Fluorinated porous organic frameworks for improved CO2 and CH4 capture

Article abstract of DOI:10.1039/c9cc03248g

A porous 3D selectively fluorinated framework (F-PAF1), robust yet flexible and with a surface area of 2050 m² g^-1, was synthesised by condensation of an ad hoc prepared fluorinated tetraphenylmethane (TPM) monomer to ensure homogenously distributed C-F dipoles in the swellable architecture. Tetradentate TPM was also the comonomer for the reaction with fluorinated difunctional monomers to obtain frameworks (FMFs) with a controlled amount of regularly spaced reorientable C-F dipoles. The isosteric heat of adsorption of CO₂ was increased by 53% by even moderate C-F dipole insertion, with respect to the non-fluorinated frameworks. CO₂/N₂ selectivity was also increased up to a value of 50 for the difluoro-containing comonomer. Moreover, methane shows optimal interaction energies of 24 kJ mol^-1.

Full text of DOI:10.1039/c9cc03248g

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Fluorinated porous organic frameworks for improved CO2 and CH4
capture
A. Comotti, F. Castiglioni, S. Bracco,* J. Perego, A. Pedrini, M. Negroni and P. Sozzani
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Porous 3D selectively-fluorinated framework (F-PAF1), robust yet owing to their tough backbone. These materials can exhibit high
flexible and with a surface area of 2050 m2/g, was synthesised by surface area, large pore volume and remarkable loading
condensation of ad hoc prepared fluorinated tetraphenylmethane capacity.11-13 However, unfunctionalized POFs have moderate
(TPM) monomer to ensure homogenously distributed C-F dipoles in CO2/N2 selectivity. Increased performances for CO2 over N2 is
the swellable architecture. Tetradentate TPM was also the crucial since flue gas streams typically contain 85% N2 and only
comonomer for the reaction with fluorinated difunctional 15% CO2. A strategy to improve selectivity consists in inserting
monomers to obtain frameworks (FMFs) with a controlled amount electron rich functional groups, by pre- and post-synthetic
of regularly spaced reorientable C-F dipoles. Isosteric heat of approaches, that are expected to increase the materials affinity
adsorption of CO2 was incremented of 53% by even moderate C-F towards CO2.14–18 A variety of functional groups, such as amines,
dipoles insertion, with respect to the non-fluorinated amides and sulfonates, have been tested for this goal.19–22
frameworks. CO2/N2 selectivity was also increased up to a Fluorine is a promising candidate since its small size is expected
value of 50 for the difluoro-containing comonomer. Moreover, to slightly reduce the total pore volume, while its high
methane shows optimal interaction energies of 24 kJmol-1.
electronegativity should establish stronger interactions with
CO2 electrical quadrupole moment. So far, a small number of
fluorine-functionalized porous organic materials have been
explored as adsorbents of CO2.15,23–25 To extend the library of
existing fluorinated organic porous materials, we report the
synthesis of new fluorinated organic porous materials by
adopting two distinct strategies: direct condensation of an ad
hoc fluorinated tetrahedral monomer, specifically designed for
this sake, and copolymerization between two complementary
functionalities of tetrahedral (A4) and fluorine-containing linear
(B2) struts such as monofluoro and difluoro-p-phenylene units.
By this synthetic strategy the fluorine atoms are regularly bound
onto each monomeric unit and are exposed to the pore volume
(Figure 1).
Carbon dioxide is undisputedly one of the major causes for the
global warming phenomenon and it is also involved in other
serious environmental issues, such as the incremented acidity
of oceans.1 Industrial activity has a critical fallout on CO2
emissions and the most employed technique to reduce its
concentration from flue gas streams utilizes amine solutions to
chemically bind carbon dioxide molecules.2 However, this
process requires high regeneration costs and produces a
negative impact on the environment. In recent years porous
materials have emerged as a viable alternative for carbon
dioxide capture.3-5 The main advantages offered by porous
solids are the low regeneration costs and superior cyclabality
provided by gas-solid physisorption phenomena and simpler
end-of-life disposal. The classes of materials proposed for this
application include Metal-Organic Frameworks (MOFs),6
HyperCrosslinked
Polymers
(HCPs),7
Covalent-Organic
Frameworks (COFs),8 and Porous Organic Frameworks
(POFs).9,10 Since thermal and chemical robustness as well as the
versatility of synthesis are required, porous organic frameworks
sustained by rigid covalent bonds were a successful choice,
Figure
1 Schematic representation of fluoro porous aromatic
framework F-PAF1. Blue spheres represent fluorine atoms.
Department of Materials Science, University of Milano Bicocca, via R. Cozzi 55,
20125, Milano, Italy.
E-mail: silvia.bracco@unimib.it
Electronic Supplementary Information (ESI) available: details of synthesis, details of
experimental conditions, additional characterization. See DOI: 10.1039/x0xx00000x
Our design was to build local C-F dipoles that imparted a dipole
moment to the whole p-phenylene moiety, wherein C-F groups
are inserted. This was made possible by arranging the dipolar
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sostituents in a non-centrosymmetric manner. The frameworks (T1=1.5 s for C3), as occurring in prototypal PAF-1 rotors.26,27
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were designed to bear a limited amount of fluorine atoms in Despite a comparable torsional flexibiliDtyOIo: 1f0f.1lu03o9r/iCn9aCteCd03r2i4n8gGs
order to keep the skeleton as light as possible and at the same about the pivotal sp2-sp2 carbon-carbon bonds, orientational
time
a
regularly-spaced fluorine substitution. Such dynamics of fluorinated rings was slower, as proved by longer
homogeneous distribution ensures that the carbon-fluorine spin-lattice relaxation times (T1>10s) owing to the increased
dipoles are exposed to the diffusing-in gases, resulting in a well- inertial mass of the rotor and long-range electrostatic
distinct behaviour as compared to the unfluorinated skeleton interactions among C-F dipoles. Overall, dynamical results
and promoting enhanced affinity for CO2 and CH4.
depict a skeleton bearing reorientable aromatic moieties,
The syntheses of the three fluorinated materials are reported in potentially adaptable after guest diffusion. In the 2-FMF
Scheme 1. In particular, the condensation of fluorinated spectrum, the C-F signal resonates upfield at 153 ppm (Figure
microporous frameworks (FMFs) employs a Sonogashira 2c), falling to the side of the dominant resonances of
coupling protocol to create an extended copolymer framework hydrocarburic aromatic carbons, as supported by 13C solution
1
between tetrakis(4-bromophenylmethane) (1) and
a
NMR spectrum of the monomer 3 (see ESI). 600 MHz H MAS
difunctional 1,4-diethynil-2-fluorobenzene (2) or 1,4-diethynil- NMR spectra with high spinning speed (35 kHz), which reduced
2,3-difluorobenzene (3) in a 1:2 ratio, leading to the formation homonuclear dipolar couplings, display exclusively the aromatic
of 1-FMF and 2-FMF, respectively. The fluorinated porous signals at =6.8 ppm, ensuring the absence of any unreacted
aromatic framework F-PAF1 was prepared by Yamamoto-type monomer or solvent entrapped in the framework as expected
homopolymerization
reaction
of
4,4’,4”-((4-bromo-3- for an empty porous structure.
fluorophenyl) methantryl)tris(bromobenzene) (4). To the best
of our knowledge, this is the first example of the fluorinated
PAF1 carrying the fluorine atoms on the tetraphenylmethane
monomer unit.
Scheme 1 Schematic synthesis of 1-FMF, 2-FMF and F-PAF1.
The high conversion efficiency of the Cu-free Sonogashira
protocol and the formation of alkyne-aryl bonds for the
preparation of 1-FMF and 2-FMF was confirmed by FTIR
spectroscopy measurements (see ESI, Figure S1). In both IR
spectra, the bands ascribable to internal (i.e. disubstituted)
alkyne groups con be appreciated at 2200 cm-1. TGA curves of
the fluoro-containing frameworks show their extremely high
stability, up to 450-500°C, as a consequence of the fully covalent
bond network (ESI, Figure S2). No periodic order was observed
in the powder X-ray diffraction patterns. SEM images of F-PAF1
highlights the narrow distribution of spherical nanoparticles
with an average diameter of 78 nm (Figure S4).
Magic angle spinning (MAS) 13C CP NMR spectra show the
chemical structure of the frameworks (Figure 2). Signal
assignments were established by comparison to solution 13C-
NMR spectra of the monomers. Besides the signals of non
fluorinated moieties, characteristic signals of the presence of
fluorine atoms on p-phenylene rings appear in the aromatic
region (highlighted orange). The peak at 65 ppm belongs to the
central quaternary carbon atom of the tetraphenylmethane
units, while the resonances in the 80-100 ppm region of 1-FMF
and 2-FMF correspond to C≡C carbon atoms. Notably, in F-PAF1
the doublet due to the 250 Hz J(13C-19F) coupling of the carbon
nucleus directly bonded to fluorine atom is apparent at ca. 160
ppm (Figure 2a). 13C T1 NMR relaxation times indicate fast 108
Hz reorientation rate for the non-fluorinated para-phenylenes
Figure 2 13C CP MAS NMR spectra of a) F-PAF1, b) 1-FMF and c) 2-FMF
(contact time= 2 ms). 600 MHz 1H MAS NMR spectra at 35 kHz spinning
speed are reported on the upper left corners. The signals of the
fluorinated p-phenylene units are highlighted in orange.
The porosity of the materials was evaluated by N2
adsorption/desorption isotherms at 77 K (Figure 3). The main
parameters derived from gas adsorption measurements are
reported in Table S1. The Langmuir and BET surface areas of F-
PAF1 are 2338 and 2054 m2/g, respectively: these values are
among the highest reported for fluorinated organic porous
materials.15,23-25 The shape shows a contribution by the
mesoporosity resulting in a total pore volume of 1.96 cm3 g-1,
that is outstanding for a fluorinated organic porous material. N2
desorption branch runs distinctly above the adsorption curve,
forming a large hysteresis loop closing only at very low
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pressures, indicative of framework flexibility owing to the ability vant’Hoff equation at low coverage for F-PAF1 is 25 kJ/mol,
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of the porous structure of breathing and swelling by absorption, which is significantly higher than the 15.6DkOJ/I:m10o.1l0d3e9t/eCr9mCCin0e3d24f8oGr
like a sponge.28 Pore size distribution analysis (PSD), carried out PAF1.21 Notably, the CO2 isotherm changes from a sigmoidal
by Non-Local Density Functional Theory (NLDFT) and carbon slit shape for PAF1 to a Langmuir profile for F-PAF1, owing to a
pore model, shows a peak centered at 11.9 Å.
higher CO2 affinity towards the fluorinated surface. Thus, the
use of a fluorinated building block leads to a 53% increase of
Qst(CO2) with respect to the non-fluorinated analogue. For 1-
FMF, the Qst(CO2) calculated at low coverage is 30 kJ/mol,
respectively, indicating favorable interactions with CO2. These
values are higher than that of the parent non-fluorinated
framework (26 kJ/mol), demonstrating the effectiveness of the
C-F dipole insertion to enhance the CO2 capture. It is expected
that two vicinal fluorine atoms further increase the binding
energy because of the cooperative interactions with the
positively charged carbon of CO2, as previously proved by
theoretical calculations.32 Indeed, for 2-FMF the Qst reached 32
kJ/mol. Futhermore, the torsional flexibility of the Csp2-Csp
bond about the monofluoro and difluoro-p-phenylene
moieities33 may allow to adjust the conformation in order to
maximize the dipole-CO2 interaction.
The higher CO2 heat of adsorption for the fluorinated matrices
Figure 3 N2 isotherms at 77 K of F-PAF1 (a) and 1-FMF and 2-FMF (b) was reflected in the higher CO2/N2 selectivity values derived by
(yellow and red diamonds, respectively). c) Hyperpolarized (HP) 129Xe
NMR spectra collected at room temperature.
the Ideal Adsorbed Solution Theory (IAST) for the case of 15/85
CO2/N2 mixture, typical of industrial fume emissions (ESI). At
273 K, the covalent frameworks exhibited a CO2/N2 selectivity
1-FMF and 2-FMF show type I isotherms characteristic of
microporous solids with Langmuir and BET surface areas of
1285 and 1132 m2g-1 for 1-FMF and 970 and 853 m2g-1 for 2-
FMF, respectively (Figure 3b). PSD analysis reveals two peaks at
ca. 5.9 -11.9 Å for 1-FMF and 2-FMF. An increase in the 5.9 Å
peak height is observed for the difluoro substituted material
(ESI), indicating that the increase of fluorine substitution selects
an ultramicroporosity range, which offers neat advantages for
the adsorption of small gas molecules. Hyperpolarized (HP)
129Xe NMR is a valuable tool to provide a highly sensitive
response to the pore size.29,30 The exploration of the restricted
environment by Xe atoms is manifested by high chemical shift
values (104-127 ppm) with respect to the gas phase (Figure 3c).
The chemical shift increase from F-PAF1 to copolymers reveals
the more effective Xe confinement in the smaller pores of the
copolymers (from 11 to 6 Å).
The new fluorinated matrices were tested for carbon dioxide
and methane capture. CO2 sorption isotherms were collected at
195 K up to 1 bar and at three other distinct temperatures (273,
283, 298 K) up to 10 bar (Figure 4a and S8). Owing to its higher
surface area, F-PAF1 shows a remarkable CO2 uptake at 195 K
and 1 bar, reaching the value of 26.3 mmol/g, that corresponds
to 115% of its weight. Interestingly, in F-PAF1, the CO2
adsorption value at 273 K and 1 bar is superior to that reported
for the unfunctionalized PAF1 (2.7 vs 2.0 mmol/g,
respectively),31 despite the lower BET surface area (2054 vs
5300 m2/g, respectively). The presence of fluorine atoms
enhances low-pressure CO2 capture through favorable
electrostatic interactions. Similarly, the CO2 uptake for 1-FMF at
273 K and 1 bar is superior to its non-fluorinated analogue
MOP1 (2.4 versus 2.1 mmol/g, respectively).14 Furthermore, the
CO2 isosteric heat of adsorption Qst, calculated using the
as high as 31 and 48 for 1-FMF and 2-FMF, respectively. The
selectivity of 1-FMF and 2-FMF is superior to the porous
materials obtained by post-synthetic fluorination methods
recently reported.24
Since enhanced interactions can be expected towards CH4 owing to
the polarity of C-F bond, CH4 adsorption measurements were
performed at various temperatures to characterize the process
(Figure 4c and S9). The Qst for F-PAF1 (17 kJ/mol) is higher compared
that of the non-fluorinated analogue (14 kJ/mol)34, which confirms
the increased CH4 affinity owing to the presence of fluorine in the
porous matrix. 1-FMF and 2-FMF show a remarkably higher Qst up to
20 and 24 kJ/mol, respectively. The presence of two adjacent fluorine
atoms on the p-phenylene moiety increases the dipole moment and
plays a key role in enhancing the interactions of the framework with
CH4. Additionally, the sub-nanometer pore size increases van der
Waals stabilisation which significantly contributes to the remarkably
favorable CH4 binding energy. The Qst values are compatitive with the
values reported for the best performing MOFs and COFs (see Table
S5 in ESI). In particular, they exceed the reported value for H-KUST-1
(18.2 Kcal/mol), a Cu(II)-based MOF whose methane adsorption
properties are considered the benchmark in the field of porous
materials and suitable for practical uses.35 Futhermore, the CH4/N2
(50:50 mixture) and CO2/CH4 (50:50 mixture) selectivities were
studied, using IAST theory, to evaluate the materials performance
towards gas purification (ESI). 1-FMF and 2-FMF show good
selectivity for both CO2/CH4 and CH4/N2 binary mixtures. In
particular, the CO2/CH4 selectivity of 1-FMF at 273 K and 298 K of 5.4
is close that of HKUST-1 (estimated as 4.8).36
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acknowledged. A.C. acknowledges support from PRIN 2016-NAZ-
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Conflicts of interest
There are no conflicts to declare.
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Table of Contents
Hyperpolarized 129Xe NMR highlights open porosity of fluorinated organic frameworks which show
CO2 and CH4 capture with high selectivity towards N2.