3 4 2 4
(BTEB) (μ -O) (μ -OH) (H O) ] (TCM-16, TCM:
2
thermogravimetric analysis carried out in a N atmosphere,
4
which shows an initial loss of solvent molecules corresponding
to 74.9 wt-% below 140 °C, followed by a ligand decomposition
step centred at ca. 460 °C. Further supplemental
characterisations of TCM-16 include powder X-ray diffraction
and FT-IR spectroscopy studies characterising the phase-purity
of as-synthesised bulk samples.
3
hours. Transparent, rod-shaped single crystals were obtained
in yields of ca. 55 %.
Single crystal X-ray diffraction studies revealed the adoption of
a three-dimensional single-framework structure composed of
Fig. 2. a) and b) Crystal structure of TCM-16 viewed in the crystallographic a- and c-directions, respectively. c) 3x3x3 supercell of TCM-16 highlighting
the available void space using space-filling representations (purple; 2x2x2 supercell).
2
| J. Name., 2012, 00, 1-3
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View Article Online
DOI: 10.1039/C9DT
O
02117E
O
Cat.
O
CO2
+
O
o
1
00 C, 16 h
R
R
R = -Ph, -CH Cl
2
Fig. 3 Topological reduction of the structure of TCM-16 to the (12,3)-
connected llj net; View in the crystallographic c-direction (left) and the
a-direction (right).
Scheme 1. Catalytic cycloaddition of CO2 to cyclic carbonates using
styrene oxide and (chloromethyl)oxirane.
The porosity of the MOF was investigated using gas sorption
within the channels may further increase the local substrate
concentrations in proximity to the catalytically active Zr sites
in the MOF. With these considerations in mind, preliminary
experiments were conducted using TCM-16 as a porous,
studies (Fig. 4). N
2
sorption analysis at 77 K revealed
4+
unambiguously that the porosity can be retained after
activation, which is unusual for MOFs solely containing highly
3
-
23,24,49,50
extended BTEB ligands.
The resulting isotherm shows
heterogeneous matrix for the cycloaddition between CO
oxirane derivatives to produce cyclic organic carbonates
Scheme 1). The catalytic test reactions were carried out for 16
hours using styrene oxide or (chloromethyl)oxirane and CO (1
2
and
clear microporosity and a steep gas uptake at low partial
2
pressures. A surface area of 1091 m /g was obtained through
(
BET analysis. CO
and 308 K, reveal CO
7 cc/g, respectively (ESI). It is noteworthy that the activation
procedure of TCM-16 is not trivial (ESI) and requires care as
the removal of the coordination H O molecules in TCM-16 can
2
sorption isotherms measured at 278 K, 293 K,
2
2
uptakes at 1 bar of 84 cc/g, 46 cc/g, and
atm, balloon pressure) in the presence of 0.5 mol% of TCM-16
1
o
and 1 mol% of tetrabutylammonium bromide (TBAB) at 100 C.
The yields of the produced cyclic carbonates were determined
2
1
by H NMR spectroscopy.
conceptually give rise to ‘open metal sites’ upon thermal
treatment. However these sites, are expected to get
instantaneously occupied by the monodentate carboxylate
In the presence of TCM-16, the yields of the cyclic carbonate
products increased significantly whereby freshly prepared
hydrated MOF samples led to almost quantitative
3
-
groups of the BTEB ligands that locate in close vicinity. This
structural transition will undoubtedly be associated with
amorphisation and loss of porosity.
transformations
reaching
styrene
carbonate
and
chloropropene carbonate yields of 92.8 and 99.5 %,
respectively (Table 1). When TCM-16 was thermally treated at
Thus, the structure of TCM-16 containing labile Lewis-acidic
o
1
00 C under reduced pressure for 4 hours, significantly lower
4
+
Zr sites, lends itself to solution studies, whereby the terminal
O molecules are replaced by substrates to promote catalytic
activity under turnover conditions. Geometrical restrains
yields of 19.4 and 58.1 % were obtained. In contrast, as-
prepared TCM-16 samples, even performed in the absence of
TBAB, resulted in styrene carbonate and chloropropene
carbonate yields of 61.3 and 78.1 %, respectively. Solvated
samples of TCM-16 maintain their structural integrity as
demonstrated by X-ray powder diffraction (ESI, Fig. S.6), are
recyclable and retain their high activity in consecutive catalysis
experiments (Table 1, entry 5). Significant leaching of Zr ions
from TCM-16 was not detectable (Energy-dispersive X-ray
spectroscopy using dried post-catalytic reaction solutions). The
experimental observations of these catalysis experiments are
H
2
2
in-line with studies that demonstrate that {Zr-H O} moieties in
MOFs can effectively promote the investigated cycloaddition
reaction whereas dehydrated, closed MOF structures or
collapsed MOF structures are expected to reveal lower
5
1
activities. Further, as the gas sorption studies demonstrate,
thermally treated samples of TCM-16 have a tendency to loose
their microporosity, thus reducing the availability of active
sites per volume and resulting in lower catalytic activity. The
outlined catalytic transformations are expected to follow the
Fig. 4. N
2
(77 K) low-pressure adsorption and desorption isotherms
general mechanism for the cycloaddition of CO
2
using
obtained for TCM-16, inset: Multi-point BET fit; slope = 3.186, intercept =
3
7
epoxides whereby the metal sites facilitate interactions with
-3
4
.307x 10 , correlation coefficient, r = 0.999996, C (constant) = 740.649.
This journal is © The Royal Society of Chemistry 20xx
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contributions of these unlocated solvent molecules.57 A solvent
2
Table 1. TCM-16-catalyzed cycloaddition of CO using epoxides, reaction
View Article Online
conditions: epoxide (5 mmol), TCM-16 (0.5 mol%), CO
2
(1 atm, balloon
mask accounting for 2421 electrons was found in a volume of 19095
Å3, in one void per unit cell. This is consistent with the presence of
DOI: 10.1039/C9DT02117E
pressure), 100 oC. TCM-16 was treated at 100 oC for 4 hours under
vacuum prior to the use as catalyst; b Moles of cyclic carbonate
produced per mole of catalyst; c Catalyst recyclability of TCM-16 was
tested under the same reaction conditions; TCM-16 retained the same
activities after three runs and yields of the cyclic carbonate of 99.5 %
a
2
ca. 30 DMF molecules per formula unit or a H O/DMF solvent
mixture. Crystallographic data can be obtained from The Cambridge
Crystallographic Data Centre (CCDC number 1916002)
via www.ccdc.cam.ac.uk /data_request/ cif.
were obtained; Substrates: styrene oxide (R
=
-Ph) or
(
2
chloromethyl)oxirane (R = -CH Cl).
Infrared data in the 4000-650 cm-1 region were obtained using a
PerkinElmer Spectrum One FT-IR spectrometer with a universal
Attenuated Total Reflectance (ATR) sampling accessory.
Thermogravimetric analyses were performed using a Perkin Elmer
Pyriss 1 TGA instrument that had been previously calibrated using
nickel and iron standards. Samples were heated in a ceramic
crucible under a nitrogen atmosphere from room temperature to
ca. 700° C, at a rate of 5°C/min.
Substrate,
TBAB
Entry
Yield
TONb
R=
-Ph
-Ph
-Ph
Co-catalyst
--
1 mol%
1 mol%
--
1
2
3
61.3 %
92.8 %
19.4 %
78.1 %
99.5 %
123
186
39
156
199
a
4
-CH
-CH
2
Cl
Cl
c
5
2
1 mol%
the O-atom of the oxirane moiety prior to the ring-opening
and followed by CO insertion to form the carbonate product.
2
6 4 3 4 3 4 2 4
Synthesis of [Zr (BTEB) (μ -O) (μ -OH) (H O) ] (TCM-16)
[
2
1
Zr
6
(BTEB)
8.8 mg of ZrCl
.465 g (12 mmol) of benzoic acid in 8 mL of dimethylformamide
4
(μ
3
-O)
4
(μ
3
-OH)
4
(H
2
O)
4
] was synthesised by dissolving
4
(0.12 mmol), 46.4 mg of H
3
BTEB (0.09 mmol), and
Conclusions
In summary, we report the synthesis and characterization of
a porous MOF, TCM-16 that is composed of hexanuclear
(
DMF) in a closed vial and heating the reaction mixture to 120 °C for
four days. Colourless crystals of [Zr (BTEB) (μ -O) (μ
OH) (H O)
].solv were obtained, washed with acetone and stored at
ambient conditions. Yield: 31 mg, ca. 55 % based on Zr.
Microanalytical data for C132 (including additional 9.5 H
6
4
3
4
3
-
Zr
6 3 4 3 4 2 4
{ (μ -O) (μ -OH) (H O) } SBUs which provide 12-conneted
4
2
4
nodes. Assembly in the presence of the trifunctional benzoate
3
-
ligand, BTEB , promotes the formation of a (12,3)-connected
net with an uncommon llj topology. The MOF structure
maintains its porous nature upon removal of constitutional
72
H O
36Zr
6
2
O
and 0.5 DMF solvent molecules), calc (%): C 53.64, H 3.19, N: 0.23;
found: C 53.46, H 2.64, N 0.15. For further characterisation see ESI.
solvent molecules and facilitates the uptake of N
experimental BET surface area of 1091 m /g. Notably are four
2
giving an
2
coordination H
2 6
O molecules at the {Zr } SBUs which may
Conflicts of interest
provide kinetically labile binding sites accessible for catalytic
transformations. We demonstrate that TCM-16 promotes the There are no conflicts to declare.
cycloaddition between gaseous CO
produce cyclic organic carbonates.
2
and oxirane derivatives to
Acknowledgements
The authors thank the Science Foundation Ireland (SFI;
Experimental
1
3/IA/1896), the European Research Council (SUPRAMOL CoG
Methods and Materials
2014 – 647719) and the SFI AMBER research centre for
financial support.
Commercially available chemicals were used as obtained in high
purity and from standard chemical suppliers without further
purification.
diyl)]tribenzoic acid (H
The
4,4’,4’’-[1,3,5-benzenetriyltris(ethyne-2,1-
BTEB) ligand was prepared using a modified
Notes and references
3
literature procedure.52 Single-crystal X-ray diffraction studies were
performed using a Bruker APEX2 Duo diffractometer equipped with
a microfocus Cu-Kα source (λ = 1.5418 Å) and a Bruker SMART
APEX2 area detector. Intensity data was corrected for absorption
by multi-scan methods using SADABS. The structures were solved
and refined using SHELXT54 and SHELXL55 as implemented in
Olex2.56 H- positions were calculated using a riding model. The
structure contains large solvent accessible void volume in which
solvent molecules could not be located reliably. To account for this,
the Platon-SQUEEZE routine was used to calculate the void volume
and re-generate the reflection file by excluding the diffraction
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