Microporous Metal-Organic Framework Stabilized by Balanced Multiple Host-Couteranion Hydrogen-Bonding Interactions for High-Density CO2 Capture at Ambient Conditions

Article abstract of DOI:10.1021/acs.inorgchem.5b02316

Microporous metal organic frameworks (MOFs) show promising application in several fields, but they often suffer from the weak robustness and stability after the removal of guest molecules. Here, three isostructural cationic metal-organic frameworks {[(Cu₄Cl)(cpt)₄(H₂O)₄]·3X·4DMAc·CH₃OH·5H₂O} (FJU-14, X = NO₃, ClO_4, BF₄; DMAc = N,N′-dimethylacetamide) containing two types of polyhedral nanocages, one octahedron, and another tetrahedron have been synthesized from bifunctional organic ligands 4-(4H-1,2,4-triazol-4-yl) benzoic acid (Hcpt) and various copper salts. The series of MOFs FJU-14 are demonstrated as the first examples of the isostructural MOFs whose robustness, thermal stability, and CO₂ capacity can be greatly improved via rational modulation of counteranions in the tetrahedral cages. The activated FJU-14-BF₄-a containing BF₄^- anion can take CO₂ of 95.8 cm³ cm^-3 at ambient conditions with an adsorption enthalpy only of 18.8 kJ mol^-1. The trapped CO₂ density of 0.955 g cm^-3 is the highest value among the reported MOFs. Dynamic fixed bed breakthrough experiments indicate that the separation of CO₂/N₂ mixture gases through a column packed with FJU-14-BF₄-a solid can be efficiently achieved. The improved robustness and thermal stability for FJU-14-BF₄-a can be attributed to the balanced multiple hydrogen-bonding interactions (MHBIs) between the BF₄^- counteranion and the cationic skeleton, while the high-density and low-enthalpy CO₂ capture on FJU-14-BF₄-a can be assigned to the multiple-point interactions between the adsorbate molecules and the framework as well as with its counteranions, as proved by single-crystal structures of the guest-free and CO₂-loaded FJU-14-BF₄-a samples.

Full text of DOI:10.1021/acs.inorgchem.5b02316

Article
pubs.acs.org/IC
Microporous Metal−Organic Framework Stabilized by Balanced
Multiple Host−Couteranion Hydrogen-Bonding Interactions for
High-Density CO Capture at Ambient Conditions
2
†
‡
‡
†
†
,†
†
Yingxiang Ye, Shunshun Xiong, Xiaonan Wu, Liuqin Zhang, Ziyin Li, Lihua Wang,* Xiuling Ma,
†
†,§
,†,§
Qian-Huo Chen, Zhangjing Zhang, and Shengchang Xiang*
†College of Chemistry and Chemical Engineering, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University,
2 Shangsan Road, Fuzhou 350007, People’s Republic of China
3
‡
Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, Sichuan 621900, People’s Republic
of China
§
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, People’s Republic of China
*
S Supporting Information
ABSTRACT: Microporous metal organic frameworks (MOFs) show promising application in several fields, but they often suffer
from the weak robustness and stability after the removal of guest molecules. Here, three isostructural cationic metal−organic
frameworks {[(Cu Cl)(cpt) (H O) ]·3X·4DMAc·CH OH·5H O} (FJU-14, X = NO , ClO BF ; DMAc = N,N′-
4
4
2
4
3
2
3
4,
4
dimethylacetamide) containing two types of polyhedral nanocages, one octahedron, and another tetrahedron have been
synthesized from bifunctional organic ligands 4-(4H-1,2,4-triazol-4-yl) benzoic acid (Hcpt) and various copper salts. The series
of MOFs FJU-14 are demonstrated as the first examples of the isostructural MOFs whose robustness, thermal stability, and CO2
capacity can be greatly improved via rational modulation of counteranions in the tetrahedral cages. The activated FJU-14-BF -a
4
containing BF4− anion can take CO of 95.8 cm cm at ambient conditions with an adsorption enthalpy only of 18.8 kJ mol .
3
−3
−1
2
−3
The trapped CO density of 0.955 g cm is the highest value among the reported MOFs. Dynamic fixed bed breakthrough
2
experiments indicate that the separation of CO /N mixture gases through a column packed with FJU-14-BF -a solid can be
2
2
4
efficiently achieved. The improved robustness and thermal stability for FJU-14-BF -a can be attributed to the balanced multiple
4
hydrogen-bonding interactions (MHBIs) between the BF4− counteranion and the cationic skeleton, while the high-density and
low-enthalpy CO capture on FJU-14-BF -a can be assigned to the multiple-point interactions between the adsorbate molecules
2
4
and the framework as well as with its counteranions, as proved by single-crystal structures of the guest-free and CO -loaded FJU-
2
1
4-BF -a samples.
4
4
INTRODUCTION
CO . However, this technology needs to cost a larger amount
2
■
Carbon dioxide (CO ) is well known as a chief perpetrator of
the greenhouse effect about the global climate. Currently,
of regeneration energy, owing to the strong interactions
2
1
between the CO and the absorbents. To date, many solid
2
carbon dioxide emissions are mainly generated from the
combustion of coal, oil, and natural gas. Carbon capture and
separation (CCS) is the most effective technique in reduction
of carbon dioxide emissions from postcombustion flue gas and
in biogas upgrading to biomethane. The state-of-the-art
2
porous adsorbent materials have achieved a dominant position
to capture and separate CO based on physical adsorption,
2
3
Received: October 12, 2015
aqueous alkanolamine solutions have been used to capture
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.5b02316
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
5
6
including zeolites, activated carbons (or carbon nanotubes),
substitution here will not obviously reduce the pore volume.
(2) These anions can provide different polar groups, especially
7
,8
and metal−organic frameworks (MOFs).
Compared with the other solid porous adsorbent materials,
the emerging porous metal−organic frameworks received grea9t
attention recently, due to their extraordinary surface area,
F atoms, to capture CO molecules in conjunction with the
2
skeleton. Interestingly, in contrast with the other two
−
isostructural MOFs, the FJU-14-BF containing BF anion
4
4
1
0
finely tunable pore surface properties, and ubiquitous
potential applications, such as gas storage and selective
separation, chemical sensing, proton conductors, and
in its tetrahedral cages exhibits improved robustness and
11
thermal stability, high uptake, and low-enthalpy CO
2
1
2
13
14
−3
adsorption. The trapped CO density of 0.955 g cm is the
2
15
heterogeneous catalysis. In addition, several strategies based
on tuning the open metal sites (OMS), polarizing functional
groups (Lewis basic sites = LBS), pore size exclusive effect, and
flexible framework backbone have been proposed, demonstrat-
ing that MOF materials are very promising for postcombustion
gas separation and purification. However, there is still a big
weakness for most of the porous MOFs, which are likely to
disintegrate or shrink into nonporous frameworks after removal
of the guest molecules. It is well known that formed rigid nodes
and ligands, interpenetrated frameworks, and highly connected
metal ion clusters (also known as secondary building units
highest value among the reported MOFs. The single-crystal
structure of its guest-free sample shows that the balanced
MHBIs between the BF4− counteranion and the cationic
skeleton play a crucial role in stabilizing its framework
robustness. Furthermore, single-crystal X-ray diffraction for
CO loaded FJU-14-BF -a sample shows that CO capture can
16
2
4
2
come from the multiple-point interactions between the
adsorbate molecules and the framework as well as its
counteranions. Dynamic fixed bed breakthrough experiments
indicate that the separation of CO /N mixture gases through a
2
2
column packed with FJU-14-BF -a solid can be efficiently
4
(
SBUs)) have been proved as effective methods to preserve the
achieved.
17
pores and avoid structural collapse. Moreover, supercritical
CO2 activation, freeze-drying treatment, and liquid-solvent
exchange have been certified as other effective methods to
stabilize the robustness of the porous frameworks during
activation. For the nonrobust MOFs, two novel ideas,
inserting neutral pillars and introducing large cationic
guests, have been recently proposed to sustain MOF
robustness with tunable porosity, but these methods would
reduce the pore volume. To date, improving the MOFs
robustness by the balanced multiple hydrogen-bonding
interactions (MHBIs) between the host and the guest
counteranions has not been observed.
EXPERIMENTAL SECTION
■
Materials and Methods. Cu(ClO ) ·6H O and Cu(BF ) ·6H O
4 2 2 4 2 2
were purchased from J&K Chemical Co., Ltd. and Cu(NO ) ·3H O,
1
8
3
2
2
1
9
N,N-dimethylacetamide (DMAc), and other reagents were purchased
from Shanghai Chemical Reagent Co. and used as received without
further purification. The ligand Hcpt was prepared according to a
2
0
22
known modified method. Powder X-ray diffraction (PXRD) was
3
carried out with a PANalytical X’Pert powder diffractometer equipped
with a Cu-sealed tube (λ = 1.541874 Å) at 40 kV and 40 mA over the
2
θ range of 5−30°. The simulated pattern was produced using the
Mercury V1.4 program and single-crystal diffraction data. The Fourier
In this article, three isostructural cationic metal−organic
transform infrared (KBr pellets) spectra were recorded in the range of
−
1
frameworks, {[(Cu Cl)(cpt) (H O) ]·3X·4DMAc·CH OH·
500−4000 cm on a Thermo Nicolet 5700 FT-IR instruments.
Thermal analysis was carried out on a METTLER TGA/SDTA 851
thermal analyzer from 30 to 600 °C at a heating rate of 10 °C min−
under nitrogen atmosphere. Elemental analyses (C, H, and N) were
performed on a PerkinElmer 240C analyzer.
4
4
2
4
3
5
H O}(FJU-14, X = NO , ClO and BF ), have been
2 3 4 4
1
synthesized from bifunctional organic ligands 4-(4H-1,2,4-
triazol-4-yl) benzoic acid (Hcpt) and various copper salts
Scheme 1) based on considering two aspects. (1) These
(
Syntheses. 4-(4H-1,2,4-Triazol-4-yl)benzoic Acid (Hcpt). Reflux-
ing a mixture of N,N′-dimethylformamide azine dihydrochloride (2 g,
Scheme 1. Schematic Diagram for the Synthesis of Three
Isostructural Metal Organic Frameworks (MOFs) by Making
Use of Different Copper Salts
9
.33 mmol) and 4-aminobenzoic acid (1.28 g, 9.33 mmol) in 25 mL of
o-xylene (reaction should be conducted in a fume hood) for 24 h gave
a pale yellow solid, which was filtered and washed with EtOH (1 × 10
mL) and Et O (1 × 8 mL); yield 1.21 g (69%). Furthermore, the pale
2
yellow solid and water (5 mL) were transferred into a Parr Teflon-
lined stainless steel vessel (23.0 mL) and heated to 150 °C for 24 h
under autogenous pressure and cooled to room temperature at a rate
−1
of 5.0 °C h . Colorless rod-shaped crystals of Hcpt suitable for single-
crystal X-ray analysis were obtained directly.
[
(Cu Cl)(cpt) (H O) ]·3NO ·4DMAc·CH OH·5H O (FJU-14-NO ). A
4 4 2 4 3 3 2 3
mixture of Hcpt (19.5 mg, 0.1 mmol) and Cu(NO ) ·3H O (25.3 mg,
3
2
2
0
.1 mmol) was dissolved in 3 mL of DMAc/CH OH (2:1, v/v) in a
3
screw-capped vial. After addition of 10 μL of HCl (3 M, aq), the vial
was heated at 80 °C for 1 day under autogenous pressure. Green
polyhedral crystals were obtained after filtration, washed with CH OH,
3
and dried in air. Yield 48% (based on Hcpt). Anal. Calcd for
Cu ClC H N O (1770.98): C, 35.91; H, 4.630; N, 15.02. Found:
4
53 82 19 31
−1
C, 36.83, H, 4.657; N, 15.05. IR (KBr, cm ): 3430 (s), 3095 (w),
919 (w) 1621 (s), 1552 (m), 1386 (s), 1253(w), 1010 (s), 785 (w)
2
−
1
cm .
(Cu Cl)(cpt) (H O) ]·3ClO ·4DMAc·CH OH·5H O (FJU-14-ClO ).
anions with the different configuration and electronegativity
within the channels may bring the MOFs with controllable
structure flexibility and robustness due to their distinct
interactions between the host and the anions. In comparison
with the methods mentioned above to sustain the nonrobust
[
4
4
2
4
4
3
2
4
The synthetic procedure was similar to that of FJU-14-NO except
3
that Cu(NO ) ·3H O was replaced by Cu(ClO ) ·6H O. Green
3
2
2
4
2
2
polyhedral crystals were obtained after filtration, washed with CH OH,
3
and dried in air. Yield 48% (based on Hcpt). Anal. Calcd for
Cu Cl C H N O (1883.32): C, 33.77; H, 4.354; N, 11.89. Found:
1
9,20
21
MOFs,
as the sizes for these anions are close, the anion
4
4 53 82 16 34
B
DOI: 10.1021/acs.inorgchem.5b02316
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
−
1
C, 34.36; H, 4.541; N, 12.33. IR (KBr, cm ): 3442 (s), 3106 (w),
t ⎛
⎞
CiV
2.4 × m
⎜1 − F ⎟dt
−1
1
629 (s), 1552 (m), 1382 (s), 1253(w), 1110 (s), 785 (w) cm .
(Cu Cl)(cpt) (H O) ]·3BF ·4DMAc·CH OH·5H O (FJU-14-BF ). The
synthetic procedure was similar to that of FJU-14-NO except that
Cu(NO ) ·3H O was replaced by Cu(BF ) ·6H O. Green polyhedral
crystals were obtained after filtration, washed with CH OH, and dried
in air. Yield 42% (based on Hcpt). Anal. Calcd for
Cu ClB F C H N O (1845.38): C, 34.46; H, 4.443; N, 12.14.
Found: C, 34.34; H, 4.268; N, 11.84. IR (KBr, cm ): 3450(s), 2930
m), 1623 (s), 1550(m), 1415(s), 1257(w), 1080(s), 785 (w) cm .
Gas Adsorption. After the bulk of the solvent was decanted, the
freshly prepared sample of FJU-14 (∼0.15 g) was soaked in methanol
for 1 h, and then the solvent was decanted. Following the procedure of
methanol soaking and decanting 10 times, the solvent-exchanged
samples were activated by vacuum at room temperature for 24 h until a
pressure of 5 μm of Hg. N and CO adsorption isotherms were
measured on Micromeritics ASAP 2020 HD88 surface area analyzer
for the guest-free FJU-14-a. The sorption measurement was
maintained at 77 K with liquid nitrogen and at 273 K with an ice−
water bath (slush). A water bath was used for adsorption isotherms at
qi = 2
×
∫
0 ⎝
F ⎠
0
(4)
[
4
4
2
4
4
3
2
4
−1
3
where q is the equilibrium adsorption capacity of gas i (mmol g ), C
i
i
3
3
2
2
4
2
2
is the feed gas concentration, V is the volumetric feed flow rate (cm
min ), t is the adsorption time (min), F and F are the inlet and outlet
gas molar flow rates, respectively, and m is the mass of the adsorbent
−1
3
0
4
3 12 53 82 16 22
(g).
−1
Single-Crystal X-ray Diffraction (SCXRD) Studies. Data
collection and structural analysis of crystal FJU-14 were collected on
an Agilent Technologies SuperNova single-crystal diffractometer
equipped with graphite monochromatic Cu Kα radiation (λ =
−1
(
1
.54184 Å). The crystal was kept at 150 or 100 K during data
25
collection. Using Olex2, the structure was solved with the Superflip
structure solution program using charge flipping and refined with the
ShelXL refinement package using least-squares minimization. The cpt
ligand is disordered over two positions (occupancy 0.5:0.5); this is due
to the fact that triazolate and the carboxylate part of the ligand show
similar coordination models and therefore can substitute each other at
the given site. Additionally, the disorder of the triazolate group leads to
the carbon and nitrogen atoms sharing the same crystallographic
positions with partial occupancies in these compounds. All non-
hydrogen atoms were refined with anisotropic displacement
parameters. The hydrogen atoms on the ligands were placed in
idealized positions and refined using a riding model. Hydrogen atoms
for the terminal coordinate water in these compounds were not able to
2
2
2
96 K.
Virial Equation Analysis. The virial equation can be written as
follows
2
3
2
ln(n/p) = A + A n + A n + ···
(1)
0
1
2
−1
where n is the amount adsorbed (mol g ) at pressure p (Pa). At a low
surface coverage, the A and higher terms can be neglected and the
26
locate as they were found to be disordered. We employed PLATON
2
2
7
and SQUEEZE to calculate the diffraction contribution of the
solvent molecules and thereby produce a set of solvent-free diffraction
intensities.
equation becomes
ln(n/p) = A + A n
(2)
0
1
SCXRD for CO -Loaded FJU-14-BF -a (FJU-14-BF -a·
2
4
4
A linear graph of ln(n/p) versus n was obtained at low surface
coverage, and this is consistent with neglecting the higher terms in eq
0
.93CO ). The solvent-exchanged single crystal of FJU-14-BF was
2
4
fixed inside a glass capillary and pretreated similarly as for the gas
adsorption measurements to get the guest-free FJU-14-BF -a. The
capillaries were cooled to cryogenic temperature (dry ice−acetone),
backfilled with CO (1 atm), and finally sealed by a torch. After that,
2
. A is related to the adsorbate−adsorbent interactions, whereas A
0
1
4
describes the adsorbate−adsorbate interactions. The virial parameters
are given in Table S3, Supporting Information.
2
Enthalpies of Adsorption. Zero Surface Coverage. The isosteric
enthalpies of adsorption at zero surface coverage (Qst,n=0) are a
fundamental measure of adsorbate−adsorbent interactions, and these
the CO -loaded single crystal was immediately removed to a dry liquid
2
nitrogen atmosphere (100 K) for structural analysis. The detailed
crystallographic data and structure refinement parameters for these
compounds are summarized in Table S1, Supporting Information
values were calculated from the A values obtained by extrapolation of
0
the virial graph to zero surface coverage.
(
CCDC 1426056−1426060).
van’t Hoff Isochore. The isosteric enthalpies of adsorption as a
function of surface coverage were calculated from the isotherms using
the van’t Hoff isochore, which is given by the equation
RESULTS AND DISCUSSION
Crystal Structures. Green polyhedral crystals of FJU-14
were solvothermally synthesized by reaction of various copper
■
ΔH
RT
ΔS
R
ln(p) = −
+
(3)
salts and Hcpt in DMAc−CH OH solution for 1 day. Single-
3
crystal X-ray study reveals that FJU-14 crystallizes in the
tetragonal space group I4/mmm. As shown in Figure 1a, there is
A graph of ln(p) versus 1/T at a constant amount adsorbed (n)
allows the isosteric enthalpy and entropy of adsorption to be
determined. The pressure values for a specific amount adsorbed
were calculated from the adsorption isotherms by (1) assuming a
linear relationship between the adjacent isotherm points starting from
the first isotherm point and (2) using the virial equation at low surface
one crystallographically independent Cu2+ ion, its octahedral
−
geometry completed by four independent cpt ligands, a μ -Cl
4
−
anion, and one terminal water molecule. The Cl anion
2+
7+
connects with four Cu ions to form [Cu Cl] square plane
4
coverage. The agreement between the two methods for FJU-14-BF -a
4
SBU. There are two types of polyhedral nanocages in FJU-14,
that is, one octahedron (Cage A) and one tetrahedron (Cage
B) (Figure 1b). Cage A with its center at the Wyckoff position
are shown in Figure S12.
Column Breakthrough Experiments. The mixed-gas break-
through separation experiment was conducted at 296 K using a lab-
scale fix-bed reactor (Scheme S2). In a typical experiment, ∼0.25 g of
7+
2
b is constructed by six [Cu Cl] SBUs as vertices and eight
4
FJU-14-BF powder was packed into a stainless steel column (the steel
cpt ligands as the edges. As its equator has no cpt occupied,
each triangle face of the octahedron is composed of two cpt
4
column was 18 cm in length with a 4 mm inner (6.4 mm outer)
diameter) with silica wool filling the void space. The sorbent was
activated in situ in the column with a vacuum pump at 296 K for 24 h.
A helium flow (5 mL min ) was used after the activation process to
purge the adsorbent. The flow of He was then turned off, while a gas
7
+
edges and three [Cu Cl] vertices. In addition, the dimension
4
of this cage is estimated to be around 14 Å. Cage B with its
center at the Wyckoff position 4d consists of four [Cu Cl]
−1
7+
4
SBUs and four cpt ligands, with a dimension of 5.8 Å. On the
whole, Cage A is linked by eight Cage B through sharing eight
triangle faces (Figure S1b). Similarly, Cage B is linked by four
Cage A by sharing four triangle faces. The connection of two
types of polyhedral nanocages extends to form a three-
dimensional (3D) cationic framework (Figure 1c). For the
−1
mixture of CO /N (15:85, V/V) at 5 mL min was allowed to flow
2
2
into the column. The effluent from the column was monitored using a
Hiden mass spectrometer (HPR 20). The complete breakthrough of
CO2 and other species was indicated by the downstream gas
composition reaching that of the feed gas. On the basis of the mass
2
4
balance, the gas adsorption capacities can be determined as follows
C
DOI: 10.1021/acs.inorgchem.5b02316
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Inorganic Chemistry
Article
−
−
−
Figure 2. Counteranions (NO , ClO , BF ) locate in the
3
4
4
tetrahedral cage and show the MHBIs between the counteranions
Figure 1. (a) Tetranuclear [Cu Cl]7 square face SBU in FJU-14. (b)
+
4
and cationic frameworks in (a) FJU-14-NO , (b) FJU-14-ClO , (c)
3
4
Two types of polyhedral nanocages observed in FJU-14: one
octahedral cage (Cage-A, red) and one tetrahedral cage (Cage-B,
blue). (c) Face-shared packing of octahedral and tetrahedral cages in
FJU-14. (d) Schematic representation of the 8-connected bcu
topology in FJU-14. Color code: Cu, sky blue; Cl, green; O, red; C,
gray; N, blue (hydrogen atoms are omitted from the structure for
clarity).
FJU-14-BF , and (d) the activated FJU-14-BF -a. The counteranion···
4
4
H O and counteranion···phenyl ring interactions are indicated as red
2
and blue dashed lines. Sky blue, green, blue, red, gray, yellow, and
bright green spheres represent Cu, Cl, N, O, C, B, and F atoms,
respectively.
from the single-crystal data, indicative of its high purity and
homogeneity (Figures 3, S6, and S7). The variable-temperature
PXRD (VT-PXRD) indicates that the framework structure of
FJU-14-NO and FJU-14-ClO can be retained at temperatures
7
+
sake of clarity, if we simplify [Cu Cl] vertices as eight-
4
connected nodes, FJU-14 adopts the bcu network with the
2
4
4
28
topological point symbol of 4 .6 (Figure 1d). After
elimination of guest solvent molecules, the total accessible
volumes in FJU-14-NO , FJU-14-ClO , and FJU-14-BF are
3.1%, 48.7%, and 46.0%, respectively, by using the PLATON
software. The anion substitution does not obviously decrease
the pore volume of FJU-14.
3
4
up to 220 °C without any phase change, while FJU-14-BF is
4
stable even above 250 °C. The balanced MHBIs between the
host skeleton and the BF4− counteranions bring FJU-14-BF4
with higher thermally stable temperature. Furthermore, the
robustness for desolvated phase of FJU-14 was observed by
PXRD after the as-synthesized samples were exchanged with
3
4
4
4
26
It is worth noting that each tetrahedral cage in FJU-14 is
occupied by the counteranions (NO , ClO , or BF ) in pair
−
−
−
CH OH several times and activated at room temperature (RT)
3
4
4
3
to balance the frameworks’ charge. The counteranions provide
its own donors D (O or F) to produce multiple D···H−A
hydrogen-bonding interactions with acceptors A (phenyl ring
or coordinated water molecule). The difference in configuration
and electronegativity for these counteranions in the series of
MOFs leads to the remarkably distinct MHBIs between the
host and the anions (Figure 2a−c). The location for the minor
planar NO3− ion is much closer to the terminal coordination
for 24 h under high vacuum. The activated FJU-14-NO -a
3
almost loses its crystallinity, while FJU-14-ClO -a still keeps
4
the crystallinity but with several peaks shifting and changing. It
indicates that the two MOFs are dynamic and partly shrink or
30
even collapse after the activation. On the contrary, the PXRD
pattern for the activated FJU-14-BF -a is in good agreement
4
with the as-synthesized one. Besides the improved thermally
stability, the balanced MHBIs also endow FJU-14-BF with
4
−
water (d[O(NO )···Ow(H O)] = 2.742 Å) than to a phenyl
enhanced robustness, in comparison with the other two MOFs.
3
2
−
ring (d[O(NO )···C(phenyl)] = 3.459 Å). In contrast, the
tetrahedral anion, especially BF4 containing more electro-
Gas Adsorption Studies. The improved robustness and
3
−
stability by the balanced MHBIs in FJU-14-BF encourage us
4
negative F atoms, can provide balanced MHBIs with the phenyl
to further examine the effect of counteranions on the pore
−
ring (d[F (BF )···C(phenyl)] = 3.133 Å) and with the
structures and CO adsorption for the three MOFs. Their N
4
2
2
−
coordinated water molecule (d[F(BF )···Ow(H O)] = 3.466
sorption isotherms at 77 K are shown in Figure 4a. FJU-14-
NO -a takes much less N gas with no pore volume. FJU-14-
4
2
2
9
Å). The balanced MHBIs between the host and the
counteranions may bring better performance to FJU-14-BF4.
Robustness and Thermal Stability. The robustness and
thermal stability for the three isostructural MOFs were
measured by using the powder X-ray diffraction (PXRD) and
thermogravimetric analysis (TGA) technologies. From TGA
3
2
ClO -a exhibits a typical type-IV behavior and the pore
4
condensation with pronounced adsorption−desorption hyste-
resis, while FJU-14-BF -a shows reversible type-I isotherm and
4
appears to have small hysteretic sorption behavior because of
3
1
dynamic features and the cage effect. FJU-14-BF -a has the
4
2
−1
curves, the as-synthesized samples FJU-14-NO and FJU-14-
BET/Langmuir surface area of 324/447 m g , 5-fold the value
3
ClO show a similar continuous weight loss upon heating, while
(62/90) for FJU-14-ClO -a, although their pore volumes are
4
4
3
−1
the as-synthesized and activated FJU-14-BF shows a plateau
closed (0.172 vs 0.125 cm g ). By the nonlocal density
4
32
up to 270 °C following with a sharp weight loss, indicating the
collapse of the frameworks (Figure S5). The PXRD patterns of
as-synthesized FJU-14 are coincident with the simulated ones
functional theory (NLDFT) method, FJU-14-BF -a shows a
4
bimodal pore-size distribution centering at 5.8 and 8.8 Å
(Figure S8). The significantly different pore structures of the
D
DOI: 10.1021/acs.inorgchem.5b02316
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 3. (a) Room-temperature conditions and (b) variable-temperature powder X-ray diffraction patterns for FJU-14-BF4.
Figure 4. (a) N sorption isotherms of FJU-14-NO -a (black), FJU-14-ClO -a (blue), and FJU-14-BF -a (red) at 77 K. (b) Comparison of CO
2
2
3
4
4
sorption isotherms of FJU-14-a at 296 K. (c) Column breakthrough experiment for a CO /N = 15/85 gas mixture carried out on FJU-14-BF -a at
2
2
4
−
1
2
96 K and 1 bar. The flow rate of CO /N gas mixture is 5 mL min . The comparison of CO uptake (d), adsorption enthalpy (e), and loaded CO
2
2
2
2
density (f) on FJU-14-BF -a with representative MOFs. Blue (green) bars represent representative MOFs with the CO volumetric uptake higher
4
2
(
lower) than FJU-14-BF -a.
4
−
1
34
FJU-14 are attributed to the various robustness nature resulted
for large CO uptake: Co Cl (bbta)(OH) (110 kJ mol ),
2 2 2
−
1
41
from the MHBIs between the hosts and the guests.
Mmen−CuBTTri (96 kJ mol ), Mg−MOF-74 (47 kJ
mol ), Bio-MOF-11 (45 kJ mol ), MPM-1-TIFSIX(44.4
kJ mol ), and Mg (dobpdc) (44 kJ mol ) (Figure 4e).
The CO density in FJU-14-BF -a at 1 atm and 296 K is
3
−1 42
−1 39
At 296 K and 1 bar, FJU-14-BF -a can take CO of 95.8 cm
4
2
−
3
−1 38
−1 40
cm (Figure 4b), three-fold more that for FJU-14-ClO -a (30
4
2
3
−3
cm cm ). The virial graphs for CO adsorption on FJU-14-
2
2
4
BF -a at 273 and 296 K are shown in Figure S11. The
estimated according to the amount of gas adsorbed and the
4
3
−1
comparison of the results from the two methods, the linear
extrapolation and the virial equation, shows very good
agreement (Figure S12). The enthalpy at zero coverage
pore volume (0.172 cm g ) of the framework from N
2
−3
adsorption at 77 K. It is 0.955 g cm , close to the liquid
−3
43
CO density of 1.032 g cm , the highest ever reported on the
2
−1
Qst,n=0 for CO adsorption on FJU-14-BF -a is 18.8 kJ mol ,
MOFs for CO capture at the same condition (Figure 4f). The
2
4
2
slightly larger than the CO vaporization enthalpy (16.5 kJ
highest CO density means FJU-14-BF -a can trap CO in the
most efficient mode into its pore to reach saturation even at
2
2
4
2
−1
33
mol ). The amount of absorbed CO in FJU-14-BF -a at
2
4
2
96 K is lower than some famous MOFs, such as Co Cl (bbta)
296 K and 1 atm, featuring FJU-14-BF -a as the very promising
2
2
4
3
−3 34
3
−3 35
(OH) (203 cm cm ), MgMOF-74 (162 cm cm ),
material for the highly selective separation of CO from the
2
3
−3 36
3
−3 37
UTSA-16 (160 cm cm ), SIFSIX-2-Cu-i (151 cm cm ),
and is comparable with the values on MPM-1-TIFSIX (115.7
cm cm ), Bio-MOF-11 (113 cm cm ), Mg (dobpdc)
light gases. The CO uptake on FJU-14-BF -a is about 14 times
2
4
3
−3
the N uptake (6.9 cm cm ) (Figure S9). To evaluate the
2
3
−3 38
3
−3 39
performance of FJU-14-BF -a in the actual adsorption-based
2
4
3
−3 40
3
−3 41
(
102 cm cm ), and Mmen−CuBTTri (83 cm cm )
separation and purification processes, dynamic column break-
(Figure 4d). However, the adsorption enthalpy value of FJU-
through experiments were performed in which a CO /N
2
2
1
4-BF -a is significantly lower than some representative MOFs
(15:85, v/v) mixture was flowed over a packed bed of FJU-
4
E
DOI: 10.1021/acs.inorgchem.5b02316
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
4-BF -a solid with a total flow of 5 mL min at 296 K. As
Article
−1
interactions between CO molecules and the BF4− anions as
1
4
2
shown in Figure 4c, the separation of a CO /N (15:85, v/v)
well as the host skeleton.
2
2
mixture through the column packed bed of FJU-14-BF -a solid
4
can be efficiently achieved. The dynamic CO adsorption
CONCLUSIONS
2
■
capacity in FJU-14-BF -a at room temperature is 0.99 mmol
4
In summary, we synthesized three isostructural microporous
cationic metal−organic frameworks (FJU-14) and first
demonstrated that the robustness, stability, and gas separation
capacity of the MOFs can be tuned by alerting the weak
interactions between the host and the counteranions. Among
the three MOFs, FJU-14-BF containing a BF4 anion in its
−
1
g , comparable with the values on MOF-890 (1.38 mmol
g ) and IRMOF-74-III-CH NH (0.8 mmol g ), and
higher than HKUST-1 (0.45 mmol g ).
−1
44
−1 45
2
2
−1
46
In order to elucidate the mechanism for the high-density
CO adsorption on FJU-14-BF -a, we employed the single-
−
2
4
4
crystal X-ray diffraction technique to solve the high-quality
tetrahedral cages can take CO with a high volume uptake (95.8
2
crystal structures for both the guest-free and the CO -loaded
3
−3
−1
2
cm cm ) but low enthalpy (18.8 kJ mol ) at ambient
FJU-14-BF -a samples at low temperature. The single-crystal
−3
4
conditions. The trapped CO density of 0.955 g cm is the
2
structure for the guest free sample (Figure 2d) reveals that the
highest value among the reported MOFs. Dynamic fixed-bed
breakthrough experiments indicate that the separation of CO2/
N mixture gases through a column packed with FJU-14-BF -a
solid can be efficiently achieved. The balanced MHBIs between
the BF4− counteranion and the cationic skeleton play a crucial
role in the stability of FJU-14-BF -a. The high-density CO
capture is mainly contributed from the multiple-point
interactions between the adsorbate molecules and the frame-
work as well as its counteranions. We do believe that our
findings will encourage further work in the control of multiple
hydrogen-bonding interactions for MOFs, especially the
nonrobust MOFs, to improve their stability and gas separation
capacity through the counterion substitution.
bond length of Cu−Ow changes from 2.332 to 2.508 Å;
−
meanwhile, the distance d[F(BF )···Ow(H O)] is shortened
4
2
2
4
−
to 3.219 Å, very close to that of d[F(BF )···C(phenyl)] (3.258
Å). After the activation, the MHBIs between the host and the
counteranion BF4 become more balanced, contrasting to the
4
−
4
2
origin sample. The more balanced MHBIs keep the framework
more robust and stable even after the activation. Single-crystal
X-ray diffraction analysis of the gas-loaded MOFs has been
demonstrated as a straightforward and convincing tool to
47
elucidate the gas adsorption mechanism, in comparison with
4
8
49
other tools including theoretical calculations, spectroscopy,
50
and synchrotron powder X-ray diffraction (SPXRD). The
single-crystal structure for the CO -loaded sample FJU-14-BF -
2
4
a·0.93CO2 reveals that it has two crystallographically
ASSOCIATED CONTENT
Supporting Information
■
independent CO molecules (Figure 5): one in an octahedral
2
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.5b02316.
Details of experimental methods and procedures, addi-
tional structural figures, FT-IR spectra, TGA curves,
PXRD patterns, and gas absorption isotherms (PDF)
X-ray crystallographic data (CIF)
AUTHOR INFORMATION
Corresponding Authors
E-mail: lhwang@fjnu.edu.cn.
E-mail: scxiang@fjnu.edu.cn.
Notes
■
Figure 5. Local environment of FJU-14-BF -a·0.93CO showing the
4
2
multipoint supramolecular interactions (green and orange dashed
*
*
lines) between the CO molecules (I and II) and the framework as
2
well as its counteranions (a and b).
The authors declare no competing financial interest.
cage (denoted as CO −I) and one-half of another in one
ACKNOWLEDGMENTS
2
■
tetrahedral cage (denoted as CO −II). The CO occupancies at
2
2
This work was financially supported by the National Natural
Science Foundation of China (21207018, 21273033, 21203024,
and 21573042) and the Fujian Science and Technology
Department (2014J06003 and 2014H6007). S.X. gratefully
acknowledges the support of the Recruitment Program of
Global Young Experts, Program for New Century Excellent
Talents in University (NCET-10-0108), and the Award
the two sites I and II were determined by free structural
refinement to be 0.29256 and 0.1744, respectively. The CO −I
2
molecule locates near to four 1,2,4-triazolyl rings, with its
electronegative O atom interacting with the electropositive C
atom of the1,2,4-triazolyl rings [O(δ−)···C(δ+) = 3.031 Å],
which is normally considered as the binding domains of CO in
2
47
MOFs (Tables S5). The CO −II molecule is surrounded with
two coordinated water and two BF4 anions from two edge-
2
“
MinJiang Scholar Program” in Fujian Province.
−
sharing tetrahedral cages. This configuration keeps both oxygen
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DOI: 10.1021/acs.inorgchem.5b02316
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DOI: 10.1021/acs.inorgchem.5b02316
Inorg. Chem. XXXX, XXX, XXX−XXX