A robust indium-porphyrin framework for CO2 capture and chemical transformation

Article abstract of DOI:10.1039/c6dt03651a

An indium based metal-porphyrinic framework, denoted NUPF-3, was prepared based on a new amido-decorated porphyrin ligand. NUPF-3 possesses a rarely seen 4-fold interpenetrated pts framework with segmented pores and dense metalloporphyrin central sites. The structure can retain its crystallinity in commonly used solvents, as well as acidic/alkaline solutions with pH ranging from 1 to 12 for 48 h, exhibiting high chemical stability. Meanwhile, thermal analysis reveals that NUPF-3 possesses relatively high thermal stability. Owing to the presence of amido groups, structural interpenetration and a charged framework, NUPF-3 exhibits relatively high CO₂ uptake. Moreover, NUPF-3 could be used as a good heterogeneous catalyst for cycloaddition of CO₂ and epoxides, under relatively mild conditions, with good recyclability.

Full text of DOI:10.1039/c6dt03651a

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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A Robust Indium-Porphyrin Framework for CO2 Capture and
Chemical Transformation
Lei Xu,a Meng-Ke Zhai,a Xin-Chao Lu,a Hong-Bin Dua*
Received 00th January 20xx,
Accepted 00th January 20xx
A indium based metal-porphyrinic framework, denoted as NUPF-3, was prepared based on a new amido-
decorated porphyrin ligand. NUPF-3 possesses a rarely seen 4-fold interpenetrated pts framework with
segmented pores and dense metalloporphyrin central sites. The sturture could remain its crystallinity in
common used solvents as well as acidic/alkaline solutions with pH ranging from 1 to 12 for 48 h, exhibiting a
high chemical stability. Meanwhile, thermal analysis reveals that NUPF-3 possesses a relative high thermal
stability. Owing to the presence of amido groups, structural interpenetration and charged framework, NUPF-
3 exhibits relative high CO2 uptakes. Moreover, NUPF-3 could be used as a good heterogeneous catalyst for
cycloaddition of CO2 and epoxides under relatively mild conditions with good recyclability.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Introduction
As a special branch of metal-organic frameworks (MOFs),1 construct stable MPFs is using high-valence metal ions as
metal-porphyrinic frameworks (MPFs) are resurging structural nodes to enhance the coordination bonds between
a
subfamily of crystalline porous materials that are composed of the carboxylic ligands and the metals.11 In this regard,
(metallo)porphyrin-decorated ligands interconnected by metal zirconium-based MPFs have been intensively investigated for
ions and/or clusters.2 Since the first MPF was constructed from their extraordinarily high stability in recent years.12 Besides
tetra-pyridylporphyrin in 1990s,3 MPFs have attracted zirconium, trivalent metal ions such as Fe,13 Al,14 Mn15 have
evergrowing research interest. Fabricating (metallo)porphyrins also been frequently used as connectors to construct stable
into crystalline multidimensional assemblies could not only MPFs. Since the high-coordination-number and low-toxic In3+
make their intrinsic characters inherited, but also introduce ion tends to generate structurally stable and appealing
preferable properties to the resulting MPFs. For example, frameworks, it has been used to construct various MOF
when MPFs used as heterogeneous catalysts, it could not only materials.16 Compared with the family of In-MOFs, the number
make the valuable (metallo)porphyrins recyclable, but also of indium based MPFs was rather limited.17 To the best of our
overcome the issues of self-aggregation (deactivation) or poor- knowledge, only a few In-MPFs based on different porphyrin
solubility that (metallo)porphyrins often suffered from in ligands have been reported so far (i.e. MMPF-7 and -8, UNLPF-
homogeneous reactions.4 Up to date, a number of MPFs have 10, In-PMOF, UNLPF-14).6c, 17-18
been elaborately fabricated and demonstrated great potential
Chemical fixation and transformation of CO2 have recently
in gas storage/separation,5 light-harvesting,6 sensing,7 become a hot research topic since it was promising in
photodynamic therapy,8 heterogeneous catalysis,9 etc. addressing the issue of greenhouse effect mainly caused by
Nonetheless, the developments of MPFs are still in the the excess CO2 in the atmosphere and reusing CO2 molecules
premature stage and the exploration of novel MPFs and their to synthesize various valuable chemicals.19 Owing to their
potential applications are still highly desirable.2, 10
outstanding catalytic property in the cycloaddition of CO2 to
In constructing MPFs, the ones with high structural stability epoxides, metalloporphyrins have attracted extensive research
are much desirable since these materials would provide robust interests in such area. However, these metalloporphyrin
platforms for various applications when subject to harsh complexes generally behave as homogeneous catalysts and
experimental environments.4b A straight-forward method to their separation from the reaction mixture is quite difficult,
owing to the high boiling point and excellent dissolving
capacity of cyclic carbonate.20 Besides, the low CO2 adsorption
capacity of such homogeneous metalloporphyrin catalysts
were also disadvantageous for the catalytic CO2 fixation
reactions.21 Using MPFs as heterogeneous catalysts could not
only address the issues above-mentioned, but also could
achieve a high catalytic efficiency under mild conditions.22
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Moreover, previous studies revealed that amido group show KBr pellets on a Bruker Tensor 27 FT-IR spectrometer. Proton
high affinity towards CO2 molecules, resulting in an enhanced nuclear magnetic resonance (1H NMR) data were collected on
CO2 uptake in MOF materials based on amido-decorated Bruker AVANCE 300 MHz spectrometer. The UV-Vis spectra
organic ligands.23 Incorporating amido group into MPFs would were recorded on Varian Cary 5000 UV-Vis-NIR
improve their CO2 adsorption capacity, and thus benefit for spectrophotometer using BaSO4 as reference. Gas adsorption
CO2 fixation reactions. In this work, we report a highly stable isotherms were collected by a volumetric method on a
indium-MPF,
[NH2(CH3)2][In2L∙(HCOO)∙(H2O)]∙(solvents)x Micromeritics ASAP 2020 sorption analyzer. The scanning
(denoted as NUPF-3, NUPF: Nanjing University Porphyrinic electron microscope (SEM) image was obtained on a Hitachi S-
Framework), based on a custom-designed amido-decorated 4800 at an accelerating voltage of 10 kV. Supercritical Fluid
porphyrin ligand (H4L). NUPF-3 possesses a rare 4-fold Technologies (SFT) HPR-100 reactor was used to perform
interpenetrated pts-type framework with large solvent- supercritical CO2 activation of the sample.
accessible voids. The framework shows high structural stability
Crystallography
and CO2 uptakes. Thanks to the dense metalloporphyrin
Single crystal X-ray diffraction measurements were carried out
centers, desired structural stability and CO2 adsorption, NUPF-
3 exhibits a high efficiency in catalyzing CO2 chemical fixation
under mild conditions.
on a Bruker D8 Venture diffractometer outfitted with a
PHOTON-100 CMOS detector using monochromatic microfocus
MoKα radiation (λ= 0.71073 Å) that was operated at 50 kV and
40 mA at 153 K by chilled nitrogen flow controlled by a
KRYOFLEX II low temperature attachment. Single crystals were
Experimental
selected and mounted on
a nylon loop in Paratone-N
Chemicals
cryoprotectant. Unit cell determination was performed in the
Bruker SMART APEX III software suite. The data sets were
reduced and a multi-scan spherical absorption correction was
implemented in the SCALE interface.24 The structure was
solved by direct methods and refined on F2 by full-matrix least
squares using the SHELXTL-2014 crystallographic software
package25 that imbedded in Olex2.26 The contribution of
disordered solvent molecules was treated as diffuse using
SQUEEZE procedure implemented in PLATON.27 The detailed
crystal data and structure refinements for NUPF-3 are given in
Table S1†. CCDC no. 1491888.
Unless otherwise specified, commercially available reagents
were purchased as analytical grade and used without further
purification. The porphyrin ligand (H4L) used in this work was
prepared according to our reported procedures.9m
In(NO3)3∙4.5H2O (99.99%) was obtained from Energy Chemical;
1,2-epoxypropane (99.5%), epichlorohydrin (99%), styrene
oxide (98%), glycidyl phenyl ether (99%), cyclopentene oxide
(98%), 1,2-epoxyhexane (96%) and allyl glycidyl ether (99%)
were purchased from Tokyo Chemical Industry Co., Ltd. Other
reagents were purchased from Sinopharm Chemical Reagent
Co., Ltd.
Chemical stability tests of NUPF-3
Synthesis of NUPF-3
Acidic solutions (pH = 1, pH = 2, pH = 3) and alkaline solutions
(NaOH aqueous solution, pH = 10, pH = 11 and pH = 12) were
firstly prepared. About 10 mg of NUPF-3 were soaked in the
acidic or alkaline solutions and different organic solvents for 2
days. The samples were filtered and washed with ethanol
several times and then PXRD measurements were performed
immediately to check the structural stability.
H4
L (13 mg, 0.01 mmol) was transferred into N,N-
dimethylformamide (DMF, 2 mL) in a small capped vial and
sonicated for ten minutes for dissolution. In(NO3)3∙4.5H2O (20
mg, 0.052 mmol), 0.5 mL H2O and formic acid (0.2 mL) were
added into the resulting solution and further sonicated for 10
minutes. The vial was placed into a Teflon-lined acid-digestion
bomb and heated at 120 °C for 3 days and then allowed to cool
to room temperature naturally. Dark purple rhombic crystals
of NUPF-3 were harvested (Fig. S1†), followed by washing
several times with DMF, ethanol, respectively. Yield: ~10 mg
(~75 %, based on porphyrin ligand). FT-IR (KBr pellet, cm-1): ν =
3404(s), 3124(w), 2366(w), 1657(w), 1599(s), 1520(s), 1398(s),
1318(m), 1251(m), 1170(m), 1102(m), 1006(m), 857(w),
701(m), 636(w), 491(w).
SCD activation and gas sorption analysis
Super-critical carbon dioxide (SCD) activation technique was
applied to activate NUPF-3. The freshly-prepared NUPF-3 was
soaked in anhydrous EtOH for solvents exchanging, with EtOH
refreshed every 12 hours. The procedure was repeated six
times. Then the samples were transferred into an SFT HPR-100
reactor. The pressure and temperature gradually rose up to
1400 psi and 40 °C, respectively, and were maintained for 2
hours. The pressure was then released slowly during a period
of 1 hour while temperature was still kept at 40 °C. This
procedure was repeated three times. The activated samples
were further activated in the analysis tube under vacuum
using the “degas” function of the adsorption analyzer at 100 °C
for 4 h.
Characterizations
Powder X-ray diffraction (PXRD) measurements were
performed on a Bruker D8-Advance diffractometer with a Cu
sealed tube (λ = 1.54178 Å) at 40 kV and 40 mA. Elemental
analysis (C, H and N) was performed by an Elementar Vario EL
III element analyzer. Thermogravimetry analysis (TGA) was
conducted on a Mettler-Toledo (TGA/DSC1) thermal analyzer
under N2 atmosphere with a heating rate of 10 °C /min.
Fourier transform infrared spectra (FT-IR) were recorded as
Catalytic reactions
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Fig. 1 (a) The 4-connected porphyrin carboxylate ligand used in NUPF-3.
(b) The 4-connected mononuclear [In(COO)4]- SBU in NUPF-3. (c) The 4-
fold interpenetrating pts framework of NUPF-3. (d) Solvent accessible
pores in NUPF-3, the connolly surfaces were calculated using a 1.7 Å
probe radius in a 2×2×1 unit cell.
Before the reaction, the catalyst NUPF-3 was activated at 120 °C
under vacuum for 6 hours. For comparison, a known In-MOF
([H2N(CH2CH3)2][In(BPDC)2]∙(solvent)x,
BPDC
=
4,4'-
biphenyldicarboxylate) was synthesized according to the reported
method (Fig. S10†),16e and its catalytic properties were tested in a
similar manner. The catalytic reactions at high pressure were
The 3D framework of NUPF-3 is constructed by a 4-
carried out in a 25 mL stainless steel high-pressure reactor. The connecting porphyrinic ligand and a 4-connecting [In(COO)4]-
activated catalyst (45 mg, ~0.03 mmol based on porphyrinic In3+ SBU. Each planar porphyrinic L ligand links four [In(COO)4]-
center or 20 mg, ~0.03 mmol for In-MOF based on [In(COO)4]- units) SBUs through its four benzoate arms, while each [In(COO)4]-
together with the epoxide (25 mmol) and co-catalyst of tetra-n- SBU is tetrahedrally connected by four porphyrinic ligands.
tertbutylammonium bromide (TBAB, 0.5 mmol) was transferred to This gives rise to a highly porous framework with pts topology.
the reactor immediately. The reactor was pressurized with CO2 up The large voids formed by the linkage of elongated porphyrin
to 2.0 MPa and stirred at 40 °C for 24 h. When the reaction was linker and mononuclear [In(COO)4]- SBU lead to the known
completed, the reactor was quickly cooled in ice water and the yield phenomenon of interpenetration,28 forming
a
4-fold
of product was determined by 1H NMR. For the catalyst recycling interpenetrated three-dimensional framework in NUPF-3 (Fig.
test, the catalyst was isolated by centrifugation and washed several 1c and S6†). Despite the interpenetration, NUPF-3 is still highly
times with EtOH and CHCl3 to fully remove the substrates, dried at porous, and rhombic channels of 12.6
×15.5 Å、13.9 × 13.5
120 °C for 4 h under vacuum and then reused in another catalytic Å and 21.6 × 11.9 Å in diagonal dimensions propagate along
run.
the b-axis (Fig. S5†). The solvent accessible pore volume
comprises of 59.7 % of its unit cell volume as calculated by
PLATON (Fig. 1d).27 The framework of NUPF-3 is anionic, like
many other In-based MOFs.16a, 16h, 29 The negatively-charged
framework is balanced by the [NH2Me2]+ cations that were
formed through the hydrolysis of DMF.30 The anionic nature of
NUPF-3 could be further confirmed by dye adsorption
experiments (S7†).6c
Results and discussion
The dark-purple rhombic crystals of NUPF-3 were prepared
by heating an acidic (HCOOH) solution of DMF/H2O containing
In(NO3)3∙4.5H2O and porphyrinic ligand H4L9m in sealed vials at
120 °C for 3 days (Fig. S1†). Single-crystal X-ray crystallographic
analysis revealed that NUPF-3 crystalizes in monoclinic P21/c
space group (Table S1†). As depicted in Fig 1a, the porphyrin
macrocycle in NUPF-3 is almost planar without obvious out-of-
plane deformation, and the porphyrinic central sites were in-
situ metallized by In3+ ions during the solvothermal process.
Such central In3+ ions were coordinated to four pyrrolic N
atoms, one water molecule and one formate anion, resulting
in a six-coordinated octahedron geometry. The adjacent
phenyl rings in each side-arm of the porphyrin linker, which
are linked by amido groups, are non-coplanar and mutually
tilted by 5.04 °, 19.66°, 17.68° and 31.37 °, respectively. The
benzoic acid moieties of the porphyrinic linker are fully
deprotonated and coordinate to four In3+ ions, which serve as
structural building nodes in NUPF-3. Meanwhile, each In3+
nodes are eight-coordinated via chelation in a bi-dentate
manner by four carboxylate groups from four different
porphyrin ligands, resulting in a typical 4-connected [In(COO)4]-
structural building unit (SBU) (Fig. 1b).
Fig. 2 PXRD patterns of the samples soaked in common used solvents
(a) and acidic/alkaline solutions (b) for 2 days. (c) TG profile of NUPF-3
under N2 atmosphere from room temperature to 800 °C. (d)
Comparison of the adsorption (solid symbols) and desorption (open
symbols) isotherms of CO2 at 273 (blue line) and N2 at 77 K (red line)
for NUPF-3.
As many other indium-based MOFs, NUPF-3 exhibits high
chemical and thermal stabilities. As shown in Fig. 2a and 2b,
after the samples immersed in common used solvents such as
MeOH, H2O, CH3CN, THF, DMSO, EtOH and acidic/alkaline
solutions with pH ranging from 1 to 12 for 2 days, the PXRD
patterns of the samples remained, verifying the high chemical
stability of NUPF-3. The strong acid/alkali resistance of NUPF-3
is comparable to some highly stable Fe3+ or Zr4+ based MPFs.7a,
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13c
(%)a
Thermogravimetric (TG) analyses in the N2 stream
demonstrated that the framework of NUPF-3 could be
maintained before 350 °C, indicating a relatively high thermal
stability (Fig. 2c). Such high chemical and thermal stabilities
can be ascribed to the strong coordination bonds between In3+
ions and the carboxylic porphyrin ligands.31
1
2
Blank
0
9
0
NUPF-3
75
Despite high chemical and thermal stabilities, NUPF-3
showed limited N2 uptake at 77 K after activation (Fig. 2d and
Fig. S6†). The limited N2 adsorption is likely due to the low
affinity of the NUPF-3 framework toward N2, similar to other
reported porous MPFs such as NUPF-1,9m ZnMn-RPM,32
UNLPF-1,33 MMPF-718a and so on.34 However, NUPF-3
exhibited large uptake for CO2 at 273 K. When the pressure
gradually approached 101 kPa, the CO2 uptake reaches 82
cm3/g at 273 K. The relatively high CO2 adsorption capacity
could be attributed to the presence of acylamide group in
NUPF-3, which could enhance the affinity of the framework
toward CO2.23 Besides, the interpenetrated structure and
charged framework of NUPF-3 could also contribute to the
high CO2 uptakes.18a, 22c, 35
3
4
5
6
7
TBAB
13
95
NUPF-
3/TBAB
791
116
775
758
In-MOF
/TBAB
14
NUPF-
3/TBAB
93b
91
NUPF-
3/TBAB
NUPF-
3/TBAB
Recently, it has been reported that In3+ sites in indium-
based MOFs could serve as Lewis acidic centers for CO2
fixation.31b Considering the high structural stability, large CO2
uptakes as well as the high density of accessible
metalloporhyrin centers, we evaluated the catalytic
performance of NUPF-3 as a Lewis acid catalyst to catalyze
cycloaddition of CO2 and epoxides to form cyclic carbonates
under relatively mild conditions. As shown in Table 1, the
yields were very low (<13%) when the reactions performed
with no catalyst or solely catalyzed by NUPF-3 or TBAB (entries
1-3) under the conditions of 40 °C and 2.0 MPa for 24 h.
However, the yield was increased to 95% (entry 4) under the
identical conditions when NUPF-3 and TBAB were used
together in the catalytic system. This phenomenon has been
known for the cycloaddition of epoxides with CO2 in many
other catalytic systems, which is attributed to the synergistic
effect between the solid catalysts and quaternary ammonium
salts.22 To evaluate the contribution of [In(COO)4]- SBU to the
catalytic reaction, control experiments were conducted over
In-MOF with coordination-saturated [In(COO)4]- SBUs. The
yield of the coordination-saturated In-MOF catalyzed reaction
was 14% (entry 5), comparable to TBAB catalyzed reaction
(entry 3). The results showed that coordination-saturated
8
9
24
87
200
725
NUPF-
3/TBAB
NUPF-
3/TBAB
NUPF-
10
11
76
69
633
575
3/TBAB
NUPF-
3/TBAB
12
63
525
a.Reaction conditions: epoxide (25.0 mmol), TBAB (0.5 mmol), and
NUPF-3 (45 mg, ~0.03 mmol based on metalloporphyrin core) or In-
MOF (20 mg, ~0.03 mmol based on [In(COO)4]- SBU), under 2 MPa of
CO2 at 40 °C for 24 h. The yield was determined by 1H NMR. b.4th
catalytic run. c. Moles of epoxide consumed per mole of catalyst.
As the stability and recyclability of the catalyst are very
important for heterogeneous catalysis, the recycling
experiments were carried out over the used NUPF-3 catalyst
recovered from the cycloaddition reaction by a washing and
drying process. Experimental results indicated that the high
catalytic activity was maintained after 4th run (entry 6 and Fig.
S8†). Moreover, the PXRD pattern of the recycled NUPF-3
showed no change in the peak intensity and position,
demonstrating the high stability of NUPF-3 under experimental
conditions (Fig. S9†).
[In(COO)4]- SBUs have
a negligible contribution to the
cycloaddition of CO2 reaction. Thus, the high catalytic activity
of NUPF-3 should be mainly ascribed to the high density of
unsaturated metalloporphyrin sites confined in the accessible
voids, the large CO2 uptakes, and the activation effect for
epoxide of acylamide groups presented in porphyrin ligand, as
demonstrated by previous reports.22
Encouraged by the high catalytic activity, we further
examined the performances of NUPF-3 in chemical fixation of
CO2 with different functional group substituted epoxides. A
high yield of 91% was observed for cycloaddition of 2-
chlorooxirane using CO2 (entry 7). However, when gradually
increasing the molecular sizes of epoxide substrates, the yields
correspondingly decreased (entry 9-12), i.e. from 87% yield of
4-ethyl-1,3-dioxolan-2-one (entry 9) to 63 % yield of 4-phenyl-
1,3-dioxolan-2-one (entry 12). The internal epoxide 1,2-
epoxycyclopentane gave a low yield of 22% (entry 8), which is
likely due to the intrinsic inert nature of the substrate.36 The
Table 1 NUPF-3 catalyzed cycloaddition of CO2 and epoxides.
Entry
Catalyst
Epoxides
Products
Yield
TONc
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shape-selective phenomenon over NUPF-3 may be attributed cycloaddition of CO2 and epoxides in the presence of TBAB
to the limited diffusion of large-sized epoxide molecules into under relatively mild conditions.
the pores of NUPF-3, proved that the catalytic reactions mainly
occurred in the pores of the structure rather than on the
external surface.37
Acknowledgements
22d, 38
According to previous studies,22b,
a tentative
The authors are grateful for financial support from the
National Natural Science Foundation of China (grant number
21471075).
mechanism was proposed for the cycloaddition of epoxides
and CO2 to form cyclic carbonate catalyzed by NUPF-3. As
illustrated in Scheme 1, the central porphyrinic In atoms in the
pores of desolvated NUPF-3 might be activated and can serve
as Lewis acid catalytic sites to activate the epoxy ring via
interactions with the oxygen atom of epoxide. Besides,
epoxide may also be activated by forming hydrogen bond
between the acylamide groups of porphyrin linker and the
oxygen atom of epoxide. The less-hindered methylene carbon
atom of the activated epoxide is then attacked by the Br- from
TBAB to open the epoxy ring. Subsequently CO2 interacts with
the oxygen anion of the activated epoxide intermediate to
form an alkylcarbonate anion, which is then converted into the
corresponding cyclic carbonate through a ring closing step.
Notes and references
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From
porphyrinic In sites and high CO2 uptakes of NUPF-3 could
facilitate the cycloaddition reaction, resulting in high
a mechanistic point of view, the dense central
a
efficiency for converting CO2 into cyclic carbonates under mild
conditions.
5 For examples, see: (a) X.-S. Wang, L. Meng, Q. Cheng, C. Kim, L.
Wojtas, M. Chrzanowski, Y.-S. Chen, X. P. Zhang, S. Ma, J. Am.
Chem. Soc., 2011, 133, 16322; (b) X.-S. Wang, M. Chrzanowski,
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Scheme 1 The schematic representation of the tentatively proposed
catalytic mechanism for the cycloaddition of epoxides and CO2 over
NUPF-3. The coordinative formic acid anions were omitted for clarity.
Conclusions
Y. Luo, S.-H. Yu, H.-L. Jiang, J. Am. Chem. Soc., 2015, 137
13440.
,
In summary, a novel indium-based MPFs, denoted as NUPF-3,
has been constructed and characterized. NUPF-3 possesses a
rare 4-fold pts topology with segmented pores and dense
metalloporphyrin central sites. The structure could maintain its
crystallinity in commonly-used organic solvents and aqueous
solutions with pH ranging from 1 to 12, exhibiting high
chemical stability. After activation, NUPF-3 exhibits a high CO2
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A
robust indium-porphyrin framework based on amido-
decorated porphyrin ligands is used for CO2 capture and
chemical fixation, showing good catalytic activity and
recyclability.
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