Syntheses, Structures and Sorption Properties of Three Isoreticular Trinuclear Indium-Based Amide-Functionalized Metal–Organic Frameworks

Article abstract of DOI:10.1002/asia.201900536

Amide-functionalized metal–organic frameworks (AFMOFs) as a subclass of MOF materials have received great interest recently because of their intriguing structures and diverse potential applications. In this work, solvothermal reactions between indium nitrate and two mixed-linkers afforded two new isoreticular 8-connected trinuclear indium-based AFMOFs of [(In₃O)(OH)(L2)₂(IN)₂]?(solv)_x (2-In) and [(In₃O)(OH)(L2)₂(AIN)₂]?(solv)_x (NH₂-2-In) (H₂L2=4,4′-(carbonylimino)dibenzoic acid and HIN=isonicotinic acid or HAIN=3-aminoisonicotinic acid), respectively. Moreover, by means of reticular chemistry, an extended network of [(In₃O)(OH)(L3)₂(PB)₂]?(solv)_x (3-In) (H₂L3=4,4′-(terephthaloylbis(azanediyl))dibenzoic acid, HPB=4-(4-pyridyl)benzoic acid) was also successfully realized after prolongation of the former dicarboxylate linker and HIN, resulting in a truly 8-connected isoreticular AFMOF platform. These frameworks were structurally determined by single-crystal X-ray diffraction (SCXRD). Sorption studies further demonstrate that 2-In and NH₂-2-In exhibit not only high surface areas and pore volumes but also relatively high carbon capture capabilities (the CO₂ uptakes reach 60.0 and 75.5 cm³ g^?1 at 298 K and 760 torr, respectively) due to the presences of amide and/or amine functional groups. The selectivity of CO₂/N₂ and CO₂/CH₄ calculated by IAST are 10.18 and 12.43, 4.20 and 4.23 for 2-In and NH₂-2-In, respectively, which were additionally evaluated by mixed-gases dynamic breakthrough experiments. In addition, high-pressure gas sorption measurements show that both materials could take up moderate amounts of natural gas.

Full text of DOI:10.1002/asia.201900536

DOI: 10.1002/asia.201900536
Full Paper
Syntheses, Structures and Sorption Properties of Three
Isoreticular Trinuclear Indium-Based Amide-Functionalized Metal–
Organic Frameworks
Zong-Hui Zhang,[a] Qian Wang,[a] Dong-Xu Xue,*[a] and Junfeng Bai*[a, b]
Abstract: Amide-functionalized metal–organic frameworks
(AFMOFs) as a subclass of MOF materials have received
great interest recently because of their intriguing structures
and diverse potential applications. In this work, solvothermal
reactions between indium nitrate and two mixed-linkers af-
forded two new isoreticular 8-connected trinuclear indium-
based AFMOFs of [(In3O)(OH)(L2)2(IN)2]·(solv)x (2-In) and
[(In3O)(OH)(L2)2(AIN)2]·(solv)x (NH2-2-In) (H2L2=4,4’-(carbony-
limino)dibenzoic acid and HIN=isonicotinic acid or HAIN=
3-aminoisonicotinic acid), respectively. Moreover, by means
of reticular chemistry, an extended network of
[(In3O)(OH)(L3)2(PB)2]·(solv)x (3-In) (H2L3=4,4’-(terephthaloyl-
bis(azanediyl))dibenzoic acid, HPB=4-(4-pyridyl)benzoic
acid) was also successfully realized after prolongation of the
former dicarboxylate linker and HIN, resulting in a truly 8-
connected isoreticular AFMOF platform. These frameworks
were structurally determined by single-crystal X-ray diffrac-
tion (SCXRD). Sorption studies further demonstrate that 2-In
and NH2-2-In exhibit not only high surface areas and pore
volumes but also relatively high carbon capture capabilities
(the CO2 uptakes reach 60.0 and 75.5 cm3 gꢀ1 at 298 K and
760 torr, respectively) due to the presences of amide and/or
amine functional groups. The selectivity of CO2/N2 and CO2/
CH4 calculated by IAST are 10.18 and 12.43, 4.20 and 4.23 for
2-In and NH2-2-In, respectively, which were additionally eval-
uated by mixed-gases dynamic breakthrough experiments.
In addition, high-pressure gas sorption measurements show
that both materials could take up moderate amounts of nat-
ural gas.
Introduction
sic structural attributes (built-in amide-functional groups with-
out sacrificing porosities and properties) and prominent
achievements toward carbon capture, methane storage and
safe handling of acetylene et al.[3]
Functionalization of metal-organic frameworks (MOFs) is of
para importance in MOF chemistry to realize/enhance relevant
targeting properties. Generally, there are two approaches to
generate functional MOFs, including direct synthesis via utiliza-
tion of pre-functionalized organic linkers[1] or indirect synthesis,
i.e., the so-called post-synthetic modification.[2] However, newly
formed MOF materials by means of above strategies always ex-
hibit improved performances accompanied by much lower sur-
face areas and pore volume. The emerging amide-functional-
ized MOFs (AFMOFs) as a subclass of MOF materials have at-
tracted more and more attentions recently due to their intrin-
The exploration and development of AFMOFs have been ini-
tiated in our research group since a decade ago. A fruitful
AFMOF library has been designed and constructed ranging
from flexible to robust ones based on judicious organic linkers
and mainly transitional metal ions.[4] To extend the scope of
AFMOF inventory, it is necessary to choose non-transitional
metal ions to target new type ones for specific applications.
Indium metal ion as a p-block metal element is an interesting
central metal to construct MOF materials due to its relatively
well-defined molecular building blocks (MBBs) encompassing
linear neutral [In(m-OH)(O2C-)2],[5] charged trimeric [In3(m3-
O)(O2C-)6][6] and tetrahedral [In(O2C-)4]/[InN4(O2C-)4],[7] respec-
tively.
Additionally, multivariate MOFs (MTV-MOFs)[8] with multiple
functional groups pioneered by Yaghi’s group have aroused
extensive investigations recently to access materials with in-
creased complexity and advanced functions. For instance, a
series of MTV-MOFs have been elaborately prepared and detail-
edly elucidated. A member of MTV-MOF-5-EHI exhibits up to
400% better selectivity for carbon dioxide over carbon monox-
ide compared with its best same-link counterparts. In contrast
to complex characterizations for mentioned MTV-MOFs, mixed-
linker strategies may provide another avenue to obtain multi-
functional crystalline framework materials along with ease
[a] Dr. Z.-H. Zhang, Dr. Q. Wang, Prof. Dr. D.-X. Xue, Prof. Dr. J. Bai
Key Laboratory of Applied Surface and Colloid Chemistry
Ministry of Education
School of Chemistry & Chemical Engineering
Normal University
Shaanxi, Xi’an 710062 (China)
E-mail: xuedx@snnu.edu.cn
bjunfeng@nju.edu.cn
[b] Prof. Dr. J. Bai
State Key Laboratory of Coordination Chemistry
Nanjing University
Nanjing 210093 (P. R. China)
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under:
https://doi.org/10.1002/asia.201900536.
This manuscript is part of a special issue on Metal–Organic Frameworks. A
link to the Table of Contents of the special issue will appear here when the
complete issue is published.
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Scheme 1. Construction Scheme of the uninodal, 8-connected network of 2-In by mixed linear organic ligands and the m3-O-centered trinuclear Indium clus-
ter.
preparation and unambiguous structural information to corre-
late the relationship between structure and property.[9]
Bearing above mentioned in mind, herein, we adopted
mixed-linker strategy and indium nitrate as metal source, both
isoreticular 8-connected trinuclear indium-based AFMOFs of
[(In3O)(OH)(L2)2(IN)2]·(solv)x (2-In) and [(In3O)(OH)(L2)2(AIN)2]·
(solv)x (NH2-2-In) (H2L2=4,4’-(carbonylimino)dibenzoic acid
and HIN=isonicotinic acid or HAIN=3-aminoisonico-
and pyridyl monocarboxylate. Indeed, solvothermal reactions
between In(NO3)3·4.5H2O and amide-functionalized dicarboxy-
late ligand L2 as well as pyridyl ligands of HIN or HAIN, both
new AFMOFs of 2-In and NH2-2-In were successfully obtained.
SCXRD analysis reveals that both 2-In and NH2-2-In are iso-
reticular 8-connected trinuclear indium-based AFMOFs. The
crystallographic data and refinement parameters are listed in
tinic acid) were solvethermally isolated (Scheme 1).
Table 1. Crystallographic Data and Structure Refinement Summary for 2-In, NH2-2-In
and 3-In.
Moreover, extended network of [(In3O)(OH)(L3)2(PB)2]·
(solv)x (3-In) (H2L3=4, 4’-(terephthaloylbis(azane-
diyl))dibenzoic acid, HPB=4-(4-pyridyl)benzoic acid)
was also successfully generated via reticular chemis-
try[10] after prolongation of previous dicarboxylate
linker and HIN, resulting in a truly new 8-connected
AFMOF platform. Sorption studies indicate that 2-In
and NH2-2-In exhibit not only high surface areas and
pore volume, but also relatively high carbon capture
capabilities due to the presences of amide and/or
amine functional groups. In addition, both materials
could uptake moderate amounts of natural gas.
MOFs
2-In
NH2-2-In
3-In
CCDC number 1910435
1910436
C42 H28 In3 N6 O16
1217.16
153.0
1910437
C240 In12 N24 O72
5748.61
153.0
Formula
FW
C42 H26 In3 N4 O16
1187.13
153.02
T (K)
Space group I-43d
I-43d
I-43d
a (ꢁ)
38.127(6)
55426(24)
24
0.854
6.250
38.0479(6)
55080(3)
24
0.881
6.305
51.057(2)
133099(16)
6
0.430
2.649
V(ꢁ3)
Z
Dc (gcmꢀ3
m (mmꢀ1
F (000)
)
)
13944
14328
16699
Crystal size
(mm3)
0.1ꢂ0.1ꢂ0.1
0.1ꢂ0.1ꢂ0.1
0.08ꢂ0.08ꢂ0.08
q range for
data collec-
tion (deg.)
3.666 to 50.346
3.285 to 54.288
2.737 to 51.143
Results and Discussion
Synthesis and crystal structures
Limiting indi- ꢀ37< =h< =22,
ꢀ40< =h< =14,
ꢀ17< =k< =37,
ꢀ25< =l< =33
32306 [Rint =0.0406]
ꢀ45< =h< =37,
ꢀ46< =k< =44,
ꢀ45< =l< =51
61628 [Rint =0.0299]
The MBB of [M3(m3-O)(O2C-)6 L3] (M=Cr, Fe, In, et al.)
is a popular trinuclear metal cluster serving as trigo-
nal prismatic secondary building unit (SBU) for delib-
erately assembling well-known 6-connected MOFs,
i.e., MIL-101,[11] MIL-88[12] and soc-MOFs series[13] via
substitution of the available carboxylate groups.
Meanwhile, the terminalL sites of the cluster can be
also ligated by bridging linear monodentate ligands
or triangular monodentate ligands to furnish higher-
connected nodes, for instance, the 9-connected
MCF-19[14] and CPM-83,[15] respectively. In view of
this, we curiously speculate that lower connected
new frameworks are possibly to be isolated while re-
acting appropriate amount/ration of dicarboxylate
ces
ꢀ33< =k< =32,
ꢀ25< =l< =38
Reflection col- 19480[Rint =0.0476]
lected
Completeness 98.9%
98.9%
5477/ 7/ 200
99.5%
11671/ 0/ 291
Data/re-
straints/pa-
rameters
GOF
4744/ 2/ 161
1.111
1.131
0.985
Final R indices R1 =0.0712,
(I>2sigma(I)) wR2 =0.2036
R1 =0.0565,
wR2 =0.1595
R1 =0.0579,
wR2 =0.1615
1.346 and
ꢀ0.706 eꢁ-3
R1 =0.0977,
wR2 =0.2834
R1 =0.0981,
wR2 =0.2837
0.83 and
R indices (all
data)
Largest diff.
peak and hole ꢀ1.574 eꢁ-3
R1 =0.0729,
wR2 =0.2072
1.308 and
ꢀ0.88 eꢁ-3
[a] R1 =SkFo jꢀjFc k/jFo j ; wR2 =[Sw(SFo ꢀFc2)2/Sw(Fo )2]1/2
.
2
2
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Table 1. For the sake of brevity, only the structure of 2-In is de-
picted. 2-In crystallizes in cubic space group I-43d and there
are two crystallographically independent, six-coordinated
indium ions in the asymmetric unit (Figures S1). Both In3+ ions
are surrouned by four carboxylate oxygen atoms, one m3-O
atom and pyridyl nitrogen or hydyoxyl occupying the sixth
site, respectively, resulting in the formation of [In3(m3-O)(O2C-
)6(OH)N2] MBBs (Figure 1a), which is also present in the struc-
tures reported by Xu and co-workers.[16] Each trinuclear indium
MBB is bridged through four depronated L22ꢀ and four depro-
nated INꢀ linkers to produce a 3D-periodic netwrok (Fig-
ure 1b). Topologically, the [In3(m3-O)(O2C-)6(OH)N2] cluster can
be simplified as a node and organic linkers as spacers, subse-
quently an eight-connected uninodal net with a Schꢃlfli
symbol of (32·417·56·63) is generated (Figure 1b and Figure S5).
Due to the different lengths of the dicarboxylat ligand and the
nitrogen-based ligand in 2-In, four types of pores with irregu-
lar shape and distinct size are formed (Figure 1c and S4). Fur-
thermore, as the presence of the unconnected third apical po-
sition for the trinuclear indium MBB, 2-In provides higher po-
rosity toward guest uptake capabilities.
It must be mentioned that the extended 3-In was fortunate-
ly achieved after prolongation the dicarboxylate and pyridyl
monocarboxylate in 2-In with bis-amide functionalized organic
ligand L3 and four nitrogen-based organic ligand PB, respec-
tively (Figures 1 and S6). Topology analysis shows that 3-In is
the exactly same topology with 2-In and NH2-2-In, exemplify-
ing a new truly eight-connected isoreticular AFMOF platform
via reticular chemistry.
Sorption and carbon capture properties
To address sorption properties, the phase purity of prepared
material must be primarily verified. The phase purity of the
bulk crystalline materials for 2-In and NH2-2-In was independ-
ently confirmed by similarities between the simulated and as-
synthesized powder X-ray diffraction (PXRD) patterns (Fig-
ure S7). Moreover, the corresponding solvent accessible free
volumes for 2-In and NH2-2-In were estimated to be 71.6%
and 66.9%, respectively, by summing voxels more than 1.2 ꢁ
away from the framework using PLATON software.
Gas sorption studies performed on the respective acetone-
exchanged 2-In and acetone-hexane-exchanged NH2-2-In (Fig-
ures 2) samples show fully reversible Type-I isotherms, repre-
sentative of microporous materials. The apparent BET surface
area and pore volume for 2-In and NH2-2-In were estimated to
be 2080 m2 gꢀ1, 0.84 cm3 gꢀ1 and 1902 m2 gꢀ1 and 0.76 cm3 gꢀ1,
respectively. As shown in Figure S10, the pore-size distributions
display four-types of cages, which is in great agreement with
the single-crystal structure determination. Clearly, the introduc-
tion of amino functional groups in the ligands slightly decreas-
es the pore sizes and surface areas of the resulting MOF of
NH2-2-In.
Considering the high porosity and functionality of both
MOFs, the varible-temperature sorption isotherms in terms of
single CO2, N2, and CH4 gases for 2-In and NH2-2-In were ex-
perimentally collected (Figures 3 and S12), respectively. It is
Figure 1. (a) The trinuclear indium cluster and molecular building fragments
of 2-In, NH2-2-In and 3-In. (b) Structural sketch of the three 8-connected tri-
nuclear indium-based AFMOFs. (c) Four different shapes of pores (left) and
the tiling graph of the structures. (d) Structural formula and simplified dia-
gram of ligands. Hydrogen atoms are omitted for clarity. N sky blue, O red,
C grey, In green.
Figure 2. N2 sorption isotherms at 77 K for 2-In (black) and NH2-2-In (red)
(filled and open symbols represent adsorption and desorption data, respec-
tively).
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Figure 4. IAST calculated selectivity toward CO2/N2 (20:80) and CO2/CH4
(50:50) in 2-In (black) and NH2-2-In (red), respectively.
Figure 3. Low-pressure CO2, N2, and CH4 adsorption isotherms at 298 K and
760 torr for 2-In and NH2-2-In, respectively.
found that both MOFs exhibit relatively high CO2 uptakes of
60.0 and 75.5 cm3 gꢀ1, in contrast to N2 uptakes of 3.9 and
5.9 cm3 gꢀ1, and CH4 uptakes of 13.5 and 17.5 cm3 gꢀ1 at 298 K
and 760 torr, respectively. It is obvious that the CO2 uptakes for
NH2-2-In are higher than that for 2-In, indicating that the dual-
functional groups in NH2-2-In certainly increase the affinity be-
tween MOF framework-CO2, consequently leading to higher
CO2 adsorption capability in spite of its reduced apparent sur-
face area and pore volume. The stronger interactions between
MOF framework-CO2 for NH2-2-In were further verified by the
slightly higher isosteric heat of CO2 adsorption (Qst), that is,
18–21 kJmolꢀ1 in comparison with that of 2-In, 15–17 kJmolꢀ1
(Figure S13).
To evaluate the practical application of both materials
toward carbon capture, the transient breakthrough experi-
ments were performed by utilization of the homemade gas
separation setup. As seen in Figure 5, the resulting break-
through curves clearly confirmed the fact that CO2 was re-
tained in a period of time, while N2 or CH4 passed through un-
encombered under the mixture of CO2/N2 (20:80) and CO2/CH4
(50:50) at 298 K and 1 bar. The calculated CO2 adsorption selec-
tivities from these dynamic breakthrough experiments are basi-
cally consistent with the IAST results, demonstrating the prom-
ising application of both new AFMOFs toward carbon capture.
Methane storage investigation.
The high porosity and high CO2 uptakes of both AFMOFs
prompted us to investigate their CO2 capture capability, which
is typically evaluated by the two-pairs mixed gases of CO2/N2
and CO2/CH4, representing two potential applications for post-
combustion CO2 capture and natural gas upgrading, respec-
tively. Consequently, the CO2 adsorption selectivities for both
materials were calculated via the well-defined approach of
Ideal Adsorbed Solution Theory (IAST). As shown in Figure S14
and Table S1, the dual-site Langmuir-Freundlich model was ap-
plied and found to be best (R2 >0.9998). The resulting selectivi-
ties for CO2/N2 (20:80) and CO2/CH4 (50:50) mixtures for both
MOFs are presented in Table 2 and Figure 4 as a function of
the total bulk pressure. The CO2/N2 and CO2/CH4 selectivities
are 10.18 and 12.43, 4.20 and 4.23 for 2-In and NH2-2-In, re-
spectively. The obvious CO2 selectivity over N2 and CH4 is con-
sistent with above high CO2 adsorption capability for 2-In and
NH2-2-In.
The recent research shows that the fine-tuning series of isore-
ticular nbo-AFMOFs could enhance the methane storage capa-
bility, which encourages us to investigate the methane storage
performance of both new materials. Therefore, high-pressure
excess adsorption isotherms were collected at 273 K and
298 K, respectively, and then empirically transformed to total
adsorption isotherms (Figure 6 and Figure S15). The total
methane uptake of 2-In and NH2-2-In reaches 137 and
94 cm3 gꢀ1 at 80 bar at 298 K, respectively. The dual-functional-
ized NH2-2-In exhitits 43 cm3 gꢀ1 lower methane uptake com-
pared with that of single amide-functionalized 2-In, which indi-
cates the high porosity dominates the methane storage capa-
bility rather than functionality between both AFMOF materials.
Meanwhile, the modest methane storage performances for
both MOFs are also probably attributed to their lower surface
areas (<3000 m2 gꢀ1), improper cage/pore sizes (ideal sizes of
4, 8 or 11 ꢁ). It is worth noting that the CH4 Qst at zero cover-
age for both materials are 12.8 and 16.6 kJmolꢀ1, respectively
(Figure S16), which is benefical for improving the methane
storage working capability.
Table 2. BET Surface Areas, Enthalpies, and CO2 adsorption Selectivity of
2-In and NH2-2-In at 298 K.
MOFs
SBET
[m2 gꢀ1
Qst
[kJmolꢀ1
]
CO2/N2 [0.2 bar]
IAST/ BT[a]
CO2/CH4 [0.5 bar]
IAST/ BT
]
2-In
NH2-2-In
2080
1902
17.09
20.83
10.18/9.00
12.43/11.30
4.20/2.18
4.23/2.26
Conclusions
In summary, a new eight-connected isoreticular AFMOF plat-
form based on trinuclear indium has been deliberately de-
[a] BT is representing Breakthrough.
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Figure 5. Experimental breakthrough curves for the mixture of CO2/N2 (20:80) and CO2/CH4 (50:50) in packed columns with 2-In (a, b) and NH2-2-In (c, d) at
298 K and 1 bar.
supporting information.[17,18] Fourier-transform infrared (FT-IR) spec-
trum (4000-400 cmꢀ1, KBr pellet) was collected in the solid state on
a Bruker Tensor 27 FT-IR spectrometer. PXRD measurements were
performed on a Rigaku MiniFlex 600 diffractometer with CuKa (l=
1.5406 ꢁ), and the X-ray tube was operated at 40 kV and 15 mA.
High resolution thermogravimetric analysis (TGA) were performed
under a continuous N2 flow and recorded on a Q600SDT thermal
analyzer.
2. Synthesis of Materials.
2.1. Ligand syntheses.
Synthesis of organic linker H2L2.
Figure 6. Total methane adsorption isotherms under high-pressure for 2-In
(black) and NH2-2-In (red) at 298 K, respectively.
signed and successfully constructed. These isoreticular AFMOFs
exhibit not only multi-functionality and high porosity but also
an appreciable carbon capture capacity and a modest amount
of methane storage. These results extend the scope of AFMOF
inventory and may further facilitate optimization of multivari-
ate MOFs toward high performance in the post-combustion
carbon capture and the purification of natural gas.
Methyl 4-Aminobenzoate (3.00 g, 19.9 mmol, 1 equiv) and potassi-
um carbonate (6.86 g, 49.7 mmol) were dissolved in 90 mL acetone
with stirring. Methyl 4-(chloroformyl)benzoate (3.94 g, 19.9 mmol,
1 equiv) was dissolved separately in 30 mL acetone by sonication
and added drop-wise to the stirring reaction mixture. The reaction
mixture was sealed and allowed to stir overnight, after which a
white solid was collected by filtration. The solid was stirred with
water and collected by filtration. The white solid was then sus-
pended in 250 mL THF and hot filtered. The THF filtrate was then
subject to rotary evaporation yielding a white solid. The white
solid was stirred with hexane, collected by filtration and dried
under vacuum, to obtain methyl 4-(4-(methoxycarbonyl)benzami-
Experimental Section
1. Materials and Methods.
All reagents were obtained from commercial sources and used
without further purification. The ligands of H2L2 and H2L3 were
prepared according to the previously reported procedure with
slight modification and the details of synthesis are given in the
1
do)benzoate. H NMR (400 MHz, [D6]DMSO, 258C): d=10.75 (s, 1H,
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CONH), 8.09 (dd, 4H, ArH), 7.96 (dd, 4H, ArH), 3.90 (s, 3H, CH3),
3.84 ppm (s, 3H, CH3).
2930(m), 2866(w), 1666(s), 1602(w), 1526(m), 1390(s), 1323(m),
1253(m), 1180(m), 1097(m), 1016(w), 865(w), 784(m), 734(w),
662(w), 536(w), 449 cmꢀ1 (w).
A solution containing methyl 4-(4-(methoxycarbonyl)benzamido)-
benzoate (4.37 g, 13.9 mmol), NaOH (1.13 g, 28.3 mmol), ethanol
(125 mL) and H2O (125 mL) was prepared and subject to reflux
overnight. The resulting transparent solution was cooled to room
temperature and acidified with a 75 mL 2m HCl/ 75 mL H2O mix-
ture, forming a white suspension. The reaction mixture was sealed
and allowed to stir for 3 hours. The product was collected by filtra-
tion and washed copiously with water until washings were neutral.
The white powder was added to a sample vial which was dried
under vacuum, to obtain 4-(4-carboxybenzamido)benzoic acid
(H2L2). 1H NMR (400 MHz, [D6]DMSO, 258C): d=13.04 (s, 2H,
COOH), 10.70 (s, 1H, CONH), 8.07 (dd, 4H, ArH), 7.94 ppm (dd, 4H,
ArH).
C
[(In3O)(OH)(L3)2(PB)2] (solv)x (3-In)
In(NO3)3·4.5H2O (76.4 mg, 0.2 mmol), H2L3 (36.36 mg, 0.09 mmol)
and HPB (35.82 mg, 0.18 mmol) were mixed in the solvent of
5.0 mL of N, N’-dimethylformamide. The mixture was sealed in a
20 mL scintillation vial and heated to 388 K for 48 h and cooled to
room temperature. The colorless polyhedron crystals obtained
were collected and washed with DMF. FT-IR: n˜ =3472(m), 2936(m),
2866(w), 1668(s), 1528 (m), 1390(s), 1256(m), 1097(m), 866(w),
785(m), 662(w), 476 cmꢀ1 (w).
3. Single-crystal X-ray structure determination.
Single-crystal X-ray diffraction data were collected on a Bruker D8
venture diffractometer at 153 K using graphite monochromated
CuKa radiation (l=1.5418 ꢁ). Indexing was performed using APEX3
(Difference Vectors method). Data integration and reduction were
performed using SaintPlus 6.01. Absorption correction was per-
formed by multi-scan method implemented in SADABS. Space
groups were determined using XPREP implemented in APEX3. The
structures were solved by direct methods and refined with full-
matrix least squares technique using the SHELXTL package.[19] Non-
hydrogen atoms were refined with anisotropic displacement pa-
rameters during the final cycles. Hydrogen atoms were located at
geometrically calculated positions to their carrier atoms and re-
fined with isotropic thermal parameters included in the final stage
of the refinement.
Synthesis of organic linker H2L3.
A summary of the crystallographic data are given in Table 1.
CCDC 1910435 (2-In), 1910436 (NH2-2-In) and 1910437 (3-In) con-
tain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre.
Solid 4-aminobenzoic acid (1.15 g, 8.37 mmol) was dissolved in
NMP (15 mL) and cooled to 58C in ice bath. The solid terephthaloyl
chloride (0.812 g, 4.00 mmol) was added slowly for 1 h and the re-
action mixture was stirred at 58C for 2 h followed by continue stir-
ring at room temperature for an additional 12 h. After that, 20 mL
of distilled water was added. The product was filtered and washed
with 20 mL of NMP, five times with 50 mL of distilled water, twice
with 20 mL of methanol and finally dried at 658C for 12 h to
obtain 4,4’-(terephthaloylbis(azanediyl))dibenzoic acid (H2L3).
1H NMR (400 MHz, [D6]DMSO, 258C): d=12.77 (s, 2H, COOH), 10.66
(s, 2H, CONH), 8.10 (s, 4H, ArH), 7.93 ppm (dd, 8H, ArH).
4. Gas sorption measurements.
4.1. Sample activation.
The as-synthesized samples of 2-In were soaked in acetone for 3
days with acetone refreshing every 8 hours. NH2-2-In was soaked
in acetone for 90 min with acetone refreshing every 30 min, and af-
terwards, the samples were soaked in n-hexane for 90 min with n-
hexane refreshing every 30 min. Then, the Acetone-exchanged
sample of 2-In was activated under vacuum at 303 K for 12 hours,
the n-hexane-exchanged sample of NH2-2-In was activated under
vacuum at 303 K for 4 hours and 323 K for 8 hours.
2.2. Preparation of 2-In, NH2-2-In and 3-In.
[(In3O)(OH)(L2)2(IN)2]·(solv)x (2-In)
In(NO3)3·4.5H2O (76.4 mg, 0.2 mmol), H2L2 (28.5 mg, 0.1 mmol) and
HIN (22.14 mg, 0.18 mmol) were mixed in the solvent of 5.5 mL of
N,N’-dimethylformamide. The mixture was sealed in a 20 mL scintil-
lation vial and heated to 358 K for 48 h and cooled to room tem-
perature. The colorless polyhedron crystals obtained were collected
and washed with DMF. FT-IR: n˜ =3490(m), 3306(w), 2930(m),
2866(w), 1668(s), 1530(m), 1387(s), 1321(m), 1254(m), 1177(m),
1095(m), 1016(w), 866(w), 783(m), 694(w), 661(w), 538(w), 452 cmꢀ1
(w).
4.2. Low-pressure adsorption.
Low pressure gas adsorption studies were conducted on a fully au-
tomated micropore gas analyzer Autosorb-iQ3 (Quantachrome In-
struments) at relative pressures up to 1 atm. The cryogenic temper-
ature was controlled using liquid nitrogen at 77 K. The bath tem-
perature for the CO2, N2 and CH4 sorption measurements was con-
trolled using a recirculating bath containing an ethylene glycol/
H2O mixture. The apparent surface areas were determined from
the nitrogen adsorption isotherms collected at 77 K by applying
the BET models. Pore size analyses were performed using a cylin-
drical/spherical NLDFT pore model system by assuming an oxidic
(zeolitic) surface.
[(In3O)(OH)(L2)2(AIN)2]·(solv)x (NH2-2-In)
In(NO3)3·4.5H2O (76.4 mg, 0.2 mmol), H2L2 (42.75 mg, 0.15 mmol)
and HAIN (34.5 mg, 0.25 mmol) were mixed in the solvent of
4.5 mL of N, N’-dimethylformamide. The mixture was sealed in a
20 mL scintillation vial and heated to 358 K for 48 h and cooled to
room temperature. The brown polyhedron crystals obtained were
collected and washed with DMF. FT-IR: n˜ =3437(m), 3312(w),
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R
to
4.3. Isosteric Heat of Adsorption.
Fi ꢂ t0Vdead
ꢀ
FeDt
0
qi ¼
m
The isosteric heat of adsorption represents the strength of the in-
teractions between adsorbate molecules and the adsorbent lattice
atoms and can be used as a measurement of the energetic hetero-
geneity of a solid surface. The isosteric heat of adsorption at a
given amount can be calculated by the Clausius-Clapeyron equa-
tion as
Where Fi is the influent flow rate of the specific gas (mLminꢀ1); t0
is the adsorption time (min); Vdead is the dead volume of the
system (cm3); Fe is the effluent flow rate of the specific gas
(cm3 minꢀ1); and m is the mass of the sorbent (g). The selectivity of
the breakthrough experiment is defined as
ꢀ
ꢁ
@ lnP
@ T
Qst
¼
ꢀ RT2
na
a ¼ ðq1= y1 Þ= ðq2= y2Þ
Where yi is the molar fraction of gas i in the gas mixture. The same
breakthrough experiments were repeated three times after the ad-
sorbent saturated with CO2 was regenerated by a pure He flow.
where Qst is the isosteric heat of adsorption (kJmolꢀ1), P is the
pressure (kPa), T is the temperature, R is the gas constant, and na is
the adsorption amount (mmolgꢀ1).
7. High-pressure adsorption.
5. IAST calculation.
High-pressure excess methane adsorption isotherms in the range
of 0–80 bar were measured with an automatic volumetric sorption
apparatus (BELSORP-HP). The measurement temperatures were
controlled by a computer-controlled glycol-water bath. Ultrahigh-
purity He was used to determine the dead space of the sample
cell. The adsorption data were corrected to give the final gravimet-
ric excess adsorption isotherm nex (P, T), by subtracting the back-
ground adsorption measured with the empty sample cell using the
same test parameters, shown in Figure S17. The total adsorption,
which represents the real gas-storage performance of the porous
material but cannot be directly measured, was calculated by
[Eq. (1)]:
IAST (Ideal Adsorption Solution Theory)[20] was used to predict
binary mixture adsorption from the experimental pure gas iso-
therms. In order to perform the integrations required by IAST, the
single-component isotherms should be fitted by a proper model.
In practice, several methods to do this are available. We found for
this set of data that the dual-site Langmuir-Freundlich equation
was successful in fitting the data. As can be seen in Table S1, the
model fits the isotherms very well (R2 >0.9998).
1
1
n1
n2
qm;1b1p
qm;2b2p
q ¼
þ
1
1
n1
n2
1 þ b1p
1 þ b2p
ntot ðP; TÞ ¼ nex ðP; TÞ þ 1gas ðP; TÞ ꢂ VP
Here, P is the pressure of the bulk gas at equilibrium with the ad-
sorbed phase (kPa), q is the adsorbed amount per mass of adsorb-
Where 1gas (P, T) is the density of bulk methane at pressure P and
temperature T, and Vp is the pore volume of the porous material
determined from N2 adsorption isotherm at 77 K. The volumetric
isotherms were obtained by multiplying the gravimetric isotherms
with the crystallography density of the host framework.[22]
ent (mmolgꢀ1), q
and q
are the saturation capacities of
2
m,
1
m,
sites 1 and 2 (mmolgꢀ1), b1 and b2 are the affinity coefficients of
sites 1 and 2 (1kPaꢀ1), and n1 and n2 represent the deviations from
an ideal homogeneous surface. The fitted parameters were then
used to predict multi-component adsorption with IAST.
The selectivity SA/B in a binary mixture of components A and B is
defined as (xA/yA)/ (xB/yB), where xi and yi are the mole fractions of
component i (i=A, B) in the adsorbed and bulk phases, respective-
ly.
Acknowledgements
This work was finacially supported by the National Natural Sci-
ence Foundation of China (No. 21771121 and 21871170),
Cheung Kong Scholars Program and the Hundred/Thousand
Talents Programs of Shaanxi Province. The authors are grateful
to Prof. Yunfeng Zhao for helpful discussions about the break-
through experiment.
The dual-site Langmuir-Freundlich parameters for CO2, N2, and CH4
isotherms at 298 K are given in Table S1.
6. Breakthrough experiments.
Breakthrough system used in this study is the homemade HP-
MC41 gas separation test system (Nanjing Hope Analytical Equip-
ment Co., Ltd). The flow rates of all gases are regulated by mass
flow controllers, and the effluent gas stream from the column is
monitored by a gas chromatography (GC). In a typical experiment,
ꢁ500 mg of porous sorbent was ground and packed into a stain-
less-steel column (12 cm lengthꢂ0.30 cm internal diameter) with
silica wool filling the void space. The sorbent was activated in situ
in the column before the temperature of the column was de-
creased to 298 K. The packed column was initially purged with
helium gas for 30 min until no other gases were detected in the ef-
fluent. Then, dry gas mixture of CO2-N2 flow at 2 mLminꢀ1
(20:80,v/v) and CO2-CH4 flow at 2 mLminꢀ1 (50:50,v/v) were dosed
into the column. The dead time was determined using the same
column after adsorption saturation. The absolute adsorbed
amount of gas i (qi) is calculated from the breakthrough curve by
the equation according literature with modification:[21]
Conflict of interest
The authors declare no conflict of interest.
Keywords: carbon capture · methane storage · metal-organic
frameworks · trinuclear indium
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Manuscript received: April 23, 2019
Revised manuscript received: May 22, 2019
Version of record online: && &&, 0000
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FULL PAPER
By means of reticular chemistry, three
isoreticular eight-connected trinuclear
indium-based amide-functionalized
metal–organic frameworks were deliber-
ately designed and successfully con-
structed. They exhibit not only multi-
functionality and high porosity but also
an appreciable carbon capture capacity
and a modest amount of methane stor-
age.
Zong-Hui Zhang, Qian Wang,
Dong-Xu Xue,* Junfeng Bai*
&& – &&
Syntheses, Structures and Sorption
Properties of Three Isoreticular
Trinuclear Indium-Based Amide-
Functionalized Metal–Organic
Frameworks
Chem. Asian J. 2019, 00, 0 – 0
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These are not the final page numbers! ÞÞ