Tailoring the pore geometry and chemistry in microporous metal-organic frameworks for high methane storage working capacity

Article abstract of DOI:10.1039/c9cc06239d

We realized that tailoring the pore size/geometry and chemistry, by virtue of alkynyl or naphthalene replacing phenyl within a series of isomorphic MOFs, can optimize methane storage working capacities, affording an exceptionally high working capacity of

Full text of DOI:10.1039/c9cc06239d

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DOI: 10.1039/C9CC06239D
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Tailoring pore geometry and chemistry in microporous metal–
organic frameworks for high methane storage working capacity
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
b
b
,a
Kai Shao, Jiyan Pei, Jia-Xin Wang, Yu Yang, Yuanjing Cui, Wei Zhou, Taner Yildirim, Bin Li,*
c
,a
Banglin Chen Guodong Qian*
DOI: 10.1039/x0xx00000x
www.rsc.org/
We realize that tailoring pore size/geometry and chemistry, by
Extensive research efforts have been devoted to developing
virtue of alkynyl or naphthalene replacing phenyl within a series new materials with high methane storage capacity in order to
of isomorphic MOFs, can optimize methane storage working meet the challenging storage target. Microporous metal–
capacities, affording an exceptionally high working capacity of 203 organic frameworks (MOFs) are known to be very promising
3
-3
cm (STP) cm at 298 K and 5–80 bar.
for methane storage because of their high surface areas,
2
-4
tunable pores, and versatile chemistry. A large number of
MOFs, such as HKUST-1, UTSA-76, Co(BDP), MOF-5, NU-125,
Al-soc-MOF-1, MAF-38, MOF-905, NJU-Bai43, and MFM-115
have been reported as outstanding storage adsorbents,
The exponential increase on global energy usage over the next
0 years has pushed the implementation of a cleaner fuel for
replacing conventional petroleum fuels to a level of utmost
importance. Natural gas (NG), primarily composed of methane,
holds the bright promise as a viable alternative fuel due to its
5
showing some of the highest gravimetric or volumetric CH
4
5-11
storage capacities. It is notable that the volumetric working
capacity is a key parameter to evaluate the performance of
methane storage materials, because it determines the driving
range of vehicles powered by natural gas. Since the
automobile industry requires an engine inlet pressure of 5 bar,
the working capacity (also called deliverable capacity) is
defined as the difference of the amount of methane adsorbed
between the target storage pressure (generally 35–80 bar) and
2
abundant reserves, low CO emission and high research octane
number (RON = 107). However, its widespread use is limited
by the relatively low volumetric energy density. Although
liquefied NG (LNG) at 113 K and compressed NG (CNG) at 250
bar are already in use, cryogenic and high-pressure storage
conditions have severely hampered practical applications. For
instance, overhigh pressures required for liquification can only
be achieved by complex and expensive multi-stage
compressors, leading to some cost, space, and safety issues for
use in passenger vehicles. In this regard, adsorbed natural gas
5
bar. Prominently, there are two pathways to improve the
methane working capacity of a given porous material. On one
hand, optimizing pore sizes or functional sites in MOFs can
enforce the strength of host–methane and methane–methane
interactions (Qst), contributing to high volumetric methane
(
ANG) systems have attracted a considerable interest to
overcome these issues, which involves filling storage tanks
with porous materials to store high density of methane at
modest pressures. To guide the research of ANG technology,
the U.S. Department of Energy (DOE) sets the ambitious
volumetric NG storage target of 263 cm (STP) cm at room
temperature (RT) assuming the adsorbent packing loss is
5,6
uptake at high pressure. Nevertheless, overhigh Qst in MOFs
leads to a rapid increase in low-pressure uptake, sometimes
delimiting their high working capacity, as exemplified by MOF-
3
−3
6
7
4 and PCN-14. On the other hand, large-pore MOFs (e.g.,
MOF-905, Al-soc-MOF-1 and NU-111) commonly show
moderate Qst for methane, giving a low CH adsorption at 5
affinity delimits total CH
uptake at high pressure, thus sacrificing the working capacity
1
ignored, equivalent to that of CNG at 250 bar and 298 K.
4
9
,10
bar;
however, too weak CH
4
4
a. State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials
and Applications, Department of Materials Science & Engineering, Zhejiang
University,
gdqian@zju.edu.cn.
NIST Center for Neutron Research, National Institute of Standards and
Technology, Gaithersburg, Maryland 20899-6102, United States.
c.Department of Chemistry, University of Texas at San Antonio, One UTSA Circle,
San Antonio, Texas 78249-0698, USA. Fax: (+1)-210-458-7428.
Electronic Supplementary Information (ESI) available: synthesis, PXRD, sorption
data, NMR, optical images and structural data for PCN-46 and ZJU-105. CCDC
943325. For ESI and crystallographic data in CIF or other electronic format see
1
0
in some cases. Evidently, it is highly desired to optimize
porous structures with suitable methane binding affinity for
Hangzhou
310027,
China.
E-mail:
bin.li@zju.edu.cn;
b.
balancing the CH adsorption amounts between high and low
4
pressure, thus targeting higher volumetric working capacity.
With this in mind, we herein used a crystal-engineering
strategy to finely modulate pore size and chemistry on a family
of isomorphic MOFs for methane storage. We chose NOTT-102
as the fundamental framework backbone because of its high
1
DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C9CC06239D
Fig. 2 (a) Nitrogen isotherms of ZJU-105a, NOTT-102a and PCN-
6a at 77 K. (b) Total volumetric CH adsorption isotherms of
4
4
PCN-46a and (c) ZJU-105a. (d) Comparison of the CH
adsorption amount of the indicated MOFs at 5 and 65 bar.
4
Fig. 1 Comparison of the organic linkers and crystal structures
of ZJU-105, NOTT-102, and PCN-46.
both of the ZJU-105 and PCN-46 frameworks are isoreticular to
NOTT-102, which consist of paddle-wheel dinuclear Cu (COO)
units linked by the carboxylates of L linkers to form 3D NbO-
2
4
methane storage capacity and easily adjustable functionality
4−
1
4
on the center phenyl rings. The purposive use of alkynyl or
naphthalene groups replacing phenyl rings in NOTT-102
afforded two porous materials (namely PCN-46 and ZJU-105),
in which the pore size and pore-chemistry can be well
modulated (Fig. 1). It was found that the expanded pore size
14d
type network.
As expected, the use of alkynyl or
naphthalene groups to replace phenyl rings on NOTT-102 can
finely modulate the pore size/geometry and chemistry. As
shown in Fig. 1, the framework of NOTT-102 has two types of
2
cages: one cuboctahedral cage of about 12.5 × 14.7 Å , and
and reduced aromatic CH
a slight decrease on low-pressure CH
4
-affinity sites in PCN-46a can enable
uptake while has a
2
another large irregular elongated cage of ≈ 9.6 × 28.6 Å . When
4
the bulky naphthalene rings were incorporated, the pores of
ZJU-105 are significantly decreased, wherein the large irregular
cage is divided into three small cages with the diameters of 3.8
and 8.0 Å. In contrast, we slim organic ligands in PCN-46 by
virtue of triple-bond spacers replacing phenyls in NOTT-102.
Relative to NOTT-102, PCN-46 exhibits a similar pore geometry
with slightly expanded pore spaces. In addition, the
incorporation of alkynyl or naphthalene groups in PCN-46 and
ZJU-105 can reduce or increase aromatic moieties that enable
negligible effect on the adsorption at 65/80 bar, leading to an
3
exceptionally high volumetric working capacity of 203 cm
(
STP) cm-3 between 5 and 80 bar at 298 K. This value is
comparable to the best-performing MOFs reported, such as
3
-3 12
3
MFM-115a (208 cm (STP) cm ) and MOF-905 (203 cm (STP)
-3 13
cm ) .
The linkers of H
4
4
L1 and H L2 were elaborately designed by
using two naphthalene or alkynyl groups replacing phenyl rings
on the linker of NOTT-102 (Fig. 1). Both of organic linkers were
synthesized through a multistep reaction procedure (Scheme
16
to provide π···CH
pore size/geometry and aromatic moieties in this series of
MOFs can systematically affect the strength of CH binding
affinities, thus optimizing the target working capacities.
Before methane adsorption measurements, we first
measured the N adsorption isotherms at 77 K on the activated
ZJU-105a and PCN-46a. As shown in Fig. 2a, the N isotherms
of ZJU-105a and PCN-46a exhibit reversible type-I character
4
interactions. Therefore, the fine-tuned
S1-S2, ESI†). Solvothermal reaction of
H
4
L1 with
O (in the presence of
4
Cu(NO
3
)
2
·2.5H
2
O in a mixture of DMF/H
2
o
HCl) at 80 C for 3 days afforded blue block crystals of a novel
MOF (ZJU-105) with a framework formula of [Cu
The high-quality crystals of PCN-46, [Cu (L2)(H
synthesized by solvothermal reaction of
2
(L1)(H
O) , were
L2 with
O (in the
2 2 n
O) ] .
2
2
2
2 n
]
2
H
4
Cu(NO
presence of HNO
3
)
2
·2.5H
2
O in a mixture of DMF/EtOH/H
2
3
-1
with the saturated uptake of 670 and 803 cm g , respectively.
The Brunauer-Emmett-Teller (BET) surface area and pore
o
3
) at 85 C for 1 day. It is worthy of note that
the sample of PCN-46 in the literature was directly synthesized
by using the precursor compound (5-ethynylisophthalic acid)
2
−1
volume of ZJU-105a were determined to be 2608 m g and
3
−1
1
1
.037 cm g , respectively, notably lower than those of NOTT-
of H
4
L2 to react with copper salts, which cannot guarantee its
2
−1
3
−1
02a (3342 m g and 1.268 cm g ) due to the incorporated
1
5
high quality of bulk samples. In this work, the phase purity of
bulk materials for ZJU-105 and PCN-46 were confirmed by
powder X-ray diffraction (PXRD) and the following surface
area/pore volume measured (Fig. S10-15, ESI†).
bulky naphthalene groups. On the contrary, PCN-46a with the
slimmed alkynyl groups shows a comparable BET surface area
2
−1
3
−1
and pore volume (3224 m g and 1.243 cm g ). We note
that these values of PCN-46a are significantly higher than the
The crystal structures of three MOFs investigated are
schematically shown in Fig. 1. Structural analysis reveals that
2
−1
3
−1
reported values (2500 m
g
and 1.012 cm g ) in the
15
previous literature, and agree well with the theoretical ones
2
| J. Name., 2012, 00, 1-3
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Table 1 Summary of some promising MOFs for high-pressure CH
4
storage.
View Article Online
DOI: 10.1039/C9CC06239D
a
b
c
MOFs
S
BET
2
Total uptake
cm /cm
Working capacity
Q
st
3
3
3
3
(
m /g)
3224
2608
3394
3490
3342
5585
1850
2820
2022
3643
4500
3120
2000
3971
1350
cm /cm
(kJ/mol)
14.2
16.58
16.3
11.7
14.90
11.0
17.0
15.5
21.6
10.4
9.9
PCN-46a
ZJU-105a
MFM-115a
MOF-905
NOTT-102a
Al-soc-MOF-1
HKUST-1
UTSA-76
MAF-38
FDM-8
MOF-177
NU-125
PCN-14
Cu-tbo-MOF-5
246 (233)
243 (228)
256 (238)
228 (206)
- (233)
221 (197)
272 (267)
- (257)
273(263)
215 (193)
205 (187)
- (232)
250 (230)
216 (199)
267 (251)
203 (190)
190 (175)
208 (191)
203 (181)
- (185)
201 (176)
200 (190)
- (197)
197(187)
193 (171)
185 (167)
- (183)
178 (157)
175 (158)
152 (129)
1
2
1
3
1
4a
9
a
4
ab
1
1
1
6a
9
b
1
0a
4
a
15.1
18.7
20.4
21.4
4
ab
1
6b
4
ab
Ni-MOF-74
Calculated from N
capacity is defined as the difference in total uptakes between 80(65) and 5 bar.
a
isotherms at 77 K. b At 80(65) bar and 298 K. c The working Fig. 3 Comparison of the volumetric CH working capacities of
2
4
PCN-46a and ZJU-105a with some best-performing MOFs
reported at 298 K.
2
−1
3
−1
(
3634 m g and 1.266 cm g ) calculated from the crystal
structure. This further confirms the high quality of bulk UTSA-20, Al-soc-MOF-1, and MOF-5, Table 1), and is
samples that we synthesized, encouraging us to retest its comparable to the benchmark HKUST-1 (190 cm
(STP) cm-3
methane storage capacities.
MFM-115 (191 cm (STP)
(STP) cm-3 12, and UTSA-76a (197 cm
Next, we collected the high-pressure methane adsorption cm-3 11. When the storage pressure is increased to 80 bar, PCN-
isotherms for ZJU-105a and PCN-46a at 273 and 298 K over the 46a exhibits an exceptionally high CH working capacity of 203
pressure range of 0−100 bar. As presented in Fig. 2b and 2c, cm
(STP) cm-3 between 80 and 5 bar at RT (Fig. 3), much
ZJU-105a and PCN-46a exhibit high total volumetric methane higher than that of ZJU-105a (190 cm
(STP) cm-3) and rivaling
uptakes of 228 and 233 cm (STP) cm at 65 bar and 298 K, the state-of-the-art materials reported, such as MFM-115a
3
4a
) ,
3
3
)
)
4
3
3
3
-3
respectively. These values are comparable to that of NOTT- (208 cm
3
(STP) cm-3
)
12 and MOF-905 (203 cm
To gain a better insight into the origin of different
3
(STP) cm-3
) .
13
-3
1
02a (233 cm3 (STP) cm ), indicating that tuning pore
size/geometry in these isomorphic MOFs shows a negligible volumetric low-pressure uptakes and working capacities on
effect on total volumetric CH uptake at high pressure. This ZJU-105a and PCN-46a, we first calculated their isosteric heats
might be attributed to the mutual compensation between of adsorption (Q ) from the temperature-dependent
4
st
porosity, crystal density and CH binding strength. With the isotherms using the virial method (Fig. S22-24, ESI†). The initial
4
pressure increasing to 80 bar, the volumetric uptake of ZJU- Qst of ZJU-105a was calculated to be 16.58 kJ mol-1, much
3
-1
1
(
05 and PCN-46 can be further increased to 243 and 246 cm
higher than that of NOTT-102a (14.90 kJ mol ) and PCN-46a
-3
-1
STP) cm , respectively, achieving 93% of the new DOE’s (14.2 kJ mol ). Due to the same framework backbone and
volumetric target assuming the packing density loss is ignored. topology, these MOFs have a similar density of open metal
These values are higher than most of promising MOFs, such as sites. The incorporation of naphthalene groups in ZJU-105a can
3
-3 13
3
MOF-905 (228 cm (STP) cm ) and Al-soc-MOF-1 (221 cm
not only notably reduce pore sizes but also offer more amount
STP) cm ) , and is approaching the best-performing MFM- of aromatic moieties to interact with CH molecules via π···CH
-3 9a
(
4
4
3
-3 12
3
-3 4b
16
1
15 (256 cm (STP) cm ) and HKUST-1 (272 cm (STP) cm ) . interactions, contributing to the enhanced CH affinity and
4
In practical applications, the driving range of an ANG vehicle thus higher CH adsorption amount at low pressure of 5 bar
4
is determined primarily by the working capacity of the than that of NOTT-102a. In contrast, the use of alkynyl groups
adsorbent. We first evaluated the volumetric working to replace benzene rings in PCN-46a can slightly expand pore
capacities of ZJU-105a and PCN-46a to compare with NOTT- sizes with no aromatic moieties, resulting in lower CH affinity
4
1
02a and some other indicated MOFs (Table 1). As shown in and uptake at 5 bar. Therefore, PCN-46a shows the lowest
Fig. 2d, due to the smaller pore spaces and more aromatic low-pressure CH4 uptake among these three MOFs, thus
3
moieties, ZJU-105a takes up more amounts of CH
(
4
(53 cm
affording the highest volumetric working capacity.
-3
3
-3
STP) cm ) at 5 bar than that of NOTT-102a (48 cm (STP) cm ).
We have also studied CO and H uptake properties of ZJU-
2
2
In contrast, PCN-46a shows a lower adsorption amount at 5 105a and PCN-46a over wide temperature and pressure ranges
3
-3
bar (43 cm (STP) cm ) relative to NOTT-102a. Therefore, PCN- (Fig. S18-21, ESI†). ZJU-105a and PCN-46a exhibit high total
3
4
(
(
6a exhibits a higher volumetric working capacity of 190 cm
2
volumetric H storage capacities of 48 g/L (6.78 wt%) and 50
-3
3
-3
STP) cm than NOTT-102a (185 cm (STP) cm ) and ZJU-105a g/L (7.47 wt%) at 65 bar and 77 K, meeting the DOE’s targets of
175 cm (STP) cm ) between 65 and 5 bar at 298 K, It is 40 g/L (5.5 wt%), albeit at 77 K rather than at ambient
3
-3
worthy of note that this working capacity of PCN-46a temperature. These volumetric values are comparable to that
outperforms most of promising MOFs (e.g., NU-125, NU-111,
of some benchmark MOFs (Table S4, ESI†). The volumetric and
gravimetric working capacities of PCN-46a, calculated from
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Journal Name
Liu, Y. He, H. Wu, T. Yildirim, B. Chen, B. Space,ViYew. PAratincl,e OMn.linJe.
(
4
T
min = 77 K, Pmax = 65 bar) to (Tmax = 160 K, Pmin = 5 bar), are
Zaworotko and J. Bai, Angew. Chem., Int. Ed., 2017, 56, 11426.
DOI: 10.1039/C9CC06239D
7.4 g/L and 7.1 wt%, rivaling the best-performing material
6
(a) H. Wu, W. Zhou and T. Yildirim, J. Am. Chem. Soc., 2009,
1
7
IRMOF-20 (47 g/L and 8.4 wt%) . In addition, ZJU-105a and
PCN-46a also exhibit high volumetric CO storage capacities of
28 and 309 cm (STP) cm (Table S5, ESI†). Finally, we 7 (a) C.-C. Liang, Z.-L. Shi, C.-T. He, J. Tan, H.-D. Zhou, H.-L. Zhou,
1
31, 4995; (b) S. Ma, D. Sun, J. M. Simmons, C. D. Collier, D.
2
Yuan and H.-C. Zhou, J. Am. Chem. Soc., 2008, 130, 1012.
3
-3
3
Y. Lee and Y.-B. Zhang, J. Am. Chem. Soc., 2017, 139, 13300;
2 2
calculated the Qst values of H and CO for both MOFs. As
(
b) L. D. Tran, J. I. Feldblyum, A. G. Wong-Foy and A. J.
shown in Fig. S25-30 (ESI†), the Qst values of ZJU-105a for both
and CO are much higher than those of PCN-46a, consistent
well with those for CH , further confirming that PCN-46a has a
Matzger, Langmuir, 2015, 31, 2211; (c) L. Li, J. G. Bell, S. Tang,
X. Lv, C. Wang, Y. Xing, X. Zhao and K. M. Thomas, Chem.
Mater., 2014, 26, 4679; (d) T. Tian, Z. Zeng, D. Vulpe, M. E.
Casco, G. Divitini, P. A. Midgley, J. Silvestre-Albero, J. C. Tan, P.
Z. Moghadam and D. Fairen-Jimenez, Nat. Mater., 2018, 17,
H
2
2
4
weaker interaction with various gas molecules.
In summary, we herein realized that the systematical tuning
of pore size and chemistry in a series of isomorphic MOFs
based on NOTT-102 can effectively regulate the methane
storage and working capacities. The use of alkynyl and
naphthalene replacing phenyl in the NOTT-102 backbone has
enabled a gradually decreased low-pressure CH uptake from
4
ZJU-105a to PCN-46a, combined with a comparable total
storage capacity at high pressure. PCN-46a thus exhibits the
1
74.
8
(a) J. A. Mason, J. Oktawiec, M. K. Taylor, M. R. Hudson, J.
Rodriguez, J. E. Bachman, M. I. Gonzalez, A. Cervellino, A.
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2
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98 K) among the isomorphic MOFs, making it among the best 9 (a) D. Alezi, Y. Belmabkhout, M. Suyetin, P. M. Bhatt, Ł. J.
3
3
highest working capacity of 203 cm (STP) cm (at 5–80 bar and
2
Weseliński, V. Solovyeva, K. Adil, I. Spanopoulos, P. N.
Trikalitis, A.-H. Emwas and M. Eddaoudi, J. Am. Chem. Soc.,
4
performing porous materials for CH storage. This work may
provide some guidance for development of new MOFs with
common alkynyl connectivity instead of phenyl to reduce low-
pressure CH absorption and thus to improve volumetric
4
working capacity.
2
015, 137, 13308; (b) B. Tu, L. Diestel, Z.-L. Shi, W. R. L. N.
Bandara, Y. Chen, W. Lin, Y.-B. Zhang, S. G. Telfer and Q. Li,
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This research was supported by the “National 1000 Young
Talent Program”, the “Zhejiang University 100 Talent Program”,
and the National Science Foundation of China (51803179).
2
013, 6, 1158.
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Conflicts of interest
There are no conflicts to declare.
11 B. Li, H.-M. Wen, H. Wang, H. Wu, M. Tyagi, T. Yildirim, W.
Zhou and B. Chen, J. Am. Chem. Soc., 2014, 136, 6207.
1
2 Y. Yan, D. I. Kolokolov, I. d. Silva, A. G Stepanov, A. J. Blake, A.
Dailly, P. Manuel, C. C Tang, S. Yang and M. Schröder, J. Am.
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Notes and references
1
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We realized that engineering pore size/geometry and chemistry in a series of MOFs can optimize the volumetric
methane storage working capacity.
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