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A series of metal–organic frameworks with high

methane uptake and an empirical equation for
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Cite this: Energy Environ. Sci., 2013, 6,

2735 predicting methane storage capacity†
Yabing He,*a Wei Zhou,*bc Taner Yildirimbd and Banglin Chen*e

A series of metal–organic frameworks (NOTT-100a (MOF-505a), NOTT-101a, NOTT-102a, NOTT-103a and

NOTT-109a) with variable open copper sites and micropore spaces have been examined as potential
adsorbents for methane storage. They exhibit high adsorption capacities for methane at 300 K and 35
bar (181–196 cm3 (STP) cm
3). Supposing that the deliverable amount of methane is defined as the
difference in the amount of methane adsorbed between 5 bar and 35 bar, NOTT-101a, NOTT-102a and
NOTT-103a exhibit excellent deliverable capacities of methane (136–140 cm3 (STP) cm
3), comparable
to the highest of all previously reported MOF materials. The gravimetric methane uptake in this MOF
series systematically increases with increasing porosity, while their methane storage pore occupancy
decreases with increasing pore size. The fact that gravimetric methane uptakes correlate well with their
corresponding pore volumes enables us to derive an empirical equation: C ¼
126.69  Vp2 + 381.62 
Vp
12.57, where C is the excess gravimetric methane storage capacity at 35 bar and 300 K in cm3
Received 5th April 2013
Accepted 11th July 2013
(STP) g
1, and Vp is the pore volume of a MOF material in cm3 g
1. This empirical equation can predict
the methane storage performance of previously reported microporous MOF materials of Vp less than
DOI: 10.1039/c3ee41166d
1.50 cm3 g
1 reasonably well, and thus provides a convenient method to screen MOFs for methane
www.rsc.org/ees storage purposes.

Broader context
Natural gas, consisting primarily of methane, is a very promising vehicular fuel, and adsorbent materials for high energy storage of natural gas are highly in
need. The main focus of this article is to study a series of MOF materials for their methane storage and delivery. We not only identify several high methane
storage MOF materials whose storage capacities (181–196 cm3 (STP) cm
3 at 300 K and 35 bar) and methane deliverable amounts (136–140 cm3 (STP) cm
3, at
300 K and from 35 to 5 bar) are among the highest ever reported, but also rationalize an empirical equation to predict methane storage capacities from the pore
volumes of the MOF materials. This work will signicantly facilitate research endeavors on pursuing extraordinarily high methane storage MOF materials in the
near future.

Introduction which consists mostly of methane, has been regarded as one of

the most attractive and promising candidates due to its relative
In recent years, considerable efforts have been devoted to abundance and less adverse effects on the environment.
develop energy carriers for mobile applications to reduce the However, its volumetric energy density under standard condi-
reliance on conventional petroleum-based fuels and lower tions is very low (only 0.11% of that of gasoline) and efficient
carbon emissions. Among the possible fuels, natural gas (NG), storage of methane in a limited volume thus becomes a major

a
College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004, † Electronic supplementary information (ESI) available: PSDs of the MOFs
China investigated (Fig. S1); high-pressure methane isotherms at various
b
NIST Center for Neutron Research, Gaithersburg, Maryland 20899-6102, USA. temperatures for NOTT-101a, NOTT-102a, NOTT-103a and NOTT-109a
E-mail: [email protected] (Fig. S2–5); comparison of methane isotherms at 300 K for all MOFs
c
Department of Materials Science and Engineering, University of Maryland, College investigated (Fig. S6); correlation of excess methane uptakes at room
Park, Maryland 20742, USA temperature and 35 bar with the pore volumes (Fig. S7); the isosteric heat for
d
Department of Materials Science and Engineering, University of Pennsylvania, methane adsorption in the MOFs investigated (Fig. S8); methane sorption in
Philadelphia, Pennsylvania 19104-6272, USA selected MOFs (Table S1); comparison of the experimental excess methane
e uptakes at room temperature and 35 bar and those predicted according to the
Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San
established empirical equation and pore volumes (Table S2); Details of GCMC
Antonio, Texas 78249-0698, USA. E-mail: [email protected]; Fax: +1-210-458-
simulations (Fig. S9–11). See DOI: 10.1039/c3ee41166d
7428

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challenge for its on-board applications. Common storage currently known adsorbent materials meet. In fact, even for
methods like liquefaction and compression suffer from the the previously widely-referred, much lower target of 180 cm3
extreme operating conditions (200–300 bar for compressed (STP) cm
3, there are only a few materials known to meet.8–10,12
methane, and 112 K for liqueed methane) and related energy Additionally, DOE sets a target concerning the gravimetric
waste. Adsorption in porous materials is considered to be one energy density, 0.5 g (methane) g
1 (adsorbent), or 700 cm3
promising method since moderately high-density methane (STP) g
1, which is equally challenging.
storage can be achieved under relatively mild conditions, viz., Considering such a new DOE target for adsorbent based
ambient temperature and moderate pressure (30–60 bar). The methane storage, it is highly desirable to develop a MOF
success of adsorption storage relies on the development of material with even higher methane uptake capacity. Further-
efficient adsorbent materials. more, the ideal materials for practical methane storage should
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Traditional porous materials including zeolites and acti- not only have high methane uptake capacities, but also very
vated carbons have been extensively examined and evaluated as importantly have high deliverable amounts of methane gas,
potential storage media for methane. However, traditional which means that we need to maximize the methane storage
zeolites exhibit methane uptake below 100 cm3 (STP) cm
3 capacities at 35 bar (supposing that the practical storage pres-
(standard temperature and pressure equivalent volume of sure is 35 bar) and at the same time minimize methane uptakes
methane per volume of the adsorbent material; STP: T ¼ at a low pressure of 5 bar (the typical working pressure for
273.15 K, P ¼ 101.325 kPa), while most porous carbon materials natural gas powered internal combustion engines). In order for
show uptake in the range of 50–160 cm3 (STP) cm
3.1 the deliverable methane storage capacity to meet the DOE
Emerging as a new type of porous material, metal–organic target, the total methane uptake at 35 bar has to be signicantly
frameworks (MOFs), which consist of metal ions or metal– higher than the target.
containing clusters linked by organic ligands through metal The overall methane storage capacities of MOF materials
coordination bonds, have attracted much attention for their depend on a variety of factors such as open metal sites, pore
potential applications in gas storage and separation,2–4 in spaces, pore metrics (pore size distributions) and framework
particular for the storage of energy carrier gases (e.g., hydrogen, densities. It is thus very important to systematically study the
methane and acetylene)2 and capture of carbon dioxide,3 effect of these factors on methane storage and delivery. In this
because of their superior merits such as exceptionally high regard, the MOFs constructed from paddlewheel Cu2(CO2)4 and
surface areas, well-dened and chemically tunable pore sizes tetracarboxylates with NbO and/or PtS topologies are of partic-
and geometries, and functionalizable/modiable pore walls. ular interest because this series of MOFs have both variable
In 1997, Kitagawa and co-workers reported for the rst time open copper sites, pore spaces and framework densities.13,14
methane sorption on the porous MOF material [Co2(4,40 -bipyr- Some of them show high hydrogen adsorption capacities, but
idine)3(NO3)4] under high pressure.5 Yaghi's group in 2002 sorption properties for other gases have been less well explored.
investigated methane storage capacities of a series of iso- Herein, we report the detailed methane storage and delivery
reticular MOF compounds.6 Since then, a number of capacities of ve representative MOFs: NOTT-100a (MOF-505a),
researchers have tried to develop MOF materials with higher NOTT-101a, NOTT-102a, NOTT-103a and NOTT-109a. Our
methane sorption capacity.7–10,12 Signicant progress appeared studies show that these MOFs have high methane storage
in 2008–2009, during which two porous MOF materials PCN-14a capacities in the range of 181 to 196 cm3 (STP) cm
3 under 35
(the letter “a” indicates activated MOF materials) by Ma et al.8 bar and 300 K. Furthermore, the deliverable amount of methane
and NiMOF-74a by Wu et al.9 exhibited extraordinarily high of NOTT-103a of 140 cm3 (STP) cm
3 is among the highest of all
methane uptakes of 230 and 200 cm3 (STP) cm
3, respectively, the MOFs reported thus far. The most surprising result is that
at ambient temperature and 35 bar, surpassing the widely- the gravimetric methane storage capacities (cm3 (STP) g
1) of
referred target of 180 cm3 (STP) cm
3 for material-based abso- these MOFs under 35 bar and room temperature can be well
lute methane storage. These results together with the interplay correlated with their corresponding pore volumes (cm3 g
1).
of both open metal sites and optimized pore spaces for high Such a discovery motivates us to examine the feasibility of a
methane storage density in UTSA-20a by Guo et al.10 open up a correlation equation for the evaluation of those reported MOFs,
bright prospect for MOFs as promising methane storage and we have identied an empirical equation that is capable of
materials. predicting the capacities of porous MOFs for methane storage
In 2012, the U.S. DOE initiated a “Methane Opportunities for once we experimentally establish their permanent porosities
Vehicular Energy (MOVE) Program”, and re-set several targets to (pore volumes) and their framework densities. This result could
guide the research on adsorbent based methane storage.11 The signicantly facilitate screening of porous MOFs for their
major target is that the adsorbent-level volumetric energy potential applications on methane storage and hopefully will
density needs to exceed 12.5 MJ L
1 and 9.2 MJ L
1 aer lead to some porous MOFs with extraordinarily high methane
packing losses (25%), at room temperature and low pressure storage and delivery capacities in the near future.
(less than 35 bar). This corresponds to a volumetric storage
capacity of 0.25 g cm
3 or 350 cm3 (STP) cm
3 for the adsorbent Experimental
material. Even if we assume no packing loss, the volumetric
storage capacity still needs to be higher than 260 cm3 (STP) Powder X-ray diffraction (PXRD) patterns were recorded using a
cm
3. Clearly, this is an ambitious target, which none of the Rigaku Ultima IV diffractometer using Cu Ka radiation operated

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at 40 kV and 44 mA with a scan rate of 1.0 deg min
1. A NOTT-102

Micromeritics ASAP 2020 surface area analyzer was used
Quaterphenyl-3,3000 ,5,5000 -tetracarboxylic acid (H4qptc, 50.0 mg,
to obtain N2 sorption isotherms at 77 K, which is maintained by
103.6 mmol) and Cu(NO3)2$2.5H2O (100.0 mg, 429.9 mmol,
a liquid nitrogen bath. High-pressure methane sorption
Aldrich) were mixed and dispersed in DMF/1,4-dioxane/H2O
measurements were performed at the Center for Neutron
(v/v/v, 2/1/1, 15.0 mL). The resulting slurry turned clear upon
Research, National Institute of Standards and Technology
addition of 2 drops of aqueous HCl (37%). The solution was
(NIST) using a computer-controlled Sieverts apparatus, details
heated to 80  C and kept at this temperature for 72 h. The fresh
of which can be found in a previous publication.15 Research- sample was guest-exchanged with dry acetone, and evacuated
grade methane was used for high-pressure measurements with under vacuum at room temperature for 24 h, and then at 100  C
purity of 99.999%.
until the degassing rate reached 5 mmHg min
1 to yield acti-
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In high-pressure studies, excess adsorption and absolute

vated NOTT-102a.
adsorption are frequently used to describe gas adsorption in
porous MOFs. Excess adsorption is the amount of adsorbed
NOTT-103
gas interacting with the frameworks, while absolute adsorp-
tion is the amount of gas both interacting with the frame- A mixture of 5,50 -naphthalene-2,6-diyl-diisophthalic acid (10.0
work and staying in pores in the absence of gas–solid mg, 21.9 mmol) and Cu(NO3)2$2.5H2O (20.0 mg, 86.0 mmol,
interaction. The surface excess adsorbed amount is measured Aldrich) was suspended in a mixed solvent of DMF/1,4-dioxane/
experimentally. The absolute adsorbed amount can be esti- H2O (2.0 mL/0.5 mL/1.0 mL) in a vial (20 mL) under sonication.
mated with the experimentally determined pore volume. Aer the addition of 40 mL of 6.0 M HCl, the vial was placed in
From the viewpoint of methane storage, the absolute amount an oven at 90  C for 24 h. The sample was solvent-exchanged
is more relevant to the practicability of using methane as a with dry acetone, and evacuated under vacuum at room
fuel. In addition, the volumetric uptakes were calculated from temperature for 24 h, and then at 100  C until the degassing rate
the directly measured gravimetric capacities using the MOF reached 5 mmHg min
1 to yield activated NOTT-103a.
crystal densities, thus representing the ideal maximal
methane storage capacities that the MOF materials can NOTT-109
generate in practice. A mixture of 5,50 -naphthalene-1,4-diyl-diisophthalic acid
All MOF samples were synthesized based on the modied (10.0 mg, 21.9 mmol) and Cu(NO3)2$2.5H2O (20.0 mg, 86.0 mmol,
methods reported in the corresponding literature.14 The Aldrich) was suspended in a mixed solvent of DMF and H2O
experimental PXRD patterns are in good agreement with (2.0 mL/1.0 mL) in a vial (20 mL) under sonication. Aer the
the simulated ones, conrming their phase purity. The addition of 40 mL of 6 M HCl, the vial was placed in an oven at
detailed synthetic procedures and activation proles are 90  C for 24 h. The sample was solvent-exchanged with dry
given below. acetone, and evacuated under vacuum at room temperature
for 24 h, and then at 100  C until the degassing rate reached
NOTT-100 5 mmHg min
1 to yield activated NOTT-109a.
Biphenyl-3,30 ,5,50 -tetracarboxylic acid (H4bptc, 50.0 mg,
151.4 mmol) and Cu(NO3)2$2.5H2O (100.0 mg, 429.9 mmol, Results and discussion
Aldrich) were mixed and dispersed in N,N-dimethyl formamide
MOF structures investigated for the methane storage
(DMF)/1,4-dioxane/H2O (v/v/v, 2/1/1, 15.0 mL). The resulting
slurry mixture turned clear upon addition of 2 drops of aqueous Crystal structures and salient pore metrics of the MOFs under
HCl (37%). The solution was heated at 80  C for 72 h. The fresh consideration are shown in Fig. 1 and Table 1, respectively. The
sample was guest-exchanged with dry acetone, and evacuated
under vacuum at room temperature for 24 h, and then at 100  C
for 24 h, and nally at 120  C for 48 h to yield activated NOTT-
100a.

NOTT-101
Terphenyl-3,300 ,5,500 -tetracarboxylic acid (H4tptc, 50.00 mg,
123.0 mmol) and Cu(NO3)2$2.5H2O (100.0 mg, 429.9 mmol,
Aldrich) were mixed and dispersed in DMF/1,4-dioxane/H2O
(v/v/v, 2/1/1, 15.0 mL). The resulting slurry turned clear upon
addition of 2 drops of aqueous HCl (37%). The solution was
heated to 80  C and kept at this temperature for 72 h. The fresh
sample was guest-exchanged with dry acetone, and evacuated
under vacuum at room temperature for 24 h, and then at 100  C Fig. 1 Two types of polyhedral cages are interconnected in an alternating
until the degassing rate reached 5 mmHg min
1 to yield acti- fashion in NOTT-100, NOTT-101, NOTT-103, NOTT-102, and NOTT-109. The
vated NOTT-101a. hydrogen atoms are omitted for clarity.

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Table 1 Structural parameters of the MOFs investigated in this work

SBETa Vpb Pore Dcd

MOFs [m2 g
1] [cm3 g
1] dimensionsc [Å] [g cm
3]

NOTT-100a 1661 0.677 13, 11 0.9265

NOTT-109a 2110 0.850 9  12, 17 0.7899
NOTT-101a 2805 1.080 13  24, 14 0.6838
NOTT-103a 2958 1.157 13  30, 16 0.6432
NOTT-102a 3342 1.268 13  34, 18 0.5872
a
BET surface areas calculated from N2 isotherms at 77 K. b Pore
volumes calculated from the maximum amounts of N2 adsorbed.
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c
Estimated from single-crystal X-ray structures, and taking into
account van der Waals radii. d Framework densities without guest
molecules and terminal waters.

Fig. 2 N2 sorption isotherms at 77 K for all MOF samples investigated. Filled and
structures have been well described in published works.13a,14
open symbols represent the adsorption and desorption data, respectively.
Briey, the frameworks NOTT-100, NOTT-101, MOF-102, and
NOTT-103 are isoreticular but differ due to the lengths of the
bridging ligands employed. In these crystal structures, the
dicopper paddlewheel secondary building blocks (SBUs) formed agreement with the values obtained from their single-crystal
in situ are connected with the rectangular organic building data, indicating that our samples are of high quality and have
blocks to form a three-dimensional noninterpenetrated NbO- been well activated. Table 1 summarizes Brunauer–Emmett–
type framework. The resulting network contains two different Teller (BET) surface areas and pore volumes estimated from N2
cuboctahedral cages. One cuboctahedral cage (red) is composed adsorption experiments at 77 K. We can see that the framework
of 12 ligands connecting 6 paddlewheel SBUs. Another cuboc- NOTT-100a shows the lowest BET surface area and pore volume,
tahedral cage (violet) is formed from 6 ligands connecting 12 while the highest pore volume and BET surface area were
paddlewheel SBUs. The two cuboctahedral cages are connected observed for NOTT-102a.
to each other by sharing three paddlewheel SBUs, and arranged
in an alternating fashion. Different from the systems described
High-pressure methane sorptions
above, NOTT-109 has a different network topology of PtS,
presumably due to the bulky central aromatic groups. In this Temperature-dependent methane sorption isotherms for
structure, there are two distinct types of polyhedral cages. The NOTT-100a as a representative MOF are shown in Fig. 3. The
octadecahedral cage (red) consists of 8 paddlewheel SBUs which corresponding isotherms for the other MOFs are included in the
are bridged by 16 organic building blocks, while the hexahedral ESI† (Fig. S2–5†). All isotherms show an absence of adsorption–
one (violet) consists of 8 dicopper paddlewheel SBUs which are desorption hysteresis, indicating a completely reversible phys-
bridged by 4 organic building blocks. The two types of cages are isorptive process. At 125 K and 2.0 bar, the absolute methane
interconnected to each other by sharing 4 paddlewheel SBUs, adsorption of NOTT-100a reaches 346 cm3 (STP) cm
3, which
and arranged in an alternating fashion. As shown in Fig. 1, corresponds to an adsorbed methane density of 0.247 g cm
3.
changing the length of the ligands in these porous materials This density is 58.4% of that of liquid methane (0.423 g cm
3) at
can dramatically inuence the size and shape of the cages 113 K. The absolute uptake of methane decreases to 326 cm3
within the structures. The pore size distributions (PSDs) for the (STP) cm
3 at 150 K and 7.3 bar. At 300 K and 35 bar, the
ve MOFs were calculated using the well-known method practical conditions for methane storage, the excess adsorption
reported by Gubbins and Bhattacharya (Fig. S1†).16 capacity of methane of NOTT-100a reaches 173 cm3 (STP) cm
3,
corresponding to an absolute adsorption capacity of 195 cm3
(STP) cm
3. Signicantly, the absolute methane uptake of
N2 sorption isotherms NOTT-100a potentially surpasses the old standard (180 cm3
For the estimation of the specic surface area and pore volume, (STP) cm
3) of porous materials for methane storage at ambient
nitrogen adsorption isotherms at 77 K were recorded using an temperature and 35 bar. In fact, the old target is already reached
ASAP 2020 surface area analyzer. Prior to gas sorption by NOTT-100a at 25 bar. The value is among the highest
measurements, all MOF samples were fully activated according reported for MOF materials thus far (Table 2): PCN-14a (230 cm3
to the procedures described above in the experimental section. (STP) cm
3), NiMOF-74a (200 cm3 (STP) cm
3), SNU-500 a (199
All N2 sorption isotherms exhibit typical Type-I sorption cm3 (STP) cm
3), NOTT-107a (196 cm3 (STP) cm
3), UTSA-20a
behavior without hysteresis (Fig. 2), characteristic of micropo- (195 cm3 (STP) cm
3), PCN-11a (191 cm3 (STP) cm
3), NU-125a
rous materials. The N2 uptake of NOTT-100a is in fairly good (183 cm3 (STP) cm
3), Cu-TDPATa (181 cm3 (STP) cm
3). Only
agreement with the reported data,13a,14a while those of NOTT- PCN-14a, SNU-500 a, and NiMOF-74a have higher methane
101a, NOTT-102a, NOTT-103a and NOTT-109a are systemati- uptake capacities than NOTT-100a. It is also worth noting that
cally higher than the reported ones,14b and are in good the methane storage density of 0.222 g cm
3 at 300 K and 35 bar

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in micropores in NOTT-100a, calculated based on the estimated

pore volumes of 0.677 cm3 g
1 using N2 sorption data at 77 K, is
also among the highest densities of methane in porous MOFs
under the same conditions (Table S1†). The value is equivalent
to the density of compressed methane at 300 K and 320 bar, and
is 52% of the density of liquid methane at 113 K and 1 bar. The
methane storage of NOTT-100a is still not saturated, and further
increases to 229 cm3 (STP) cm
3 at 300 K and 63 bar, which is
87% of the DOE's new target of 263 cm3 (STP) cm
3.
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Comparison of high-pressure methane sorptions

A comparison of the methane sorption isotherms for all
measured MOF materials at 300 K is presented in Fig. 4 and S6.†
Let us rst consider the gravimetric methane adsorption
capacity. We can see from Fig. 4a that the augmentation of pore
size from NOTT-100a to NOTT-102a results in a decrease in
gravimetric methane uptake at low pressures (<10 bar), indi-
cating that the methane uptake capacity at low loadings is
mainly controlled by the methane affinity towards the frame-
work likely caused by small pore spaces and high concentration
of accessible copper sites. Of these MOFs, NOTT-100a has the
smallest pore size and the highest density of open copper sites
(4.088 mmol cm
3), thus leading to the highest gravimetric
Fig. 3 Excess (a) and absolute (b) high-pressure methane sorption isotherms of methane uptake capacity in the low pressure regions. However,
NOTT-100a at various temperatures. Filled and open symbols represent adsorp-
tion and desorption data, respectively.

Table 2 Methane adsorption in selected MOFs

Excess CH4 Absolute CH4 Deliverable

uptakea uptakea capacityb
MOFs (cm3 cm
3) (cm3 cm
3) (cm3 cm
3) Reference

PCN-14ac 220 230 137 rer. 8

NiMOF-74a 190 200 84 ref. 9
SNU-500 a 172 199 133 ref. 12d
NOTT-109a 175 196 125 This work
NOTT-107a 172 196 110 ref. 12c
NOTT-100a 173 195 104 This work
UTSA-20a 178 195 101 ref. 10
NOTT-101a 171 194 138 This work
NOTT-103a 169 193 140 This work
PCN-11a 171 191 125 ref. 12a
NU-125a 157 183 130 ref. 7q
NOTT-102a 156 181 136 This work
Cu-TDPATa 157 181 106 ref. 12b
ZJU-25a 155 180 131 ref. 12f
PCN-61a 145 172 127 ref. 7o
SDU-6a 148 172 124 ref. 7n
SDU-7a 137 160 112 ref. 7n
UTSA-40a 134 156 103 ref. 13h
SDU-8a 125 147 99 ref. 7n
NU-111a 109 138 109 ref. 7p
PCN-66a 110 136 101 ref. 7o
PCN-68a 99 128 98 ref. 7o
DUT-49a 82 114 50 ref. 7j
Fig. 4 Absolute gravimetric (a) and volumetric (b) high-pressure methane
a
At room temperature and 35 bar. b Dened as the difference of the sorption isotherms at 300 K for all MOFs investigated. Inset: an enlargement of
amount of methane adsorbed between 35 bar and 5 bar. c At 290 K. the low-pressure region of the sorption isotherms.

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when the pressure goes from 20 bar to 63 bar, the hierarchy of storage amount, Csat, which was determined at 150 K. As shown
the gravimetric methane uptake capacities is reversed, indi- in Fig. 5b, the more porous the MOF, the lower the pore occu-
cating that the pore volume starts to play a dominant role. pancy. That is reasonable, because the pore spaces within MOFs
At low temperature, the saturated methane uptake (cm3 of large pore volumes are basically larger in dimension than
(STP) g
1) correlates well with the N2 pore volume (cm3 g
1). those of small pore volumes, so the larger spaces are less effi-
This is expected because CH4 and N2 can be considered as two ciently utilized for methane storage under 35 bar and room
different probes to evaluate their permanent porosities. From temperature. Furthermore, we found that the pore occupancy is
the collected temperature-dependent methane sorption linearly related with the corresponding pore volume: O ¼ 0.709
isotherms, it was observed that the methane uptakes can be
0.238  Vp, where O is methane storage pore occupancy,
saturated at 150 K under several bar, so we used these data at dimensionless, and Vp is pore volume in cm3 g
1. Thus, the
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150 K as the saturated methane storage capacities to correlate excess methane storage capacity of a specic MOF at room
their relationship with pore volumes. As shown in Fig. 5a, there temperature and 35 bar can be calculated by the equation: C ¼
is a linear data t between the saturated methane storage at O  Csat ¼ (0.709
0.238  Vp)  (
17.728 + 532.234  Vp) ¼
150 K and pore volume: Csat ¼
17.728 + 532.234  Vp, where
126.693  Vp2 + 381.616  Vp
12.571. It can be seen from
Csat is the excess saturated methane uptake at 150 K in cm3 Fig. S7† that when the pore volume is less than 1.50 cm3 g
1, the
(STP) g
1, and Vp is the pore volume in cm3 g
1. In order to gravimetric methane storage capacity increases once the pore
rationalize the relationship between the gravimetric methane volume increases.
storage under 35 bar and room temperature and pore volume, Of course, the high gravimetric methane storage capacity of a
let us dene the pore occupancy, O, under 35 bar and room porous MOF does not secure its high volumetric methane
temperature, as excess methane storage amount under 35 bar storage capacity, because the framework density should be
and room temperature, C, divided by excess saturated methane taken into account for the volumetric one (volumetric methane
storage capacity ¼ gravimetric methane storage capacity 
framework density). The gravimetric methane storage capacity
increases in the order from NOTT-100a, NOTT-109a, NOTT-
101a, NOTT-103a to NOTT-102a; at the same time, their
framework density decreases accordingly. At 300 K and 35 bar,
their volumetric methane uptakes are 195 cm3 (STP) cm
3, 196
cm3 (STP) cm
3, 194 cm3 (STP) cm
3, 193 cm3 (STP) cm
3, and
181 cm3 (STP) cm
3 for NOTT-100a, NOTT-109a, NOTT-101a,
NOTT-103a and NOTT-102a, respectively (Fig. 4b). It needs to be
mentioned that the real packing density of an MOF material is
lower than its crystal density, so the exact volumetric methane
storage capacities of these MOFs are lower than the above
reported ones, and comparison with other microporous mate-
rials such as activated carbons should be careful.

Comparison of deliverable amounts

When evaluating the performance of an adsorbent for vehicular
application, the deliverable capacity of methane gas is more
important because it determines the driving range of natural
gas vehicles (NGVs). Obviously, in a fuel system, the tank
pressure will not reduce to a level below atmosphere pressure,
and typical working pressures for natural gas powered internal
combustion engines are around 5 bar. Therefore, for vehicular
ANG technologies, the deliverable amount of methane may be
referred to as the difference in the amount of methane adsorbed
between 5 bar and the upper working limit of the system,
typically 35 bar. Using room temperature adsorption isotherms,
we can estimate the deliverable amount under isothermal
conditions, as illustrated in Fig. 6, using NOTT-100a as an
Fig. 5 (a) Saturated excess gravimetric methane adsorption capacity at 150 K example. The specic capacities are presented in Table 2, along
(cm3 (STP) g
1) versus pore volume (cm3 g
1) of the MOFs investigated. (b) Pore with similarly estimated capacities based on literature reports
occupancy versus pore volume (cm3 g
1). Pore occupancy is defined as the
of MOFs. Of all the ve MOFs studied here, NOTT-100a has the
excess gravimetric methane uptake at 300 K and 35 bar divided by the
saturated excess gravimetric methane uptake at 150 K. The solid lines show
poorest deliverable amount of methane due to the smallest pore
the linear fitting results. 1: NOTT-100a; 2: NOTT-109a; 3: NOTT-101a; 4: NOTT- size and the highest density of open copper sites. When the pore
103a; 5: NOTT-102a. sizes are enlarged from NOTT-100a to NOTT-102a, the

2740 | Energy Environ. Sci., 2013, 6, 2735–2744 This journal is ª The Royal Society of Chemistry 2013
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Paper Energy & Environmental Science

less than 1.50 cm3 g
1, so extending such an empirical equation

beyond this region might not be applicable; (2) MOFs with even
larger pore volumes above 1.50 cm3 g
1 in general cannot take
up a large amount of methane volumetrically because of their
signicantly low framework densities and weak gas-framework
interactions. The detailed comparison of the experimentally
determined excess methane uptakes at room temperature and
35 bar and the ones predicted from this empirical equation is
listed in Table S2.† As shown in Fig. 7, the calculated methane
uptakes from this empirical equation systematically match with
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the experimentally determined methane storage ones well (the

average deviation is 8.1%), indicating that with this empirical
equation it is feasible to predict the methane storage capacities
of microporous MOF materials once we establish their perma-
nent porosities (pore volumes) and framework densities. The
Fig. 6 Schematic of the determination of the deliverable amount using NOTT- methane storage capacity predicted by this empirical formula
100a as an example, which is defined as the difference between the absolute inevitably has an error bar, due to the diverse chemistry of the
adsorption amount between 35 bar and 5 bar under isothermal conditions.
MOF structures. In spite of this, we emphasize that the empir-
ical formula is still very useful, as a simple calculation can
provide a valuable initial clue about the methane storage
deliverable amount of methane rstly increases and then capacity of a given microporous MOF. This is very important for
decreases. NOTT-103a has the highest deliverable amount of the community to screen the potential MOFs for high methane
140 cm3 (STP) cm
3, close to 3/4 of the absolute uptake, indi- storage; we can then concentrate on those very promising ones
cating NOTT-103a has a more optimal pore geometry, which is and study their activation prole and methane storage carefully,
suitable for methane delivery. The amount of delivered
methane for NOTT-101a (138 cm3 (STP) cm
3), NOTT-102a
(136 cm3 (STP) cm
3) and NOTT-103a (140 cm3 (STP) cm
3) are
among the highest ones for the reported MOF materials such as
PCN-14a (137 cm3 (STP) cm
3), SNU-500 a (133 cm3 (STP) cm
3),
ZJU-25a (131 cm3 (STP) cm
3), NU-125a (130 cm3 (STP) cm
3),
PCN-61a (127 cm3 (STP) cm
3), PCN-11a (125 cm3 (STP) cm
3)
and SDU-6a (124 cm3 (STP) cm
3) (Table 2). It is worth noting
that NiMOF-74a has the second high volumetric methane
uptake of 200 cm3 (STP) cm
3; however, the deliverable amount
of methane is only 84 cm3 (STP) cm
3, less than a half of the
absolute uptake. The relatively high retention of methane in
NiMOF-74a at low pressures can be explained considering that
it possesses the highest density of open metal sites. Therefore,
to maximize the deliverable capacity of the sorbent, it is
necessary to minimize the amount of methane stored at unus-
able pressure, i.e. below 5 bar. Because the open metal sites play
the most important role in methane storage below 5 bar,
pursuing MOFs with high open metal sites will not be a good
strategy to target MOFs with high methane delivery.

Empirical equation to predict methane storage capacity under

35 bar and room temperature
The fact that the excess methane storage capacities of the ve
examined MOFs can be well correlated by the equation C ¼

126.693  Vp2 + 381.616  Vp
12.571 with their corre-
sponding pore volumes encourages us to examine the applica-
bility of this empirical equation to other MOFs reported in the
literature for methane storage. We apply this equation to those
MOFs in the microporous regions with pore volume less than Fig. 7 Comparison of the experimentally determined excess methane uptakes
1.50 cm3 g
1. Such a selection is based on the following at ambient temperature and 35 bar and those predicted according to the
considerations. (1) The ve examined MOFs have pore volumes established empirical equation and pore volumes.

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Energy & Environmental Science Paper

and thus target the most practically useful MOF materials for methane delivery amounts are among the highest ever reported,
methane storage within a short period of time. Because the but also rationalizes an empirical equation to predict methane
porosities of MOFs are very sensitive to the activation proles storage capacities from the pore volumes of the MOF materials.
due to their exible structural nature, this empirical equation This work will signicantly facilitate research endeavors on
might also provide us some guidance on whether an optimized pursuing extraordinarily high methane storage MOF materials.
activation can further enhance the methane storage perfor- It might also provide some guidance for the search of other
mance of a microporous MOF. porous framework materials such as covalent-organic frame-
works (COFs) for methane storage at room temperature. It is
foreseen that new porous MOFs with even higher methane
GCMC simulations
storage capacity and delivery amount will be developed and
To study the methane adsorption and storage mechanism of the
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some may have the potential to be practically implemented for

ve MOFs, we perform detailed computational investigations. natural gas powered vehicles in the near future.
Previous studies on methane storage in other MOFs with
dicopper paddlewheel units have well established that the open
copper site binds methane strongly, and is one of primary
Acknowledgements
methane adsorption sites.9,10,17 The same is expected for the ve This work was supported by an Award AX-1730 from Welch
MOFs studied here since they also contain the same dicopper Foundation (BC). T. Y. acknowledges partial support from the
units. Direct binding of one methane molecule at each copper DOE BES Grant no. DE-FG02-08ER46522.
site produces the storage capacity of 92, 61, 58, 50 and 43 cm3
(STP) cm
3 for NOTT-100a, NOTT-109a, NOTT-101a, NOTT-103a
and NOTT-102a, respectively. Structurally, adsorption on the Cu
Notes and references
sites would fully occupy the surface of one of the two pores (the 1 (a) D. Lozano-Castelló, J. Alca~
niz-Monge, M. A. d. l. Casa-
pore denoted by the red polyhedral cage in Fig. 1) in these Lillo, D. Cazorla-Amorós and A. Linares-Solano, Fuel, 2002,
MOFs. Our grand canonical Monte Carlo (GCMC) simulations 81, 1777–1803; (b) V. C. Menon and S. Komarneni, J. Porous
(see ESI† for details) show that other strong methane adsorp- Mater., 1998, 5, 43–58.
tion sites are mainly located at the channels interconnecting the 2 (a) L. J. Murray, M. Dincă and J. R. Long, Chem. Soc. Rev.,
two pores. The number of these channel sites is equal to 2/3 of 2009, 38, 1294–1314; (b) J. Sculley, D. Yuan and H.-C. Zhou,
that of the Cu sites. Interestingly, the experimental methane Energy Environ. Sci., 2011, 4, 2721–2735; (c) M. P. Suh,
uptake measured at 300 K and 5 bar in these MOFs roughly H. J. Park, T. K. Prasad and D.-W. Lim, Chem. Rev., 2012,
corresponds to the full adsorption capacity of the Cu sites, 112, 782–835; (d) X. Lin, N. R. Champness and
suggesting that the two strong adsorption sites (Cu sites and M. Schröder, Top. Curr. Chem., 2010, 293, 35–76; (e) S. Ma
channel sites) are 60% populated under this condition. This and H.-C. Zhou, Chem. Commun., 2010, 46, 44–53; (f)
conrms that methane adsorption at low pressure is indeed W. Zhou, Chem. Rec., 2010, 10, 200–204; (g) T. A. Makal,
dominated by strong adsorption sites, and high density of open J.-R. Li, W. Lu and H.-C. Zhou, Chem. Soc. Rev., 2012, 41,
metals is detrimental to the methane delivery capacity, as dis- 7761–7779; (h) K. Konstas, T. Osl, Y. Yang, M. Batten,
cussed earlier. GCMC simulations also show that at higher N. Burke, A. J. Hill and M. R. Hilla, J. Mater. Chem., 2012,
pressure, methane molecules start to populate the surface of the 22, 16698–16708; (i) R. B. Getman, Y.-S. Bae, C. E. Wilmer
other pore (denoted by the violet polyhedral cage in Fig. 1), and R. Q. Snurr, Chem. Rev., 2012, 112, 703–723; (j) Y. He,
followed by the pore lling of the void space at the pore center. W. Zhou, R. Krishna and B. Chen, Chem. Commun., 2012,
These secondary adsorption sites have relatively low adsorption 48, 11813–11831; (k) Z. Zhang, S. Xiang and B. Chen,
energy, but their contributions to the methane capacity, in CrystEngComm, 2011, 13, 5983–5992.
particular delivery capacity, are probably more important than 3 (a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald,
previously believed.17 As it has been pointed out before,18,19 the E. D. Bloch, Z. R. Herm, T.-H. Bae and J. R. Long, Chem.
gas populating process on different adsorption sites depends Rev., 2012, 112, 724–781; (b) D. M. D'Alessandro, B. Smit
strongly on temperature. At higher temperature, the difference and J. R. Long, Angew. Chem., Int. Ed., 2010, 49, 6058–6082;
between primary adsorption sites and secondary adsorption (c) Y.-S. Bae and R. Q. Snurr, Angew. Chem., Int. Ed., 2011,
sites becomes small for gas adsorption. At room temperature, 50, 11586–11596; (d) Y. Liu, Z. U. Wang and H.-C. Zhou,
the CH4 adsorption locations identied are essentially the same Greenhouse Gases: Sci. Technol., 2012, 2, 239–259; (e)
as those at 200 K, while the gas populations on different sites Z. Zhang, Y. Zhao, Q. Gong, Z. Li and J. Li, Chem.
become less distinctive. Commun., 2013, 49, 653–661; (f) S. Xiang, Y. He, Z. Zhang,
H. Wu, W. Zhou, R. Krishna and B. Chen, Nat. Commun.,
Conclusions 2012, 3, 954; (g) J. M. Simmons, H. Wu, W. Zhou and
T. Yildirim, Energy Environ. Sci., 2011, 4, 2177–2185; (h)
Microporous MOFs are certainly very promising materials for J.-R. Li, J. Sculley and H.-C. Zhou, Chem. Rev., 2012, 112,
methane storage at room temperature. Our work not only 869–932.
reveals several high methane storage MOF materials whose 4 (a) D. Britt, H. Furukawa, B. Wang, T. G. Glover and
storage capacities can be up to 196 cm3 (STP) cm
3 and O. M. Yaghi, Proc. Natl. Acad. Sci. U. S. A., 2009, 106,

2742 | Energy Environ. Sci., 2013, 6, 2735–2744 This journal is ª The Royal Society of Chemistry 2013
 View Article Online

Paper Energy & Environmental Science

20637–20640; (b) O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, I. Senkovska and S. Kaskel, Chem. Commun., 2012, 48,
H. K. Chae, M. Eddaoudi and J. Kim, Nature, 2003, 423, 10841–10843; (k) P. D. C. Dietzel, V. Besikiotis and
705–714; (c) S. Kitagawa, R. Kitaura and S.-i. Noro, Angew. R. Blom, J. Mater. Chem., 2009, 19, 7362–7370; (l) C. Tan,
Chem., Int. Ed., 2004, 43, 2334–2375; (d) S. Horike, S. Yang, N. R. Champness, X. Lin, A. J. Blake, W. Lewis and
Y. Inubushi, T. Hori, T. Fukushima and S. Kitagawa, Chem. M. Schröder, Chem. Commun., 2011, 47, 4487–4489; (m)
Sci., 2012, 3, 116–120; (e) P. L. Llewellyn, S. Bourrelly, H. J. Park, D.-W. Lim, W. S. Yang, T.-R. Oh and M. P. Suh,
C. Serre, Y. Filinchuk and G. Férey, Angew. Chem., Int. Ed., Chem.–Eur. J., 2011, 17, 7251–7260; (n) X. Zhao, D. Sun,
2006, 45, 7751–7754; (f) S.-T. Zheng, J. T. Bu, Y. Li, T. Wu, S. Yuan, S. Feng, R. Cao, D. Yuan, S. Wang, J. Dou and
F. Zuo, P. Feng and X. Bu, J. Am. Chem. Soc., 2010, 132, D. Sun, Inorg. Chem., 2012, 51, 10350–10355; (o) D. Yuan,
17062–17064; (g) Q. Lin, T. Wu, S.-T. Zheng, X. Bu and D. Zhao, D. Sun and H.-C. Zhou, Angew. Chem., Int. Ed.,
Published on 12 July 2013. Downloaded by University of Ottawa on 1/29/2022 7:21:31 PM.

P. Feng, J. Am. Chem. Soc., 2012, 134, 784–787; (h) 2010, 49, 5357–5361; (p) Y. Peng, G. Srinivas, C. E. Wilmer,
H.-L. Jiang and Q. Xu, Chem. Commun., 2011, 47, 3351– R. Q. Snurr, J. T. Hupp, T. Yildirim and O. K. Farha, Chem.
3370; (i) J.-P. Zhang and X.-M. Chen, J. Am. Chem. Soc., Commun., 2013, 49, 2992–2994; (q) C. E. Wilmer,
2009, 131, 5516–5521; (j) J. An, S. J. Geib and N. L. Rosi, O. K. Farha, T. Yildirim, I. Eryazici, V. Krungleviciute,
J. Am. Chem. Soc., 2010, 132, 38–39; (k) W.-Y. Gao, W. Yan, A. A. Sarjeant, R. Q. Snurr and J. T. Hupp, Energy Environ.
R. Cai, K. Williams, A. Salas, L. Wojtas, X. Shi and S. Ma, Sci., 2013, 6, 1158–1163; (r) J. I. Feldblyum, D. Dutta,
Chem. Commun., 2012, 48, 8898–8900; (l) Y. He, R. Krishna A. G. Wong-Foy, A. Dailly, J. Imirzian, D. W. Gidley and
and B. Chen, Energy Environ. Sci., 2012, 5, 9107–9120; (m) A. J. Matzger, Langmuir, 2013, 29, 8146–8153.
E. D. Bloch, W. L. Queen, R. Krishna, J. M. Zadrozny, 8 S. Ma, D. Sun, J. M. Simmons, C. D. Collier, D. Yuan and
C. M. Brown and J. R. Long, Science, 2012, 335, 1606–1610; H.-C. Zhou, J. Am. Chem. Soc., 2008, 130, 1012–1016.
(n) Y.-S. Bae, C. Y. Lee, K. C. Kim, O. K. Farha, P. Nickias, 9 H. Wu, W. Zhou and T. Yildirim, J. Am. Chem. Soc., 2009, 131,
J. T. Hupp, S. T. Nguyen and R. Q. Snurr, Angew. Chem., 4995–5000.
Int. Ed., 2012, 51, 1857–1860; (o) C. Y. Lee, Y.-S. Bae, 10 Z. Guo, H. Wu, G. Srinivas, Y. Zhou, S. Xiang, Z. Chen,
N. C. Jeong, O. K. Farha, A. A. Sarjeant, C. L. Stern, Y. Yang, W. Zhou, M. O'Keeffe and B. Chen, Angew. Chem.,
P. Nickias, R. Q. Snurr, J. T. Hupp and S. T. Nguyen, J. Am. Int. Ed., 2011, 50, 3178–3181.
Chem. Soc., 2011, 133, 5228–5231; (p) E. Q. Procopio, 11 See DOE MOVE program at https://arpa-e-foa.energy.gov/.
F. Linares, C. Montoro, V. Colombo, A. Maspero, E. Barea 12 (a) X.-S. Wang, S. Ma, K. Rauch, J. M. Simmons, D. Yuan,
and J. A. R. Navarro, Angew. Chem., Int. Ed., 2010, 49, 7308– X. Wang, T. Yildirim, W. C. Cole, J. J. López, A. d. Meijere
7311; (q) S. Qiu and G. Zhu, Coord. Chem. Rev., 2009, 253, and H.-C. Zhou, Chem. Mater., 2008, 20, 3145–3152; (b)
2891–2911. B. Li, Z. Zhang, Y. Li, K. Yao, Y. Zhu, Z. Deng, F. Yang,
5 M. Kondo, T. Yoshitomi, K. Seki, H. Matsuzaka and X. Zhou, G. Li, H. Wu, N. Nijem, Y. J. Chabal, Z. Lai,
S. Kitagawa, Angew. Chem., Int. Ed., 1997, 36, 1725–1727. Y. Han, Z. Shi, S. Feng and J. Li, Angew. Chem., Int. Ed.,
6 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, 2012, 51, 1412–1415; (c) C. E. Wilmer, M. Leaf, C. Y. Lee,
M. O'Keeffe and O. M. Yaghi, Science, 2002, 295, 469–472. O. K. Farha, B. G. Hauser, J. T. Hupp and R. Q. Snurr, Nat.
7 (a) K. Seki, Chem. Commun., 2001, 1496–1497; (b) Chem., 2012, 4, 83–89; (d) T. K. Prasad, D. H. Hong and
S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, M. P. Suh, Chem.–Eur. J., 2010, 16, 14043–14050; (e) D. Liu,
T. Loiseau and G. Férey, J. Am. Chem. Soc., 2005, 127, H. Wu, S. Wang, Z. Xie, J. Li and W. Lin, Chem. Sci., 2012,
13519–13521; (c) P. L. Llewellyn, S. Bourrelly, C. Serre, 3, 3032–3037; (f) X. Duan, J. Yu, J. Cai, Y. He, C. Wu,
A. Vimont, M. Daturi, L. Hamon, G. D. Weireld, W. Zhou, T. Yildirim, Z. Zhang, S. Xiang, M. O'Keeffe,
J.-S. Chang, D.-Y. Hong, Y. K. Hwang, S. H. Jhung and B. Chen and G. Qian, Chem. Commun., 2013, 49, 2043–2045.
G. Férey, Langmuir, 2008, 24, 7245–7250; (d) H. Kim, 13 (a) B. Chen, N. W. Ockwig, A. R. Millward, D. S. Contreras
D. G. Samsonenko, S. Das, G.-H. Kim, H.-S. Lee, and O. M. Yaghi, Angew. Chem., Int. Ed., 2005, 44, 4745–
D. N. Dybtsev, E. A. Berdonosova and K. Kim, Chem.–Asian 4749; (b) Y.-G. Lee, H. R. Moon, Y. E. Cheon and
J., 2009, 4, 886–891; (e) I. Senkovska and S. Kaskel, M. P. Suh, Angew. Chem., Int. Ed., 2008, 47, 7741–7745; (c)
Microporous Mesoporous Mater., 2008, 112, 108–115; (f) Y. Hu, S. Xiang, W. Zhang, Z. Zhang, L. Wang, J. Bai and
K. Gedrich, I. Senkovska, N. Klein, U. Stoeck, A. Henschel, B. Chen, Chem. Commun., 2009, 7551–7553; (d) D. Sun,
M. R. Lohe, I. A. Baburin, U. Mueller and S. Kaskel, Angew. S. Ma, J. M. Simmons, J.-R. Li, D. Yuan and H.-C. Zhou,
Chem., Int. Ed., 2010, 49, 8489–8452; (g) N. Klein, Chem. Commun., 2010, 46, 1329–1331; (e) D. Zhao,
I. Senkovska, K. Gedrich, U. Stoeck, A. Henschel, D. Yuan, A. Yakovenko and H.-C. Zhou, Chem. Commun.,
U. Mueller and S. Kaskel, Angew. Chem., Int. Ed., 2009, 48, 2010, 46, 4196–4198; (f) S. Yang, X. Lin, A. Dailly,
9954–9957; (h) N. Klein, I. Senkovska, I. A. Baburin, A. J. Blake, P. Hubberstey, N. R. Champness and
R. Grünker, U. Stoeck, M. Schlichtenmayer, B. Streppel, M. Schröder, Chem.–Eur. J., 2009, 15, 4829–4835; (g)
U. Mueller, S. Leoni, M. Hirscher and S. Kaskel, Chem.–Eur. M. Xue, G. Zhu, Y. Li, X. Zhao, Z. Jin, E. Kang and S. Qiu,
J., 2011, 17, 13007–13016; (i) R. Grünker, V. Bon, Cryst. Growth Des., 2008, 8, 2478–2483; (h) Y. He, S. Xiang,
A. Heerwig, N. Klein, P. Müller, U. Stoeck, I. A. Baburin, Z. Zhang, S. Xiong, C. Wu, W. Zhou, T. Yildirim,
U. Mueller, I. Senkovska and S. Kaskel, Chem.–Eur. J., 2012, R. Krishna and B. Chen, J. Mater. Chem. A, 2013, 1,
18, 13299–13303; (j) U. Stoeck, S. Krause, V. Bon, 2543–2551.

This journal is ª The Royal Society of Chemistry 2013 Energy Environ. Sci., 2013, 6, 2735–2744 | 2743
 View Article Online

Energy & Environmental Science Paper

14 (a) X. Lin, J. Jia, X. Zhao, K. M. Thomas, A. J. Blake, 16 S. Bhattacharya and K. E. Gubbins, Langmuir, 2006, 22,
G. S. Walker, N. R. Champness, P. Hubberstey and 7726–7731.
M. Schröder, Angew. Chem., Int. Ed., 2006, 45, 7358–7364; 17 H. Wu, J. M. Simmons, Y. Liu, C. M. Brown, X.-S. Wang,
(b) X. Lin, I. Telepeni, A. J. Blake, A. Dailly, C. M. Brown, S. Ma, V. K. Peterson, P. D. Southon, C. J. Kepert,
J. M. Simmons, M. Zoppi, G. S. Walker, K. M. Thomas, H.-C. Zhou, T. Yildirim and W. Zhou, Chem.–Eur. J., 2010,
T. J. Mays, P. Hubberstey, N. R. Champness and 16, 5205.
M. Schröder, J. Am. Chem. Soc., 2009, 131, 2159–2171. 18 J. R. Karra and K. S. Walton, Langmuir, 2008, 24, 8620–8626.
15 W. Zhou, H. Wu, M. R. Hartman and T. Yildirim, J. Phys. 19 S. M. P. Lucena, P. G. M. Mileo, P. F. G. Silvino, J. Célio and
Chem. C, 2007, 111, 16131–16137. L. Cavalcante, J. Am. Chem. Soc., 2011, 133, 19282–19285.
Published on 12 July 2013. Downloaded by University of Ottawa on 1/29/2022 7:21:31 PM.

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