Optimal Binding of Acetylene to a Nitro-Decorated Metal-Organic Framework

Article abstract of DOI:10.1021/jacs.8b08504

We report the first example of crystallographic observation of acetylene binding to -NO₂ groups in a metal-organic framework (MOF). Functionalization of MFM-102 with -NO₂ groups on phenyl groups leads to a 15% reduction in BET surfac

Full text of DOI:10.1021/jacs.8b08504

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Communication
Optimal binding of acetylene to a nitro-decorated metal-organic framework
Thien D Duong, Sergey A. Sapchenko, Ivan da Silva, Harry G.W. Godfrey, Yongqiang Cheng,
Luke L. Daemen, Pascal Manuel, Anibal J. Ramirez-Cuesta, Sihai Yang, and Martin Schröder
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b08504 • Publication Date (Web): 04 Oct 2018
Downloaded from http://pubs.acs.org on October 4, 2018
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Optimal binding of acetylene to a nitro-decorated metal-organic
framework
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†
†,┴,♯
‡
†
Thien D. Duong, Sergey A. Sapchenko,
Ivan da Silva, Harry G.W. Godfrey, Yongqiang
§
§
‡
§
†,∗
Cheng Luke L. Daemen, Pascal Manuel, Anibal J. Ramirez-Cuesta, Sihai Yang, and Martin
†
,∗
Schröder
†
School of Chemistry, Oxford Road, University of Manchester, Manchester, M13 9PL, UK.
┴
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Acad. Lavrentieva
Ave., 3, 630090, Novosibirsk, Russia.
♯
Faculty of Natural Sciences, Novosibirsk State University, Pirogova St., 2, 630090, Novosibirsk, Russia.
‡
ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX11 0QX, UK.
§
Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.
Supporting Information
1
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13
13
14
dine-, pyrazine-, pyridazine-, naphthalene groups have
been tested for acetylene adsorption. However, molecular
insights into the precise role of these moieties on the binding
of acetylene is largely lacking, thus restricting the design of
improved materials.
ABSTRACT: We report the first example of crystallographic
observation of acetylene binding to -NO groups in a metal-
2
organic framework (MOF). Functionalisation of MFM-102
with –NO groups on phenyl groups leads to a 15% reduction
2
in BET surface area in MFM-102-NO . However, this is cou-
2
3
-1
pled to a 28% increase in acetylene adsorption to 192 cm g
Acetylene is relatively electron-rich due to its triple bond,
and we argued that MOFs incorporating electro-positive or
electron withdrawing groups would be a promising approach
to facilitate C H binding. The nitro group (-NO ) is one of
at 298 K and 1 bar, comparable to other leading porous mate-
rials. Neutron diffraction and inelastic scattering experi-
ments reveal the role of -NO groups, in cooperation with
2
2
2
2
open metal sites, in the binding of acetylene in MFM-102-
NO2.
the most powerful electron-withdrawing groups. However,
the direct visualisation of gas binding to -NO2 groups in
MOFs has not been reported to date and adsorption of acety-
15
lene in NO -decorated MOFs remains unexplored. Here, we
2
report the study of acetylene adsorption in a family of four
iso-structural MOFs (the MFM-102 series) bearing different
functional groups, including nitro, amine, and alkane groups.
The selection of these functional groups gives a wide cover-
age in terms of their electron donating and withdrawing
power. We found that functionalisation of the parent MFM-
Acetylene is an important chemical for the production of
polymers and other advanced materials. However, it is high-
ly explosive and cannot be compressed beyond 2 atm at room
temperature, thus making its storage and transport a chal-
lenge. Acetylene storage is achieved currently by dissolving
acetylene gas in acetone under high pressure (equivalent to
1
1
02 with NO -groups leads to a 16% reduction in the BET
2
~
10 atm) in a heavy-duty tank filled with porous materials,
surface area in MFM-102-NO , but a 28% improvement in
2
3
2
-1
such as firebrick. This enables the transport of acetylene in
liquid form. However, such processes are not only costly but
also limit the purity of stored acetylene to ~95%, making it
unsuitable for many applications unless a secondary purifica-
tion process is applied. Porous metal-organic frameworks
(MOFs) are emerging sorbents for a variety of gases owing to
their high porosity, well-defined pore size, their design flexi-
acetylene adsorption to 192 cm g at 298 K and 1 bar, compa-
rable to the leading materials for acetylene storage. The
binding domains for adsorbed acetylene molecules in MFM-
1
02-NO have been studied by in situ neutron powder diffrac-
2
tion and inelastic scattering experiments. In comparison,
other functional groups (i.e., amine and alkane groups in
MFM-102-NH2 and MFM-111, respectively) have neutral or
detrimental effects on acetylene adsorption compared to
3
bility and ability to incorporate active binding sites. Recent-
ly, there has been an increasing interest on the study of
MOFs for acetylene storage, and the introduction of organic
MFM-102-NO . Importantly, we describe the first example of
observation of direct binding of acetylene molecules to the -
2
4
functional groups is an efficient approach to increase the gas
NO groups in a MOF material, leading to the optimal ad-
sorption of this substrate.
2
5
6
binding within pores. MOFs incorporating –OH, –NH , –
2
7
8
9
10
11
12
CONH–, –CC–, R–CO–R, –R, –OR, pyridine-, pyrimi-
1
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2
H L and H L were synthesised using our previously report-
(Figures 1, 2) with introduction of functional groups leading
to reduction in porosity. These values are higher than other
reported MOFs with NbO-topology, such as NJU-Bai-17 (2423
4
4
1
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1
1
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9
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ed methods. Introduction of nitro and amine groups to H L
4
yielded H L and H L , respectively. Single crystals of MFM-
102, MFM-111, MFM-102-NO and MFM-102-NH were synthe-
3
4
4
4
2
-1 17
2
-1 18
2
-1 19
m g ), UTSA-88 (1771 m g ), and ZJU-7 (2209 m g ).
2
2
sised from Cu(NO ) ·6H O and the corresponding ligand in
3
2
2
DMF or DMF/DMSO under solvothermal conditions. Single
crystal X-ray diffraction analysis indicated that all these
MOFs are iso-structural, crystallise in the hexagonal space
1
000
a) N -77 K
2
800
600
400
ꢀ
group R3m, and adopt a NbO-type structure (Figure 1).
MFM-102
MFM-111
MFM-102-NH
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200
0
MFM-102-NO
0
.0
0.2
0.4
0.6
0.8
1.0
Pressure (bar)
200
175
150
125
100
75
b) C H -298 K
2
2
MFM-102
MFM-111
MFM-102-NH
50
2
2
25
MFM-102-NO
0
0.0
0.2
0.4
0.6
0.8
1.0
Pressure (bar)
2
2
1
1
50 c) CH -298 K
4
00
50
00
50
0
MFM-102
MFM-111
MFM-102-NO
2
2
MFM-102-NH
Figure 1. Views of organic linkers and the crystal structure for MFM-
1
2 2
02, MFM-111, MFM-102-NO and MFM-102-NH . The added func-
0
5
10
15
20
tional groups are highlighted in ball-stick mode. The BET surface
area for each MOF is shown at the bottom. (C, dark grey; O, red; N,
blue; Cu, turquoise; all coordinated waters and hydrogen atoms are
Pressure (bar)
Figure 2. Adsorption isotherms for desolvated MFM-102, MFM-111,
MFM-102-NO and MFM-102-NH . (a) N at 77 K; (b) C at 298 K;
c) CH at 298 K. Solid and open symbols represent adsorption and
omitted for clarity, except for the hydrogen atoms on the -NH
group, green).
2
2
2
2
2 2
H
(
4
desorption, respectively.
The crystal structure of MFM-102-NO is described here in
2
detail. Two Cu(II) ions are bridged by four carboxylate
groups to form a paddlewheel [Cu (OOCR) (OH ) ]. This
Uptakes of C H at 273 K and 1 bar were recorded as 292, 261,
51 and 241 cm g for MFM-102-NO , MFM-102-NH , MFM-
02 and MFM-111, respectively (Figure S8). Significantly, the
C H uptake of MFM-102-NO (292 cm g ) is among those of
2
2
3
-1
2
4
2 2
2
1
2
2
serves as a 4-connected node that is further linked to other
-connected nodes to construct a 3D NbO-type open struc-
4
3
-1
2
2
2
ture. All these MOFs are constructed by the alternative pack-
ing of 2 types of metal-ligand cages (A and B) (Figure 1). Cage
the best-performing MOFs under the same conditions (Table
3
-1 17
3
-
S3), such as NJU-Bai17 (295 cm g ), MFM-188a (297 cm g
A, constructed by six linkers and six {Cu } paddlewheels, has
1
7
3
-1 20
2
)
, and FJI-H8 (277 cm g ). Interestingly, although the
a cylindrical shape with a diameter of 14 Å and length of 19 Å.
Cage B (length of 32 Å) has a shuttle-shape with 12 {Cu2}
paddlewheels residing at the vertices and 6 ligands on the
faces. It is noteworthy that the cages in MFM-111, MFM-102-
NH and MFM-102-NO are decorated with alkane, –NH and
introduction of NO -groups to MFM-102 leads to a 15% re-
2
duction of BET surface area in MFM-102-NO , it results in a
2
2
8% enhancement on C H adsorption under ambient condi-
2 2
tions, strongly demonstrating the positive effect of NO2-
groups on C H2 binding. With similar BET surface areas,
MFM-102-NO , MFM-102-NH , and MFM-111 provide an ex-
cellent platform to directly examine the role of functional
group on C H adsorption. Compared to the parent MFM-
2
2
2
2
–NO2 groups, respectively, pointing into both cages, thus
providing additional binding sites for gas molecules. Phase
purity of each complex has been confirmed by PXRD data
2
2
2
2
(
see SI). The coordinated water molecules and solvent mole-
102, introduction of the amine group shows a small increase
(5.3%) in adsorption of C H , while the alkane group leads a
cules in the pores can be removed under heating to generate
open Cu(II) sites in the desolvated materials.
2
2
moderate reduction (-12%) in C H adsorption. The isosteric
heats of C H adsorption (Q ) for these MOFs are around 31
2 2 st
to 33 kJ mol , comparable to reported MOFs with open
Cu(II) sites (Table S3). The Qst plots shows little variation as
2
2
N2 isotherms at 77 K confirms that desolvated MFM-102,
MFM-111, MFM-102-NH and MFM-102-NO show BET sur-
-
1
2
2
2
-1
face areas of 3412, 2930, 2928, and 2893 m g , respectively
2
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a function of uptake, indicating the presence of cooperativity
of host-guest and guest-guest binding.
–CH bond of the NO -decorated phenyl ring [–
CH···CC(centroid) = 3.11(4) Å]. Moreover, there is a weak
2
21
1
2
3
4
5
6
7
8
9
π···π interaction between CC bond of C D (IV) and the
To establish the role of these functional groups on C H2
2
2
2
NO2-decorated phenyl ring [ring centroid···CC(centroid) =
.46(8) Å]. Site V (occupancy = 0.16) is at the window be-
binding, adsorption of CH , as a non-interacting gas probe,
4
4
was also measured. At 298 K and 20 bar, MFM-102 shows a
3
-1
tween the cylindrical and spherical cages involving similar
CH4 uptake of 236 cm g , which is higher than that for
MFM-102-NO , MFM-102-NH and MFM-111 (188, 179 and 173
side-on mode interactions with the –CH group of the NO2-
2
2
3
-1
decorated phenyl ring [–CH···CC(centroid) = 2.63(5) Å] and
cm g , respectively). The trend in uptake of CH is con-
4
the hydrogen bond to the -NO group [D···ONO2 = 3.05(10),
sistent with the variation of BET surface areas of these mate-
rials, and suggests potential binding interactions between the
2
3.17(7) Å]. Site VI (occupancy = 0.09) is located in the center
of the elongated cage, interacting directly with the -NO2
-
NO functional group and unsaturated C H .
2 2 2
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group from three surrounding ligands with D···ONO dis-
2
tances ranging from 2.37(1) to 2.56(3) Å. Overall, C D mole-
2
2
cules at sites III-VI are all directly associated with the –NO2
groups in the pore, confirming the positive effect of -NO2
group on achieving optimal acetylene binding.
-1)
Neutron energy loss (cm
0
200 400 600 800 1000 1200 1400 1600
Diff-C H
2
2
Solid C H
2
2
0
25
50
75
100 125 150 175 200
Neutron energy loss (meV)
Figure 4. INS spectra for MFM-102-NO
son of difference INS plots derived by subtracting INS spectra for
-loaded MFM-102-NO and bare MFM-102-NO spectra (black),
with condensed C in the solid state (red).
2 2 2
with C H loading. Compari-
C
2
H
2
2
2
2 2
H
Figure 3. View of the binding sites for adsorbed C
D
2 2
molecules in
The binding dynamics of C H -loaded MFM-102-NO were
2 2 2
MFM-102-NO . (C, dark grey; O, red; N, blue; Cu, turquoise and C D
2
2 2
also studied by in situ inelastic neutron scattering (INS). The
INS spectrum of bare MOF shows excellent agreement with
that obtained from DFT calculations, thus allowing assign-
ment of vibrational modes (Figure S12). The INS spectrum of
C H -loaded MFM-102-NO shows a significant increase in
2 2 2
intensity (Figures 4 and S11). The INS peaks at 80 and 95 meV
(assigned as the asymmetric and symmetric C-H bending
molecules at site I (light blue), site II (orange), site III (light green),
site IV (dark green), site V (purple) and site VI (sapphire).
Six independent binding sites (I to VI) for adsorbed C D2
2
molecules in MFM-102-NO have been determined by in situ
2
neutron powder diffraction (NPD) (Figure 3). Sites I and II
(
occupancies of 0.41 and 0.40, respectively) are located at the
open Cu(II) sites with a side-on interaction between the CC
bond and Cu(II) [Cu···CC(centroid) = 3.98(5) and 2.93(8) Å
for site I and II, respectively]. Interestingly, sites I and II have
very different bonding distance to the open Cu(II) site. A
closer examination revealed that site I also forms supramo-
lecular interactions to two aromatic –CH groups from two
adjacent phenyl rings [–CH···CC(centroid) = 3.23(2), 3.48(3)
Å] and becomes the most populated location owing to this
cooperativity between sites. Site III (occupancy 0.31) is stabi-
lised by a combination of three types of interactions to the
mode of C
adsorption of C
sides and a shift to lower energy. In addition, the translation-
al modes of C molecules, represented by the INS peaks at
low energy region (below 25 meV), show restricted motion
on adsorption, with adsorbed C molecules well-ordered in
the pore as these peaks all shift to lower energy but still re-
main a three-fold feature as found in solid C . Moreover,
in the difference spectra, peaks at 164 and 189 meV (Figure
S12) develop upon inclusion of C molecules in the pore,
and this enhancement of both symmetrical and anti-
symmetrical stretching modes of -NO groups confirms the
formation of host-guest interactions between the -NO
groups and adsorbed C molecules. Overall, these results
are highly consistent with the crystallographic studies show-
H , respectively) show significant broadening on
2 2
H
2 2
with the appearance of shoulders on both
H
2 2
H
2 2
H
2 2
H
2 2
+
host: (i) hydrogen bonds between the D(δ ) of C D mole-
2
2
-
cules and O(δ ) center of the –NO group [D···O = 1.99(9),
2
2
2.35(6) Å]; (ii) supramolecular interactions between the CC
2
bond and the –CH group on adjacent NO -decorated phenyl
H
2 2
2
rings [–CH···CC(centroid) = 2.47(9), 2.80(4) Å]; (iii) inter-
molecular dipole interactions between π-electrons on CC
bond (site III) and D-atoms of C D at site IV. Site IV (occu-
ing various binding sites (I-VI) of C
action between the –NO group and C
VI) in the pore of MFM-102-NO
D
and the strong inter-
2
2
D
2
molecules (site III-
2
2
2
2
pancy 0.26) is also stabilised by hydrogen bonds between
C D molecules and –NO groups [D···O = 1.69(2) Å] and a
.
2
2
2
2
NO2
3
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Achieving optimal gas adsorption and binding in porous
materials requires integration of high porosity and appropri-
ate binding sites. However, introduction of functional groups
to MOF pores naturally reduces the porosity of decorated
MOFs, leading to a trade-off between these two factors. In
this study, the effect of amine, alkane and nitro groups on
3. Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Park, J.; Park, J.; Tian, J.;
1
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Zhang, M.; Zhang, Q.; Gentle III, T.; Bosch, M.; Zhou, H.-C.,
Chem. Soc. Rev. 2014, 43, 5561.
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.
(a) Xu, H.; Cai, J.; Xiang, S.; Zhang, Z.; Wu, C.; Rao, X.; Cui, Y.;
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adsorption of C H has been examined in a family of isostruc-
2
2
tural MOFs showing high BET surface areas. The first exam-
ple of binding between electron-rich C H2 molecules and
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Chem. 2016, 241, 152.
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Chen, B.; Qian, G. RSC Adv. 2015, 5, 77417.
2
electron withdrawing –NO groups in the MOF, MFM-102-
2
NO , at crystallographic resolution has been established. The
2
0
1
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0
1
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combination of high BET surface area, high density of open
7.
Moreau, F.; da Silva, I.; Al Smail, N. H.; Easun, T. L.; Savage, M.;
Godfrey, H. G. W.; Parker, S. F.; Manuel, P.; Yang, S.; Schröder,
M. Nat. Commun. 2017, 8, 14085.
Cu(II) sites and accessible NO -groups leads to excellent
2
adsorption capacity of C H in MFM-102-NO , making it one
2
2
2
of the best-performing acetylene adsorbents to date.
8. Hu, Y.; Xiang, S.; Zhang, W.; Zhang, Z.; Wang, L.; Bai, J.; Chen, B.
ChemComm. 2009, 7551.
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ASSOCIATED CONTENT
Supporting Information
Synthesis procedures, characterization, and additional analy-
sis of crystal structures. Single crystal data of MFM-102-NO2
and MFM-102-NH2 are deposited at Cambridge Crystallo-
graphic Data Centre (CCDC) as 1857304 and 1857305, respec-
tively, with NPD data deposited as 1857872 and 1857873 for
C D -loaded MFM-102-NO and activated MFM-102-NO2,
1
2. Rao, X.; Cai, J.; Yu, J.; He, Y.; Wu, C.; Zhou, W.; Yildirim, T.;
Chen, B.; Qian, G. Chem. Commun. 2013, 49, 6719.
3. Song, C.; Jiao, J.; Lin, Q.; Liu, H.; He, Y. Dalton Trans. 2016, 45,
4563.
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AUTHOR INFORMATION
Corresponding Authors
Sihai.Yang@manchester.ac.uk;
M.Schroder@manchester.ac.uk
Author Contributions
Notes
1
The authors declare no competing financial interests.
ACKNOWLEDGMENT
We thank EPSRC (EP/I011870, EP/P001386, EP/K038869),
ERC (AdG 226593) and University of Manchester for funding.
We thank ISIS/STFC and ORNL for access to Beamlines
WISH and VISION, respectively. We thank D. Rizzo and Dr.
Iñigo J. Victórica-Yrezábal for helpful discussions.
1
1
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