A Gyroidal MOF with Unprecedented Interpenetrating utc-c Network Exhibiting Exceptional Thermal Stability and Ultrahigh CO2 Affinity

Article abstract of DOI:10.1021/acs.inorgchem.9b02515

A zeolite-like gyroidal MOF (denoted as SCNU-1) constructed with Cu ions and 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol has a featured interpenetrating uninodal utc-c network which is for the first time found in the real structure. Moreover, SCNU

Full text of DOI:10.1021/acs.inorgchem.9b02515

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
A Gyroidal MOF with Unprecedented Interpenetrating utc‑c
Network Exhibiting Exceptional Thermal Stability and Ultrahigh CO2
Affinity
Wei Xu,† Yin-Jiang Tang,† Lian-Qing Zheng,† Jia-Ming Xu,† Jian-Zhong Wu,*,† Yong-Cong Ou,*,†
and Ming-Liang Tong‡
†School of Chemistry, South China Normal University, Guangzhou 510006, China
‡MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yet-Sen University, Guangzhou 501275,
China
S
* Supporting Information
for realizing a new prototype of gyroid. However, precise
ABSTRACT: A zeolite-like gyroidal MOF (denoted as
SCNU-1) constructed with Cu ions and 4-(1H-imidazo-
[4,5-f ][1,10]phenanthrolin-2-yl)phenol has a featured
interpenetrating uninodal utc-c network which is for the
first time found in the real structure. Moreover, SCNU-1
exhibits high thermal (>773 K), solvent, and acid/base
stabilities; the largest CO2 affinity, 90 kJ/mol, among the
MOFs functionalized with an aromatic hydroxyl group;
and excellent CO2/N2 selectivity.
assembly of modifiable frameworks, especially new topological
gyroid, is still a great challenge. From a mathematical point of
view, discrete minimal patches could be used in constructing a
wealth of minimal surfaces.36 Similarly, assembling MOFs with
rigid and planar ligands, which coordinate with metal atoms in
certain angles, would be an effective way to target gyroidal
products. In recent years, imidazo[4,5-f ][1,10]phenanthroline
(IP) derivative ligands, used to synthesize MOFs by our
group,37,38 were identified as multidentate ligands with a large
conjugate surface which should be prospective candidates. To
verify the construction strategy and extend the relationship
between G minimal surface and adsorption properties, herein
we presented a new gyroidal MOF, [Cu3(IP-POH)2]·NO3·
9H2O, namely, SCNU-1 (SCNU = South China Normal
University), under solvothermal conditions by mixing Cu-
(NO3)2 with 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-
phenol (HIP-POH; Scheme S1). Single crystal structural
analysis revealed that SCNU-1 is composed of two inter-
penetrating utc networks, which to the best of our knowledge
is the first example found in the real structure,39 with opposite
helical channels. This rare gyroidal MOF also showed high
thermal stability (>773 K) and excellent water and chemical
stabilities. In addition, gas adsorption experiments indicated
that SCNU-1 possessed an ultrahigh affinity of carbon dioxide,
with an adsorption enthalpy of 90 kJ/mol, which is the largest
in the MOFs functionalized with aromatic hydroxyl groups,
and excellent CO2/N2 selectivity.
opology is an abstract but aesthetic multidimensional
Tspace which can be more effectively understood through
assembling specific substances.1 Being such a complex
geometric topology, gyroid (G minimal surface), which was
first found by Schoen in a crystallographic cell,2 has attracted
much attention recently not only because it shows potential
fantastic photonic, magnetic, and electrochemical properties3−5
but also because it can be realized by various topologies which
have been theoretically calculated6−8 and summarized in
RCSR.9 It should be noted that although they exist
ubiquitously in natural matter,10−15 such as cell membranes
and butterfly wing scales, these structures are referred to only
one network, srs.16 Even in artificial structures there are still
very few topological networks, for instance, extensively studied
zeolites,17−20 which are concentrated on four nets: srs, gie, fcz,
and ana. Therefore, constructing new types of topology for
gyroidal structures remains important but challenging work.
Carbon dioxide, one of the predominant greenhouse gases,
has brought the attention of many researchers to controllable
emission and reduction. One effective approach for CO2
capture21 is to use porous materials, such as aluminosilicate
zeolites, activated carbons, and metal/covalent-organic frame-
works (MOFs/COFs). Constructing MOFs with open metal
sizes (OMS) and/or functional groups, such as amino and
hydroxyl groups, should be a good way to improve the CO2
affinity.22−25 In addition, MOFs have been widely investigated
in creating new topologies26−30 due to the multivariate
connecting modes of both metal atoms and organic ligands.
Recently sporadically reported by Li and other groups,31−35
gyroidal MOFs show two more geometric networks, bcs32 and
lcs.33 It suggests that MOFs should be an optimistic selection
̅
SCNU-1 crystallizes in cubic space group Ia3d (Table S1).
The asymmetric unit contains one and a half Cu+ atoms, one
−
IP-POH− monoanionic ligand, one-half NO3 anion, and 4.5
lattice water molecules, which were confirmed via elemental
analysis, thermogravimetric analysis (TGA), and IR spectrum
(detailed in SI, Figure S1). Obviously, the Cu−N bond
lengths, between 1.856(2) and 2.018(2) Å, indicate that Cu2+
ions have been reduced to Cu+ ones, the valences of which
were determined by bond valence sum (BVS).40 As shown in
Figure S2, an IP-POH− ligand, acting as a “Y-shape” linker,
connects three Cu+ atoms. Interestingly, this coordination type
was rarely reported in the structure based on IP derivative
Received: August 20, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b02515
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Inorganic Chemistry
Communication
ligands.41 The Cu1 atom in tetrahedral geometry is surrounded
by four nitrogen atoms from two chelated phenanthroline
groups with a dihedral angle of 89.3(4)°, whereas two other
cuprous atoms, Cu2 and Cu3, are linearly coordinated with
two nitrogen atoms of different imidazole groups. Notably, the
Cu3 atom is not coplanar with the linking IP group (torsion
angle of Cu3−N4−C13−N3 is 162.1(2)°), while the Cu2
atom and IP group are nearly horizontal (Figure S3). In
addition, the dihedral angles of adjacent IP groups, meeting at
Cu2 and Cu3 atoms, are 40.4(4)° and 49.6(2)°, respectively,
which means that three running IP groups are at a right angle
(Figure S4). Accordingly, along the a, b, and c axes, eight such
consecutive IP-POH− ligands and eight 2-coordinated cuprous
atoms compose a repeat unit of 41 helices, which can shape
left-handedness as well as right-handedness and are further
connected into a three-dimensional framework via the 4-
coordinated Cu1 atoms (Figures 1 and S5). It is noted that the
Figure 2. (a) Interpenetrated utc networks in SCNU-1 (left-handed
and right-handed separated networks are represented in green and
purple color, respectively). (b) Tiling representation of half tiles with
two kinds of faces colored differently (this half corresponds to the
green network in a, while the rest of the tiles are frozen in the empty
space).
symbol of 82.9 and a vertex symbol of 8.8.9, which are collected
in RCSR as the utc nets (single network), and also identified as
sphere packing type 3/8/c2 and EPINET symbol sqc9269. To
the best of our knowledge, SCNU-1 is the first real structure
with utc networks even though some theoretical studies have
been presented.6−8,39 In addition, as a G minimal surface, the
symmetry of the labyrinth graph utc is a chiral space group
̅
I4132, but for the whole networks in SCNU-1 it is Ia3d due to
the existence of two opposite chiral utc networks. Therefore,
the topological symbol for SCNU-1 could be denoted as utc-c
net (-c represented a catenated pair). The tiles in Figure 2b,
depicting just half of the tiles (another is shown in Figure S8),
illustrates that the utc-c network lies on the gyroidal channel,
which is separated by the G minimal surface. The construction
of a new network can expand the understanding about the
relationship between topology and minimal surface.
The stability properties, including thermal and chemical
stabilities, have been investigated. The TGA curve of as-
synthesized SCNU-1 (Figure 3a) under a nitrogen atmosphere
shows a weight loss of 15% before 473 K and 6% more until
573 K, corresponding to the release of nine water molecules
and HNO3, respectively. The PXRD data (Figure S9) of the
activated samples at 373 and 573 K were consistent with that
of as-synthesized samples, indicating that the crystallinities of
SCNU-1 were maintained after a loss of water and HNO3
molecules. Interestingly, the weight loss was less than 2% until
773 K under a N2 atmosphere, revealing that the frameworks of
SCNU-1 could remain intact at such a high temperature, which
was well beyond that of Cu+-based MOFs, only agreeing with
several nonoxidizing metal-based MOFs.43−46 Comparably,
under an oxygen atmosphere, the approximate decomposition
Figure 1. Two 3D frameworks in opposite handedness in SCNU-1
(the left-handed helices in a are colored in light green, brown, and
blue, while the right-handed ones in b are highlighted in purple,
turquoise, and yellow), composed of pure left-handed (c) and right-
handed (e) helices respectively along a, b, and c directions of the
coordinate system (Cu1 atoms are shown in green tetrahedra)
incorporated in a 2-fold interpenetrated porous structure ((d) space-
filling view along (111) direction) in which the hydroxyl groups (red)
are fronting the cavity space.
3D structure of SCNU-1, lacking in chiral features, is
comprised of two separated interpenetrating frameworks
which exhibit opposite handedness originating from homo-
chiral helices and is stabilized through C−H···π interactions
(Figure S6). Even though the large square cavity spaces (about
2.5 nm) are reduced by 2-fold interpenetration of the 3D
framework, according to the calculation of PLATON,42 the
solvent-accessible volume remains 39 007 Å 3, ca. 54.7% of the
cell volume, which includes two kinds of pore cavities,
spherical polyhedral cages (inner diameter, 1.8 × 1.6 × 1.4
nm3) and 1D channels (inner diameter, 0.5 nm; Figures 1d and
S7). Notably, all of the aromatic hydroxyl groups of ligands
front the cavity space and become partitions of spherical cages,
which can be strung together by 1D channels.
−
temperature of NO3 and organic ligands indicated that the
Cu−N bonds under a N2 atmosphere are more stable.
Meanwhile, in order to examine the chemical stabilities,
activated samples have been immersed into aqueous solutions
with different pH values ranging from 2 to 14, common
organic solvents at ambient temperature, and boiling water for
24 h, respectively. The resulting PXRD patterns (Figures S10−
S12) were the same as that of the as-synthesized material,
demonstrating the good maintenance of crystallinity, high
acidic and basic stabilities, and excellent resistance to
hydrolysis and/or solvation.47
As described above, each ligand is linked to three adjacent
ones through metal ions, acting as connectors, and in this way
the SCNU-1 framework can be simplified into a uninodal 3-
connected interpenetrated network (Figure 2a) with a point
The architectural rigidity and consequently the permanent
porosity of activated SCNU-1 were unequivocally in evidence
via gas sorption analysis. Type I nitrogen sorption isotherm
B
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behavior was observed at 77 K for SCNU-1 (Figure S13),
which revealed its microporous nature. The Langmuir and
BET surface areas based on the data in the low-pressure range
(P/P0 = 0.06−0.25) were 1123 and 774 m2/g, respectively.
The pore volume calculated from the N2 isotherm was 0.45
cm3 g−1, in good agreement with the value (0.47 cm3 g−1)
obtained from single-crystal data, which further confirmed the
good sample crystallinity and purity.
On the basis of the existence of pore-surface active sites,
including 2-coordinated Cu+ OMS and the hydroxyl group, the
CO2 sorption properties at different temperatures were
studied. At 1 bar, SCUN-1 exhibited a CO2 uptake of 2.75
mmol/g at 273 K and 1.78 mmol/g at 298 K (Figure 3b).
Because the isotherms showed relatively large slopes at low
pressures, the CO2 binding affinity was confirmed through the
coverage-dependent heat of adsorption of CO2 (Qst) calculated
via both Virial and dual-site Langmuir (DSL) analyses (Figure
S14 and 3c). At zero coverage, the maximum adsorption
enthalpy of SCUN-1 for the Virial/DSL method reached 78/
90 kJ/mol, which is the highest value in hydroxyl-function-
alized (Table S3) and amine-functionalized24,48 MOFs. To the
best of our knowledge, the ultrahigh CO2 affinity surpasses
many porous materials containing nucleophilic M−OH groups,
such as Zn−OH (71 kJ/mol)23 and Al−OH (40 kJ/mol),49
but is only lower than two MOFs22 containing Co−OH (124
kJ/mol) and Mn−OH (120 kJ/mol). It can be ascribed to the
stronger interaction between OMS and CO2 molecules in
SCNU-1, which was calculated through the Adsorption locat0r
module in Materials Studio 8.050 (Figure S15). Furthermore,
the CO2 affinity can be assigned to the chemisorption
interaction, which was probed by in situ IR spectra (Figure
S16). In a CO2 atmosphere, new adsorption peaks appeared at
3597, 3625, 3700, and 3725 cm−1, ascribable to the stretching
vibration of the H−OCO2 group. The bands at 2329, 2343,
2353, and 2368 cm−1, red-shifted and blue-shifted from the
unperturbed value of the CO2 asymmetric stretch (2349
cm−1), also confirmed the interactions between CO2 and
hydroxyl groups and OMS, respectively.51
The selectivity for adsorption of CO2 over N2 is the primary
condition for MOFs applicable as carbon dioxide capture
materials. To evaluate the potential for separating CO2/N2
mixtures, the N2 sorption isotherm for SCNU-1 was measured
at 298 K, which showed uptakes of 0.09 mmol/g at 1 bar, and
the CO2/N2 selectivity under conditions of a typical
composition of flue gas (CO2/N2, 15:85) was predicted from
the experimental one-component isotherms using the ideal
adsorption solution theory (IAST).52 Due to the strong
adsorption sites occupied at low pressure, CO2/N2 selectivity
of SCNU-1 decreased with increasing pressure (Figure 3b). At
298 K, the CO2/N2 selectivities at 1 bar were up to 108, which
was comparable with some typical MOFs with OMS and/or
hydroxyl groups, such as HKUST-1 (101),53 UiO-66(Zr)-
(OH)2 (105),54 and Mg-MOF-74 (148).55
The regeneration of the CO2 adsorption−desorption
process in SCNU-1 during the gas cycling at 304 K was
carried out by TGA with a purge gas swinging between a 15:85
CO2/N2 mixture and a pure N2 flow. About a 2.8 wt % weight
change was observed and maintained well over repeated cycles
(Figure 3d), indicating that SCNU-1 was able to withstand
cyclic exposure to the mixed gas stream and more importantly
can be regenerated only by flushing with N2 at low
temperatures.
Figure 3. (a) Thermogravimetric plots of as-synthesized sample,
activated samples under a N2 atomsphere, and as-synthesized samples
under a O2 atomsphere. (b) CO2 adsorption (solid) and desorption
(open) isotherms at 273 K (red rectangle) and 298 K (blue triangle),
compared with that of N2 at 298 K (green rhombus), and IAST
selectivities of CO2/N2 (dark-yellow). (c) CO2 adsorption enthalpy
(Qst) and (d) adsorption−desorption cycling for SCNU-1 between a
15:85 CO2/N2 (v/v) flow and a pure N2 flow at 304 K.
C
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ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b02515.
Experimental and calculation details and supplementary
figures (PDF)
Accession Codes
CCDC 1919463 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: ouyongcong@m.scnu.edu.cn.
*E-mail: wujianzhong@m.scnu.edu.cn.
ORCID
Yong-Cong Ou: 0000-0001-9773-0090
Ming-Liang Tong: 0000-0003-4725-0798
Notes
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O’Keeffe, M. A mesoporous germanium oxide with crystalline pore
walls and its chiral derivative. Nature 2005, 437, 716.
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
This work was supported by NSFC (21401058) and South
China Normal University. We thank the staff from the BL17B
beamline at Shanghai Synchrotron Radiation Facility (SSRF)
for assistance during data collection. We thank Mr. W.-Q.
Zhang of Sun Yet-Sen University for gas adsorption and
discussion.
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DOI: 10.1021/acs.inorgchem.9b02515
Inorg. Chem. XXXX, XXX, XXX−XXX