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Methane storage in metal–organic frameworks

Cite this: Chem. Soc. Rev., 2014,
Yabing He,a Wei Zhou,bc Guodong Qiand and Banglin Chen*e
43, 5657
Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications.
Realization of safe, cheap and convenient means and materials for high-capacity methane storage can
significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based
Received 19th January 2014 process involving porous materials offers an efficient storage methodology and the emerging porous
DOI: 10.1039/c4cs00032c metal–organic frameworks have been explored as potential candidates because of their extraordinarily
high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide
www.rsc.org/csr an overview of the current status of metal–organic frameworks for methane storage.
1. Introduction power plants and automobile transport is a growing environ-

mental issue. Considerable efforts have been devoted to
With the booming development of economy, the demand for develop alternative cleaner fuels to alleviate the pressure on
crude oil has increased steadily, and as a result concern has environment and reduce the strong reliance on crude oil.
arisen about the sustainability of oil reserves. Furthermore, Hydrogen is considered as an ideal clean energy source since
the anthropogenic emission of CO2 from fossil fuel burning in no greenhouse gases or other environmentally harmful mole-
cules are released during energy extraction. However, the
current technology is still far from commercialization. Natural
a
College of Chemistry and Life Sciences, Zhejiang Normal University,
gas (NG), which mainly consists of methane, is considered as a
Jinhua 321004, China
b
NIST Center for Neutron Research, Gaithersburg, Maryland 20899-6102, USA.
preferable alternative fuel since it is naturally abundant and
E-mail: [email protected] relatively environmentally friendly compared to conventional
c
Department of Materials Science and Engineering, University of Maryland, liquid hydrocarbon fuels. It may serve as a bridge fuel to
College Park, Maryland 20742, USA help us through the transition from crude oil to future clean/
d
State Key Laboratory of Silicon Materials, Department of Materials Science &
renewable energy.
Engineering, Zhejiang University, Hangzhou 310027, China
e
Department of Chemistry, University of Texas at San Antonio, One UTSA Circle,
Among all hydrocarbons, methane has the highest hydrogen
San Antonio, Texas 78249-0698, USA. E-mail: [email protected]; to carbon ratio and consequently the higher research octane
Fax: +1-210-458-7428 number (RON = 107), and combustion of methane produces the
Yabing He earned his PhD in Wei Zhou received his PhD in

organic chemistry from Changchun 2005 from the University of
Institute of Applied Chemistry, Pennsylvania, under the super-
Chinese Academy of Sciences, vision of Prof. John E. Fischer.
under the direction of Prof. From 2005 to 2007, he was a
Lianxun Gao in 2010. After that, post-doctoral researcher at the
he worked in the group of Prof. NIST Center for Neutron Research
Banglin Chen at University of (NCNR), working with Dr Taner
Texas at San Antonio as a post- Yildirim. After that, he was
doctoral Research Fellow. In 2012, appointed to his current position
he joined the Faculty of Zhejiang as a research scientist at NCNR
Normal University. His current and the University of Maryland.
Yabing He research focuses on the design and Wei Zhou His research interests are in the
synthesis of porous materials and areas of novel porous materials,
the study of their gas adsorption computational materials design,
and separation properties. and neutron spectroscopy.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev., 2014, 43, 5657--5678 | 5657
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smallest amount of CO2 for each unit of heat that is released. practical application in methane storage. As for activated
However, the relatively low volumetric energy density of carbon, difficulty in tuning pore shapes and sizes has limited
methane under normal conditions, only 0.11% of that of gaso- the utility. Typically, traditional zeolites exhibit methane
line, severely exerts constraints on its applications in various uptake below 100 cm3 (STP) cm3 (standard temperature and
possible fields, particularly on-board applications. Therefore, pressure equivalent volume of methane per volume of the
for large scale usage, it is necessary to develop a safe and adsorbent material; STP: T = 273.15 K, P = 101.325 kPa), while
efficient technology to obtain a competitive volumetric energy most porous carbon materials show methane uptake in the
density. Four different methods have been proposed for the range of 50–160 cm3 (STP) cm3.1,2
storage of natural gas, i.e., Liquefied Natural Gas (LNG), Com- Recently, the Advanced Research Projects Agency – Energy
pressed Natural Gas (CNG), Adsorbed Natural Gas (ANG) and (ARPA-E) of the U.S. Department of Energy (DOE) reset the new
Natural Gas Hydrate (NGH). CNG is stored as a supercritical methane storage target to guide the research on adsorbent
fluid at room temperature and 200–300 bar by using a steel based methane storage.3 The adsorbent level volumetric energy
cylinder. The main disadvantages of CNG storage are the need density needs to exceed 12.5 MJ L1 and 9.2 MJ L1 after
for expensive and heavy high pressure storage vessels, costly packing losses at room temperature. This corresponds to a
multistage compression facilities, and potential safety con- volumetric storage capacity of 350 cm3 (STP) cm3 for the
cerns. LNG is obtained by cryogenic techniques and stored as adsorbent material. Even if there is no packing loss, the volu-
a boiling liquid at 112 K and 100 kPa. Even though LNG has metric storage capacity still needs to be higher than 263 cm3
high energy density, LNG needs special Dewar containers, and (STP) cm3, equivalent to that of CNG at 250 bar and 298 K. The
low temperature should be maintained. Moreover, periodic volumetric storage target is significantly higher than the previous
venting is needed because of pressure buildup in a cryogenic one of 180 cm3 (STP) cm3 at 35 bar.4 Additionally, DOE sets a
fuel tank. NGH is also undesirable for practical applications target concerning the gravimetric energy density, 0.5 g (CH4) g1
due to the rigorous formation conditions and low formation (adsorbent). Accordingly, new porous adsorbents are required to
rate. Besides, the stored gas cannot be released from hydrate meet these challenging storage targets in order for the ANG
just by reducing pressure. The ANG technology is a booming technology to become practical.
technology that combines much lower pressures than those Emerging as a new class of porous materials, metal–organic
required for CNG and may be achieved at room temperature, frameworks (MOFs) have been intensively studied during the
unlike liquefaction. This reduction in pressure allows using past decades. They comprise metal ions or metal containing
lightweight, inexpensive, conformable fuel tanks and single clusters (generally termed as secondary building blocks (SBUs))
stage compressors, and also facilitates at-home refuelling. linked by multitopic organic ligands to form 3D networks.
Development of efficient adsorbent materials is key to the A large number of possible organic linkers combined with a
success of the ANG technology. Many different porous materials plenty of metal ions and metal ion clusters lead to a huge range
have been extensively examined and evaluated as potential of potential porous materials with a variety of pore surface
methane storage media. The early studies have mainly focused properties and chemically tunable structures, which have been
on traditional porous materials such as zeolites and activated assessed for a number of applications including gas storage
carbons. Despite relatively high packing densities, the low and separation, catalysis, drug delivery, optical and electronic
micropore and extreme hydrophilicity of zeolites limit its applications, and sensing.5–25 For gas storage application,
Guodong Qian was born in Banglin Chen was born in

Zhejiang, China. He received his Zhejiang, China. He received his
bachelor’s (1988) and master’s BS (1985) and MS (1988) degrees
(1992) degrees in Materials in Chemistry from Zhejiang
Science from Zhejiang University University in China, and PhD
in China. He joined the Materials from National University of
Department of Zhejiang Singapore in 2000. He has worked
University after obtaining his with Professors Omar M. Yaghi at
PhD degree from Zhejiang University of Michigan, Stephen
University in 1997. He was Lee at Cornell University
promoted to associate professor, and Andrew W. Maverick at
full professor and Cheung Kong Louisiana State University as a
Guodong Qian professor in 1999, 2002 and Banglin Chen postdoctoral fellow during
2011, respectively. His current 2000–2003 before joining the
research interests include hybrid organic–inorganic photonic func- University of Texas-Pan American in 2003. He moved to the
tional materials, cathode or anode materials of lithium-ion University of Texas at San Antonio in August 2009, and now he
batteries, and multifunctional porous materials. is the Professor of Chemistry.
5658 | Chem. Soc. Rev., 2014, 43, 5657--5678 This journal is © The Royal Society of Chemistry 2014
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early research on these materials was mostly related to H2. packing densities and crystallographic densities for three
However, the weak interaction between H2 and the surface of MOFs.27 Also, mercury intrusion porosimetry can lead to pro-
MOFs has limited H2 storage to low temperature, typically 77 K. blems in that the values obtained are strongly dependent on the
Unlike hydrogen, the interaction energy between methane and mercury pressure at which the intrusion is measured. For
the surface of MOFs is already large enough to give reasonable example, Seki et al. used this technique to obtain a density
adsorption at room temperature. A growing number of MOFs that is even higher than the ideal crystal density.28
have been reported for methane storage. Significantly, several

MOFs exhibit methane adsorption capacities comparable to or 2.3 Deliverable capacity and storage capacity
exceeding those of the best activated carbons. A good methane storage material should not only possess a high
maximum adsorption capacity but more importantly should
have a high deliverable capacity. The deliverable capacity, or
2. Fundaments of ANG storage working capacity, is defined as the amount of gas released when
2.1 Excess, absolute and total adsorption the pressure is reduced. Obviously, the deliverable capacity is
less than the storage capacity. On the one hand, the delivered
In evaluating the methane storage capacities of porous materials, amount depends on the conditions used to trigger the gas
the measurement of adsorption isotherms is a fundamental step. release. For example, use of heat or vacuum may trigger much
Two different experimental techniques used to measure the more gas to be desorbed. On the other hand, the deliverable
amount adsorbed are the volumetric measurement using Sieverts capacity is sensitive to the thermal effects produced due to
apparatus and the gravimetric method using a microbalance. charge and discharge. If the heat of adsorption released during
In reported literatures, the terms such as excess, absolute, and charge is not removed from the storage system, less methane is
total have frequently been used to describe the gas adsorption adsorbed. If the heat of adsorption is not resupplied during
capacities.8,26 The excess adsorption corresponds to the amount discharge, the residual amount increases. A possible method
of gas interacting with the framework, while the absolute adsorp- proposed to address this issue consists of introducing in the
tion is the amount of gas both interacting with the framework adsorbent bed an encapsulated phase change material that has a
and staying in the adsorbed region in the absence of gas–solid relatively high heat of fusion at ambient temperature. This
interactions. Total adsorption corresponds to the amount of all material would be capable of adsorbing the heat of adsorption
gas in the pore. The surface excess adsorbed amount is measured released during charge and resupplying it during discharge.
experimentally. Since the experimental techniques applied The volumetric deliverable capacity is more important for
cannot determine the boundary between the adsorbed phase improving the driving range of natural gas vehicles (NGVs). For
and the bulk gas phase, the absolute adsorption uptake cannot MOFs, the delivery amounts are frequently calculated as the
be determined accurately. For gas uptake and delivery purpose, difference in the amount of methane adsorbed between the upper
the total adsorbed amount is a more relevant quantity com- and lower limiting working pressure at isothermal conditions
pared to the excess one. instead of the practical conditions. Recognizing that a sufficient
pressure differential must be provided to drive a sufficient
2.2 Gravimetric and volumetric uptakes methane flow rate from the adsorbent to the engine, and that a
Gas adsorption capacities can be expressed in gravimetric typical working pressure for natural gas powered internal com-
or volumetric uptake. Gravimetric uptake is the mass of gas bustion engines is around 5 bar, 5 bar has been taken as the lower
adsorbed per unit mass of adsorbent; while the volumetric one is limiting working pressure by several groups.8,29,30 A pressure of
the volume of gas adsorbed under standard conditions divided around 35 or 65 bar is considered the upper limiting working
by the volume of adsorbent. The volumetric uptake seems to be pressure because this can be achieved through a typical single-
the most appropriate one to quantify the adsorption capacity of stage or two-stage compressor. Obviously, to maximize the deliver-
the adsorbents, especially for ANG vehicular application. able capacity of the sorbent, it is necessary to maximize the
Gas adsorption measurement typically gives a gravimetric methane storage at say 65 bar and at the same time minimize
result. In order to calculate the volumetric uptake, a range of the amount of methane stored at around 5 bar.
different material densities such as crystal density, packing
density, and densities derived from mercury intrusion poro- 2.4 Methane/natural gas storage
simetry, have been used. For MOFs, the ideal crystal density has In most of the ANG studies, methane is used as the test gas to
commonly been used to convert gravimetric adsorption capa- measure the amount of gas stored. However, in actual systems,
cities to volumetric ones as their crystallographic densities are natural gas, consisting of a complex gas mixture, will be used as
readily available, representing the ideal maximum storage a fuel for storage. Consequently, natural gas storage is different
capacities that MOF materials can generate in practice. The from methane storage. The heavy hydrocarbons present in
crystallographic density of MOFs is the upper limit of packing natural gas are preferentially adsorbed upon charging, thus
density, and cannot be actually achieved for MOF powders. decreasing the methane storage capacity. In addition, these
Basically, the low packing density of MOFs may greatly reduce components cannot be totally desorbed upon discharging.
their volumetric storage capacity. Indeed, obvious differences Therefore, a protective device, i.e., a guard bed, needs to be
were observed between volumetric uptakes based on the practical placed at the adsorbent tank’s inlet when storing natural gas in
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a porous adsorbent. The guard bed removes these compounds dabco ligands, connecting the 2D layers into a 3D structure
and other trace amount of poisonous impurities (H2S, H2O, with a primitive cubic net topology. Using the short tripod-
etc.) from the gas stream upon fueling, and then releases these shaped dabco as a pillar ligand can effectively prevent frame-
compounds back to the fuel stream using the internal heater. work catenation, resulting in noninterpenetrated structures
with high porosity. Otherwise, introduction of bidentate pillar
2.5 Technological requirements linkers longer than dabco will lead to the formation of multiple
interpenetrated frameworks.40 A systematic modulation of
Methane adsorption capacity is not the sole property that has to

be considered in the development of porous materials for ANG dicarboxylate linkers leads to a series of porous isomorphous
applications. Once the material meets the storage capacity, the MOFs with varying size of pores.
following characters must be considered: (a) quantitative NG Seki et al. reported a series of this type of Cu-containing MOFs
desorption under mild conditions, (b) low adsorption heat, Cu2(L)2(dabco) (L = fma, bdc, sdc, or bpdc; fma = fumarate; bdc =
(c) high heat capacity, (d) high packing density, (e) high mecha- benzene-1,4-dicarboxylate; sdc = styrene dicarboxylate; bpdc =
nical stability, (f) low affinity for strong adsorbing species, and biphenyl-4,40 -dicarboxylate), and examined their high-pressure
(g) reasonable cost. methane adsorption properties.28,35,36 At 298 K and 35 bar, the
Usually, as a common industrial practice, it is essential to amount of methane adsorbed increases when the pore size
compact powdered MOFs into pellets or monoliths under an increases. However, two MOF materials Cu2(bpdc)2(dabco) and
external pressure to increase the packing density. Meanwhile, Cu2(sdc)2(dabco) constructed from bpdc and sbc linkers exhibit
the textural properties and even the crystal structures might be nearly the same methane uptake, despite that the former has
affected by this compression process. The research in this higher porosity than the latter, indicating that the interaction
respect is very limited. Tagliabue et al. studied the influence of energy of Cu2(bpdc)2(dabco) for methane is lower than that of
MOF shaping on physico-chemical characteristics and methane Cu2(sdc)2(dabco) because of larger pore size. This result also
adsorption properties of CPO-27-Ni.31 Compression under 0.1 GPa means that there exists an optimal pore size in this system for
does not dramatically affect the adsorption kinetics and crystal struc- methane adsorption storage. At 298 K and 35 bar, the amounts
ture. The obtained tableted MOF exhibits a gravimetric methane of methane adsorbed are 212 and 213 cm3 (STP) g1 for
adsorption capacity close to that of the as-synthesized MOF powder. Cu2(bpdc)2(dabco) and Cu2(sdc)2(dabco), respectively.
This result is different from those observed for MOF-5 and HKUST-1 Methane adsorption properties were examined in three
materials where the compression drastically decreases the gravi- isostructural MOFs M2(bdc)2(dabco) (M = Zn, Cu, Co).27,35,37–39
metric methane uptake.29,32 This different behaviour might be Guest dependent dynamic behavior has been observed in Zn
related to the differences in the mechanical strength. Therefore, and Co-based MOFs but not in the Cu-based MOF.38,128 The Zn
for industrial implementation of MOFs as natural gas storage and Co based frameworks shrink upon guest inclusion and
materials, MOFs should have good mechanical properties. expand upon guest release. Different methane uptakes of each
MOF were reported by different groups. At room temperature
and 35 bar, excess methane uptakes of 12.2% and 12.5% were
3. Porous MOFs for methane storage reported by Kim37 and Senkovska,27 respectively, for the Zn
based MOF, while excess methane uptakes of 12.2% and 10.8%
Prior to MOFs, the benchmark materials for methane sorption were reported by Wang38 and Zhu,39 respectively, for the Co
are activated carbons. In 1997, Kitagawa and co-worker reported based MOF. Due to non-existence of open coordination sites in
for the first time methane sorption on the porous MOF material this system, it is reasonably expected that the different metal
[Co2(4,4 0 -bipyridine)3(NO3)4] under high pressure.33 Yaghi’s centers have little effect on methane storage. Therefore, such a
group in 2002 investigated methane storage capacities of a series discrepancy in methane uptakes should have mainly originated
of isoreticular MOF materials.34 After these early reports, there from the sample quality and/or the degree of activation, indicating
have been some remarkable demonstrations of high methane the significance of the synthesis and activation procedure.
adsorptions in porous MOFs by various groups. Table 1 Another set of isostructural MOFs M2(2,6-ndc)2(dabco) (M = Ni,
summarises the textural properties, and methane storage and Co, Zn, Cu; 2,6-ndc = naphthalene-2,6-dicarboxylate) named as
working capacities of porous MOFs. In the following section, DUT-8(M) with different metal nodes was synthesized by Kaskel
we will discuss several types of important MOFs for methane et al.77 PXRD and gas adsorption experiments indicated that
storage purposes, with the focus placed on the methane storage these MOFs exhibited significantly different structural flexi-
mechanism. bility, depending on the metal ions comprising the nodes.
Upon removal and adsorption of guest molecules, DUT-8(Cu)
3.1 M2(dicarboxylate)2(dabco) remained intact, DUT-8(Ni) and DUT-8(Co) showed reversible
Studies have shown that pillar-layered MOFs M2(dicarboxylate)2- structural transformation, while DUT-8(Zn) exhibited irreversi-
(dabco) (dabco = 1,4-diazabicyclo[2.2.2]octane) are very promis- ble one. Within the DUT-8 series, DUT-8(Cu) has the highest
ing for methane storage.27,28,35–39 The compounds are composed surface area and pore volume as a result of the rigid framework,
of dinuclear paddle-wheel units linked by four dicarboxylates leading to the highest methane uptake. At 298 K, the methane
into two-dimensional square-grid layers. The axial sites of the uptakes of DUT-8(Cu) reached 147 and 188 cm3 (STP) cm3 at
paddle-wheels are occupied by nitrogen atoms of the neutral 35 bar and 65 bar, respectively.77
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Table 1 Crystal density, pore volume, surface area and methane adsorption in porous MOFsa
Methane adsorption Methane adsorption

Dc Vp BET Uptakeb Deliveryc T P Uptakeb Deliveryc T P Qst
MOF (g cm3) (cm3 g1) (m2 g1) (cm3 cm3) (cm3 cm3) (K) (bar) (cm3 cm3) (cm3 cm3) (K) (bar) (kJ mol1) Ref.
HKUST-1 0.883 0.78 1850 227 150 298 35 267 190 298 65 17.0 29
HKUST-1 0.881 0.77 225 149 298 35 264 188 298 65 17.0 8
HKUST-1 0.881 0.75 1663 220 141 295 35 259 180 295 65 41
HKUST-1 0.89 0.67 1850 217 152 303 35 42
HKUST-1 0.88 0.76 1502 198 132 303 35 236 170 303 65 27
HKUST-1 0.881 0.72 197 303 35 234 303 65 43
HKUST-1 0.881 0.71 1555 190 303 35 254 303 65 20.7 44
HKUST extrudates 0.582e 94d 303 35 45
HKUST-1 0.881 0.73 1587 89d 298 18 46
NiMOF-74 1.195 0.56 230 115 298 35 260 142 298 65 20.6 8
NiMOF-74 1.206 0.51 1350 228 106 298 35 251 129 298 65 21.4 29
NiMOF-74 1.206 0.47 1218 214 94 298 35 236 116 298 65 47
NiMOF-74 1.206 0.44 1027 208 100 298 35 20.2 48
PCN-14 0.871 0.87 1753 230 290 35 30 49
PCN-14 0.829 0.83 1984 202 125 298 35 239 160 298 65 17.6 8
PCN-14 0.829 0.85 2000 195 122 298 35 230 157 298 65 18.7 29
CoMOF-74 1.173 0.51 221 110 298 35 249 136 298 65 19.5 8
CoMOF-74 1.169 0.48 1056 193 92 298 35 19.6 48
MgMOF-74 0.909 0.69 200 113 298 35 230 142 298 65 18.5 8
MgMOF-74 0.909 0.63 1542 188 104 298 35 211 127 298 65 47
MgMOF-74 0.909 0.61 1332 168 95 298 35 18.5 48
Zn(bdc)(ted)0.5 0.893 0.73 1794 222 168 298 35 15.1 50
Zn2(bdc)2(dabco) 0.87 0.75 1448 174 303 35 212 303 65 27
Zn2(bdc)2(dabco) 0.826 0.68 1450 160 117 296 35 13.6 37
NJU-Bai10 0.667 1.11 2883 199 107 290 35 14.9 51
NOTT-107 0.756 0.767 1770 196 110 298 35 52
NOTT-109 0.790 0.850 2110 196 125 300 35 242 170 300 65 17.1 30
NOTT-100 0.927 0.677 1661 195 104 300 35 230 139 300 65 18.1 30
UTSA-20 0.910 0.63 1156 195 101 300 35 17.7 53
UTSA-20 0.909 0.66 1620 184 124 298 35 230 170 298 65 18.2 29
PCN-11 0.749 0.91 1931 194 125 298 35 235 166 298 60 14.6 54
NOTT-101 0.684 1.08 2805 194 138 300 35 239 183 300 65 15.5 30
NOTT-103 0.643 1.157 2958 193 140 300 35 236 183 300 65 15.9 30
[Zn3(OH)]4(tbcppm)
(H2tbcppm)2 0.676 1.14 2718 192 146 298 35 275 230g 298 65 55
PCN-16 0.724 1.06 2273 191 134 300 35 56
ZJU-5 0.679 1.074 2823 190 130 300 35 228 168 300 65 15.3 57
ZnMOF-74 1.231 0.41 885 188 102 298 35 18.3 48
NU-135 0.751 1.02 2530 187 127 298 35 230 170 298 65 16.6 58
MIL-53(Al) 0.978 0.54 1235 186d 303 35 59
MIL-53(Al) 0.978 155d 304 35 17 60
NU-125 0.578 1.29 3120 182 133 298 35 232 183 298 65 15.1 29
NU-125 0.578 1.29 3120 181 133 298 35 228 180 298 58 15.5 61
NOTT-102 0.587 1.268 3342 181 136 300 35 237 192 300 65 16.0 30
Cu-TDPAT 0.783 0.93 1938 181 122 298 35 222 163 298 65 62
ZJU-25 0.622 1.183 2124 180 132 300 35 229 181 300 63 15.1 63
ZJU-35 0.657 1.156 2899 177 132 300 35 227 182 300 64 64
IRMOF-6 0.65 0.92 177 134 298 36.5 34
Zn4O(L1)2 0.801 0.80 2151 177 117 298 35 213 153 298 65 11.30 65
MnMOF-74 1.084 0.50 1102 176 100 298 35 19.1 48
PCN-46 0.619 1.012 2500 172 132 298 35 206 166 298 65 66
SDU-6 0.611 1.17 2826 172 127 298 35 67
PCN-61 0.56 1.36 3000 171 127 298 35 219 174 298 65 68
UiO-66(Zr)-NH2 1.36 0.40 1080 166 100 303 35 204 138 303 65 42
Ni(ndc)(ted)0.5 0.789 1.34 2307 165 129 298 35 13.8 50
MIL-53(Cr) 1.04 165d 304 35 17 60
MIL-53(Cr) 1.017 106d 304 20 69
Zn4O(L1-Cl)2 0.839 0.71 1791 164 105 298 35 195 136 298 65 12.55 65
Zn4O(L1-CH3)2 0.807 0.75 1908 162 110 298 35 196 144 298 65 11.81 65
Co2(bdc)2(dabco) 0.815 0.82 1600 161 121 303 35 199 159 303 65 38
Co2(bdc)2(ted) 0.847 128d 298 36 39
NOTT-140 0.677 1.07 2620 159 293 20 16.6 70
UTSA-34b 0.840 0.542 991 159 99 290 35 71
PMOF-3 0.882 0.718 1840 159 101 298 35 72
SDU-7 0.606 1.10 2713 159 114 298 35 67
UTSA-40 0.827 0.65 1630 156 102 300 35 192 138 300 65 73
MOF-5 0.621 1.4 150 118 298 35 214 182 298 65 12.3 8
MOF-5 0.59 1.55 3800 132 298 35 74
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Table 1 (continued)

b c
Dc Vp BET Uptake Delivery T P Uptakeb Deliveryc T P Qst
HNUST-3 0.686 0.99 2412 149 298 20 15.4 75
PCN-80 0.574 1.47 3850 147 117 296 35 196 166 296 65 76
SDU-8 0.639 1.02 2516 147 105 298 35 67

DUT-8(Cu) 0.680 1.04 2535 147 112 298 35 188 153 298 65 77
UiO-66(Zr) 1.32 0.36 970 146 303 35 42
UiO-67(Zr) 0.708 0.69 1575 146 303 35 78
UiO(bpdc) 0.765 1.057 2646 146 293 20 15 79
MIL-100(Cr) 0.7 1.10 1900 144 114 303 35 202 172 303 65 19 80
MIL-100(Cr) 0.7 0.87 1767 100d 298 35 81
MIL-100(Cr) 0.7 0.61 1200 55d 303 20 82
ZJU-36 0.496 1.599 4014 142 114 300 35 203 175 300 65 64
MIL-125(Ti) 0.81 0.67 1820 141 303 35 42
FJI-H5 0.456 1.92 4255 139 106 298 35 199 166 298 65 10.8 83
NU-140 0.426 1.97 4300 138 108 298 35 200 170 298 65 14 84
NU-111 0.409 2.09 4930 138 111 298 35 206 179 298 65 15.2 85
NU-111 0.409 2.09 4930 138 111 298 35 206 179 298 65 14.2 29
PCN-66 0.45 1.63 4000 136 101 298 35 187 152 298 65 68
DUT-23(Co) 0.403 2.03 4850 135 112 298 35 197 174 298 65 86
MIL-101c(Cr) 0.44 2.15 4230 130 104 303 35 198 172 303 65 18 80
MIL-101(Cr) 0.45 1.92 4183 130 106 298 35 81
MIL-101(Cr) 0.45 1.57 3870 88 68 303 35 130 110 303 65 42
MIL-101(Cr) 0.31 1.303 2693 55 42 303 35 82 69 303 65 27
PCN-68 0.38 2.13 5109 128 98 298 35 187 157 298 65 68
SNU-50 0 0.650 1.08 2300 126 298 35 26.8 87
MOF-177 0.43 1.89 4500 126 108 298 35 193 175 298 65 74
Cu(SiF6)(4,4 0 -bpy)2 0.859 0.56 1337 125 82 298 36 16.2 88, 89
NPC-5 0.822 0.496 1140 124 293 20 16.1 90
UTSA-38 0.962 0.61 1090 124b 300 35 91
Cu(GeF6)(4,4 0 -bpy)2 0.925 124 298 36 16.2 88
DUT-4 0.773 0.68 1308 122 82 303 35 164 124 303 65 92
MOF-205 0.38 2.16 4460 119 100 298 35 183 164 298 65 74
DUT-51(Zr) 0.655 1.08 2335 118 87 298 35 161 130 298 65 93
(Et2NH2)3
[(Cu4Cl)3(ttca)8] 0.736 0.639 1680 118d 298 35 145d 298 65 18.08 94
MIL-100(Fe) 0.7 0.99 2410 117 92 303 35 158 133 303 65 42
MIL-100(Fe) 0.7 0.9 1942 88d 298 35 81
Zn4O(bfbpdc)3
(4,4 0 -bpy)0.5 1.054 0.59 1450 116 93 298 35 160 137 298 65 95
DUT-5 0.634 0.81 1613 114 94 303 35 134 114 303 65 92
IRMOF-8 0.448 1.827 4326 114 71 298 35 96
PCN-69 0.355 2.17 3989 114 94 298 35 298 65 97
DUT-49 0.309 2.91 5476 112 92 298 35 176 156 298 65 98
FJI-1 0.405 1.43 4043 111 90 298 35 164 143 298 65 99
PCN-16 0 0.764 0.84 1760 111 70 300 35 56
Cu3(L2)2(dabco) 0.603 1.13 2703 111 298 20 100
Cu4(L3) 0.706 0.97 111d 298 25 101
SNU-70 0 0.408 2.17 5290 107 91 298 35 9.4 102
NOTT-119 0.361 2.35 4118 106 86 298 35 154 134 298 65 103
Cd(bpydb) 1.206 0.35 346 105 69 298 35 125 89 298 65 104
DUT-6 0.386 2.02 105 89 298 35 163 147 298 65 105
MTAF-4 0.670 0.65 1590 105 79 300 35 136 110 298 65 106
DUT-9 0.358 2.18 102 83 298 35 155 136 298 65 107
NJU-Bai12 0.522 1.135 3038 100 298 20 15.7 108
Zn4O(fma)3 0.812 1120 98d 300 28 12.0 109
ZJU-32 0.434 1.482 3831 97 77 300 35 140 120 300 60 14.6 110
DUT-13 0.385 1.98 96 80 298 35 150 134 298 65 111
HNUST-2 0.570 0.97 2366 96 298 20 15.0 112
Cu3(tatb) 0.416 1.91 3360 91 273 20 113
Cu3(btb) 0.4071 1.77 3288 90 273 20 113
SDU-1 0.830 0.353 779 88 293 20 17.6 90, 114
Cu(dhbc)2(4,4 0 -bpy) 1.233 86 298 35 115
UTSA-28a-Cu 0.504 1.33 3179 85 65 300 35 16.9 116
MOF-210 0.25 3.60 6240 83 71 298 35 143 131 298 65 74
Co2(L4) 1.243 0.221 535 80 293 20 16.9 117
MIL-96(Al) 1.223 80d 303 20 16 118
Cu4(H4L5) 0.928 0.47 79d 298 25 101
Li3[(Cu4Cl)3(ttca)8] 0.699 0.724 1870 76d 298 35 85d 298 65 15.34 94
Ni3L2(tpt)2 0.601 1206 71d 298 35 21.0 119
View Article Online
Table 1 (continued)

b c
Dc Vp BET Uptake Delivery T P Uptakeb Deliveryc T P Qst
MOF-200 0.22 3.59 4530 67 56 298 35 117 106 298 65 74
Cd2(azpy)3(NO3)4 1.539 62 44 298 35 16.33 120
Zn2(L6) 1.105 0.155 367 34b 298 35 121

[Cu2(PF6)(NO3)(4,4 0 -bpy)4] 1.057 559 33 298 36 17.0 88
1.4PF60.6NO3
d
Cu2(pzdc)2(pyz) 1.745 31 298 31 122
SNU-30 0.381 0.28 704 29 298 35 123
Cu(Hoxonic)
(4,4 0 -bpy)0.5 1.84 21d 273 25 124
SNU-31 0.459 0.14 308 11 298 35 123
Cu2(sdc)2(ted) 0.983 f 1.07 3129 (213)d 298 35 28
Cu2(sdc)2(ted) 1.07 3129 (213)d 298 35 16.48 36
Cu2(bpdc)2(ted) 1.18 3265 (213)d 298 35 16.67 36
Cu2(bpdc)2(ted) 1.18 3265 (212)d 298 35 28
MIL-53(Cu) 0.65 1150 (191)d 298 35 125
Cu2(bdc)2(ted) 0.71 1891 (185)d 298 35 16.25 36
Cu(bdc)(ted)0.5 0.58 1548 (180)d 298 35 16.19 35
MIL-47(V) 0.5 1030 (143)d 303 35 126
Cu2(fma)2(ted) 0.23 606 (103)d 298 35 17.04 36
Cu(fma) 0.17 416 (82)d 298 35 15.70 127
MIL-96(Cr) (72)d 303 20 82
Cu(bdc) 0.22 545 (71)d 298 35 16.96 127
Cu(cdc) 0.15 347 (60)d 298 35 26.57 127
a
Dc: crystal density; Vp: pore volume. b Total volumetric uptake; the data in bracket are total gravimetric uptakes. c The deliverable amount is
defined as the difference in total uptake between 5 bar and the specified upper limiting working pressure under isothermal conditions. d Not
specified whether uptake is in terms of excess, total or absolute adsorption. e Real packing density. f Densities derived from mercury intrusion
porosimetry. g The methane storage capacity of this MOF will need to be carefully and thoroughly re-evaluated independently by other groups;
bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine; dabco = 1,4-diazabicyclo[2.2.2]octane; tbcppm = tetrakis{3,5-bis[(4-carboxyl)phenyl]-
phenyl}methane; tdpat = 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine; H3L1 = 4-[N,N-bis(4-methylbenzoic acid)amino]benzoic acid; H3L1-Cl =
4-[N,N-bis(4-methylbenzoic acid)amino]-2-chlorobenzoic acid; H3L1-CH3 = 4-[N,N-bis(4-methylbenzoic acid)amino]-2-methylbenzoic acid; ndc =
naphthalenedicarboxylate; 4,4 0 -bpy = 4,4 0 -bipyridine; H3ttca = triphenylene-2,6,10-tricarboxylic acid; H2bfbpdc = 2,2 0 -bis-trifluoromethyl-biphenyl-
4,4 0 -dicarboxylic acid; H3L2 = [1,1 0 :3 0 ,100 -terphenyl]-4,400 ,5 0 -tricarboxylic acid; H8L3 = 5,5 0 ,500 ,5 0 0 0 -[1,2,4,5-phenyltetramethoxy]tetraisophthalic acid;
H2bpydb = 4,40 -(4,40 -bipyridine-2,6-diyl)dibenzoic acid; fma = fumarate; tatb = 5,50 ,500 -[1,3,5-triazine-2,4,6-triyl-tris(benzene-4,1-diyl)-tris(carbonylimino)]-
tris-1,3-benzenedicarboxylic acid; btb = 5,50 ,500 -[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)-tris(carbonylimino)]tris-1,3-benzenedicarboxylic acid; Hdhbc =
2,5-dihydroxybenzoic acid; H4L4 = 2,2 0 ,200 ,2 0 0 0 -(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(azanetriyl)tetraacetic acid; H12L5 = 5,5 0 ,500 ,5 0 0 0 ,5,5 0 -
[1,2,3,4,5,6-phenylhexamethoxy]hexaisophthalic acid; tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine; azpy = 4,4 0 -azopyridine; H4L6 = tetrakis[4-(carboxy-
phenyl)oxamethyl]methane acid; pzdc = pyrazine-2,3-dicarboxylate; pyz = pyrazine; H3oxonic = 4,6-dihydroxy-1,3,5-triazine-2-carboxylic acid;
sdc = styrenedicarboxylate; bpdc = 2,2 0 -bipyridine-5,5 0 -dicarboxylate; cdc = trans-1,4-cyclohexanedicarboxylate.
Kim et al. investigated methane binding sites in the Zn based

MOF compound Zn2(bdc)2(dabco) at low temperature.37 X-Ray
structure analysis of methane adsorbed sample by synchrotron
radiation at 90 K revealed three independent methane sorption
sites (Fig. 1). Two primary adsorption sites are near the
Zn2(COO)4 paddlewheel units (site I), and the center of the small
windows along the a and b axes (site II), respectively. The center
of cavity (site III) is a secondary sorption site. Methane molecules
located in site I interact not only with the paddlewheel units in
van der Waals contact but also with the phenyl rings of the bdc
linker through p H–C interaction. Methane molecules occupy-
ing site II interact with the side of the phenyl rings through van
der Waals interaction. Methane molecules occupying site III
are in van der Waals contact with those in sites I and II. Full
saturation of these three adsorption sites gives a value which is
consistent with what is measured experimentally. Fig. 1 X-ray crystal structure of methane-adsorbed [Zn2(bdc)2(dabco)]
showing three methane sorption sites (site I: orange, site II: green, site III:
3.2 Zn4O-based MOFs purple). Reprinted with permission from ref. 37. Copyright 2009, Wiley.
Zn4O(COO)6 SBU is one very useful inorganic building block for

the construction of highly porous MOFs. A combination of this isoreticular MOFs (IRMOFs) whose pore spaces can be system-
type of SBU with a number of dicarboxylates affords a series of atically tuned by changing the length of the dicarboxylates.
View Article Online
The high-pressure methane adsorption properties of three and hex sites on the top of the benzene ring of the organic
numbers in the IRMOF series (IRMOFs-1, 3, and 6) have been linkers. Different from the methane molecules at the primary
examined, among which IRMOF-6 has the highest excess adsorption site, those adsorbed at the secondary adsorption
methane uptake of 155 cm3 (STP) cm3 (240 cm3 (STP) g1) at sites are orientationally disordered, implying a weak inter-
298 K and 36.5 bar.34 Such high methane uptake in IRMOF-6 is action between methane and the framework. Methane confined
attributed to the high surface area and the hydrophobic nature inside the central cavity is totally disordered and stabilized by
of C2H4 groups. These promising results prompt Snurr et al. to the intermolecular interactions with surrounding methane.
perform computational simulations to evaluate the methane Interestingly, lowering the temperature below 60 K leads to a
adsorption capacities of many hypothetical IRMOFs. They pre- rearrangement of the confined methane molecule in the central
dict that one specially designed MOF material IRMOF-993, pores of the framework, and accordingly a structural phase
based on 9,10-anthracene dicarboxylate linker, performs better transition in the MOF–host lattice (Fig. 2c), which is unusual.
than IRMOF-6 in terms of volumetric storage capacity.129 How- However, Raman spectroscopic studies point to the critical
ever, attempts to synthesize this proposed MOF result in an role that the linkers play in the methane adsorption in IRMOFs
ultramicroporous material PCN-13 with very limited methane at room temperature and high pressure.132 Upon adsorption,
uptakes.130 the symmetrical stretching band of methane is downshifted
In practice, framework interpenetration might be an obstacle relative to the free methane due to the interaction between
in maximizing the porosity of these IRMOF materials. For methane and the framework. If methane adsorption occurred
example, when an extended organic linker such as 2,6-naphthalene- dominantly at the metal oxide clusters, methane would experience
dicarboxylate was used instead of 1,4-benezenedicarboxylate in the the same frequency shift, independent of IRMOF structures.
original IRMOF-1, typical solvothermal synthesis at high tempera- However, different frequency shifts were observed, revealing
ture afforded an interpenetrated framework. Recently, Feldblyum that the methane adsorption is dominated by the organic linker
et al. discovered a room temperature synthesis approach that at room temperature in these IRMOFs.
allowed for the synthesis of phase-pure noninterpenetrated A combination of Zn4O(COO)6 SBU with tricarboxylate linkers
IRMOF-8-RT, and examined its gas sorption properties.96 At 298 K yields another class of highly porous MOFs such as MOF-177, MOF-
and 35 bar, excess methane uptake is 193 cm3 (STP) g1, corre- 180, and MOF-200.74,133 Matzger, Kaskel and Yaghi et al. have even
sponding to a relatively low volumetric uptake of 87 cm3 (STP) cm3. been able to assemble two different types of organic carboxylates,
Thus, a combination of both linker extension and linker function- namely, triangular tricarboxylate and linear dicarboxylate, leading
alization might be needed to simultaneously maximize both gravi- to a number of exceptionally highly porous noninterpenetrated
metric and volumetric uptakes. MOFs. Notable examples include UMCM-1,134 UMCM-2,135
Using neutron powder diffraction, Wu et al. directly deter- DUT-6105/MOF-205,74 and MOF-210.74 The framework of the
mined the methane sorption sites in IRMOF-1 (MOF-5) at low material consists of Zn4O(COO)6 clusters linked together by
temperature.131 Methane is preferentially adsorbed at the Zn4O 2 dicarboxylate and 4 tricarboxylate linkers arranged in an
clusters (the primary adsorption site, termed as ‘‘cup site’’) octahedral geometry. The Langmuir surface area of MOF-210
where methane molecules possess well defined orientations. is up to 10 400 m2 g1. Of the Zn4O-based MOFs reported for
With increasing methane loading, extra methane molecules methane storage, MOF-210 has the highest total methane
occupy the ZnO2 site and the hex site (the secondary adsorption uptake of 476 mg g1 at 298 K and 80 bar. Due to the low
sites) and are confined inside the central cavity (Fig. 2). ZnO2 framework density, the volumetric methane uptake is quite low.
sites are located above the O–O edge of the ZnO4 tetrahedra,
3.3 MOF-74 series
MMOF-74, also known as CPO-27-M, is one of the most well
studied families of MOFs bearing the highest concentration of
open metal sites reported so far. ZnMOF-74 was firstly synthe-
sized by Rosi et al.,136 and subsequently other analogues were
reported.48,137–140 Each of these materials is composed of the
infinite helical SBUs bound by 2,5-dioxido-1,4-benzenedicarboxylate
(DOBDC) to form a 1D honeycomb-like pore structure of B1.1 nm
diameter. The coordination solvent molecules can be easily removed
by thermal treatment under vacuum, resulting in an activated stable
Fig. 2 (a) The primary methane adsorption site (cup site, cyan) and the
secondary methane adsorption sites (hex site, yellow; ZnO2 site, green) in
framework with a high concentration of coordinatively unsaturated
MOF-5. (b) [001] view of the I4/mmm structure of MOF-5 with more CD4 metal sites. These unsaturated metal centers can offer primary
loading at 80 K. Extra methane molecules (pink) were populated near the binding sites to the guest gas molecules, as has been demon-
center of the pores. (c) [001] view of the P4mm structure of MOF-5 with strated in a number of diffraction studies involving various
higher CD4 loading below 60 K. Confined methane sites (orange) were
host–guest combinations.48,141–144
aligned along the c axis and further lowered the symmetry to P4mm.
Orientationally disordered methane molecules are shown as spheres for
Wu et al. compared the methane adsorption properties of
clarity. Reprinted with permission from ref. 131. Copyright 2009, American the MMOF-74 series (M = Mg, Mn, Co, Ni, Zn).48 Their excess
Chemical Society. adsorption capacities of methane at 298 K and 35 bar range
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from 149 to 190 cm3 (STP) cm3, NiMOF-74 exhibiting the 3.4 Copper–carboxylate frameworks
highest one. All five compounds have very similar heats of 3.4.1 HKUST-1. The well-known material HKUST-1, a MOF
adsorption in the range of 18.3–20.2 kJ mol1 at low loading, firstly reported by Chui et al.,146 consists of dicopper paddle-
which is less dependent on the metal identity relative to hydrogen wheel SBUs which are connected by 1,3,5-benzenetricarboxylate
binding energies.141 This is attributed to the large size and linkers to form a 3D network containing three different types
geometrical constraint of the methane molecule, increasing the of cages (Fig. 4a). The small octahedral cage is surrounded by
distance between the metal center and the methane molecule, 4 dicopper paddlewheel SBUs and 4 organic linkers with a
and thereby decreasing the interaction potential. Also, the high diameter of approximately 5 Å. The middle cuboctahedral cage of
heat of adsorption results in a rapid increase in the isotherm at around 10 Å diameter is encapsulated by 12 dicopper paddle-
low pressure, which is obviously unfavorable to methane delivery. wheel SBUs and 8 organic linkers, whereas the large cubocta-
The deliverable amount of methane is less than half of the hedral cage of about 11 Å diameter is constructed from 12 dicopper
storage amount.145 Dietzel et al. also studied the methane paddlewheel SBUs and 24 benezenedicarboxylate units. These
adsorption in NiMOF-74 and MgMOF-74, and similar results cages are interconnected at windows. Furthermore, upon removal
were obtained.47 Recent studies of Peng29 and Mason8 showed of the axial water molecules, the copper ions become coordina-
a higher methane uptake of about 230 cm3 (STP) cm3 for tively unsaturated for binding gas molecules. Note that only the
NiMOF-74 at 298 K and 35 bar, again confirming the signifi- large cuboctahedral cage has open copper coordination sites
cance of the sample activation on gas adsorption. pointing to the pore.
The neutron diffraction experiments clearly indicate that the The high-pressure methane adsorption on HKUST-1 has been
methane molecules are primarily bound to the open metal sites widely studied,8,27,29,43,147 but inconsistent data were reported by
(site I, Fig. 3a) in the framework through the Coulomb inter- different groups, which was typically due to the sample quality
action.48 Fig. 3b shows a secondary adsorption site (site II) and/or the degree of activation. More recently, Peng et al.
where the methane molecules interact with both the framework re-checked the methane adsorption properties of HKUST-1 and
and the adjacent methane molecules occupying the site I. In found that it exhibited exceptionally high volumetric methane
these MOFs, open metal sites play a major role in the adsorp- uptake exceeding any material reported thus far (Fig. 4b).29 This
tion of methane. indicates that optimizing the synthesis and activation procedure
is very crucial to realize the full potential of MOFs for gas storage.
To achieve a high gas uptake, it is necessary to synthesize a high-
quality phase-pure crystalline sample via adjusting the solvothermal
reaction conditions, and to optimize carefully the activation profiles
including the activation solvent, temperature and time, or to take
advantage of the mild activation techniques such as supercritical
CO2 drying148 and freeze drying.149 At 298 K and 35 bar, the total
methane uptake is about 230 cm3 (STP) cm3. Under higher
pressure of 65 bar, HKUST-1 can reach much higher methane
storage capacity up to 267 cm3 (STP) cm3 at room temperature,
which meets the new volumetric target recently set by the U.S.
DOE if the packing efficiency loss is ignored. Supposing 65 bar
Fig. 4 (a) Three different types of cages in HKUST-1 and (b) methane
Fig. 3 Crystal structure showing (a) the primary adsorption site (site I) adsorption isotherms for HKUST-1 at various temperatures. The orange color
and (b) the secondary adsorption site (site II) for methane in MgMOF-74. lines represent isotherms obtained from He-cold volume with the sample
Reprinted with permission from ref. 48. Copyright 2009, American inside while the other isotherms are using empty-cell cold volumes. Reprinted
Chemical Society. with permission from ref. 29. Copyright 2013, American Chemical Society.
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and 5 bar are taken as the upper and lower limiting pressures,
respectively, for methane delivery, HKUST-1 also shows an
excellent deliverable capacity of methane of 190 cm3 (STP) cm3.
Kaskel et al. investigated the methane adsorption sites in
HKUST-1 at low temperature using high-resolution neutron
powder diffraction (NPD).43 Retiveld analysis of the samples
loaded with different amounts of CD4 revealed that methane

molecules sequentially occupied distinct adsorption sites, and
more importantly, showed the existence of preferential adsorp-
tion sites at the open metal positions for methane. For a sample
fully filled with methane molecules, different adsorption sites
were unambiguously identified, among which four primary
adsorption sites are located inside the pore cages and the
windows between the middle and large cages. With decreasing
methane loadings, the primary adsorption sites still remain
nearly unchanged, but the majority of the methane occupies
the large pore cage instead of the small one and open copper
sites, which is unexpected considering that the small pore
cages and the open metal sites have higher affinity towards
methane molecules. The unusual behavior is attributed to
the gas adsorption kinetics. During the methane filling process,
some adsorbed molecules do not occupy equilibrium sites
but are frozen at locations with higher adsorption rate and
accessibility.
Zhou et al. also performed a comprehensive mechanistic
study of methane adsorption in HKUST-1.147 NPD experiments
Fig. 5 Two primary adsorption sites for methane: (a) open copper site
in combination with a grand canonical Monte Carlo simulation
and (b) the small cage window site in HKUST-1. Reprinted with permission
(GCMC) unambiguously reveal that besides the open copper from ref. 147. Copyright 2010, Wiley.
coordination site, the window site of the small octahedral cage
is also one primary methane adsorption site (Fig. 5). These
window sites bind methane strongly due to several close inter- cages pack alternatively. One is an octahedral cage consisting of
actions in the range of 2.7–3.2 Å between framework O atoms 12 ligands and 6 paddlewheel SBUs, while another is a cub-
and an adsorbed methane molecule. Moreover, the number of octahedral cage constructed from 6 ligands and 12 paddlewheel
these small cage window sites is equal to 2/3 of that of the open SBUs, if the centers of dicopper paddlewheel SBUs are taken
copper sites. Full saturation of the two primary sites will as vertices of polyhedra. These NbO-type frameworks have
contribute a methane capacity of around 160 cm3 (STP) cm3, shown excellent framework stability, porosity and gas adsorption
which is approximately 70% of the experimental uptake measured capacity.
at 298 K and 35 bar. The remaining 30% of methane uptake is Wang et al. reported a porous NbO-type MOF PCN-11 con-
attributed to the secondary adsorption sites. structed from dicopper paddlewheel SBUs and a CQC double
Recently, two HKUST-1 analogues ZJU-35 and ZJU-36 were bond coupled diisophthalate linker, trans-stilbene-3,3 0 ,5,5 0 -
constructed based on less symmetrical tricarboxylates.64 Signifi- tetracarboxylate.54 When the NQN double bond was used as
cantly, ligand extension enlarges the porosities. At 300 K and a spacer instead of the CQC double bond between two iso-
64 bar, the methane uptake capacities of ZJU-35 and ZJU-36 phthalate units, an isostructural but thermally less stable MOF
reach up to 227 and 203 cm3 (STP) cm3, respectively, which are PCN-10 was formed, leading to its lower porosity. Upon the
among those of the best MOFs for methane storage. guest removal, PCN-11 shows a remarkable total methane
3.4.2 NbO-type copper–tetracarboxylate frameworks. Tetra- uptake of 194 cm3 (STP) cm3 at 298 K and 35 bar. Due to
carboxylates have been widely employed to construct porous the high methane uptake capacity, Wu et al. employed the NPD
framework materials. Chen et al. reported the first example of experiment and computational simulation to investigate the
MOF-505, which is self-assembled from dicopper paddlewheel methane adsorption mechanism in PCN-11, and concluded
SBUs and 3,3 0 ,5,5 0 -biphenyltetracarboxylate, exhibiting high that the open metal sites, the cage window sites and the large
H2 adsorption capacity.150 Subsequently, a series of tetra- cage corner sites provide the major adsorption sites for methane
carboxylates have been designed and synthesized by several in PCN-11.147
well-known research groups.49,54,58,87,151–153 A combination of The same group also synthesized several other NbO-type
them and dicopper paddlewheel SBUs usually leads to excep- MOFs derived from diisophthalate linkers containing CRC
tionally high porous frameworks. Most of them have a (4,4)- triple bonds.56,66 The assembly of dicopper paddlewheel SBUs
connected NbO-type structure in which two different types of and a diisophthalate linker incorporating one CRC triple bond,
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5,5 0 -(1,2-ethynediyl)bis(1,3-benzenedicarboxylate), under differ- on methane storage and delivery (Fig. 6a), we studied the methane
ent solvothermal conditions yielded a pair of supermolecular storage and delivery capacities of five representative MOFs: NOTT-
isomers, PCN-16 and PCN-16 0 , respectively.56 Despite rather 100, 101, 102, 103 and 109.30 As shown in Fig. 6b, augmentation of
subtle structural difference, the two isomers exhibited signifi- the pore size from NOTT-100 to NOTT-102 results in a decrease in
cantly different gas adsorption properties. PCN-16 has a much gravimetric methane uptake at low pressure (o10 bar), indicating
higher excess methane adsorption capacity of 175 cm3 (STP) cm3 that the methane uptake capacity at low loading is mainly con-
at 300 K and 45 bar, compared to just 97 cm3 (STP) cm3 for
trolled by the methane affinity towards the framework. However,

PCN-16 0 under the same conditions. The superior gas adsorption when the pressure goes from 20 bar to 65 bar, the hierarchy of the
properties of PCN-16 can be mainly due to its smaller pore size gravimetric methane uptake capacities is reversed, indicating that
providing more adsorption sites for methane molecules. the pore volume starts to play a dominant role. At 300 K and
A combination of dicopper paddlewheel SBUs and a diiso- 35 bar, they exhibit high volumetric methane adsorption capacities
phthalate linker incorporating two CRC triple bonds, 5,5 0 - ranging from 181 to 196 cm3 (STP) cm3, and excellent methane
(buta-1,3-diyne-1,4-diyl)diisophthalic acid, in situ formed via deliverable capacities in the range of 104–140 cm3 (STP) cm3.
copper catalyzed oxidative coupling of 5-ethylisophthalic acid, At 300 K and 65 bar, the volumetric methane adsorption and
gives rise to a porous MOF PCN-46.66 Replacement of phenyl deliverable capacities are 230 and 139 cm3 (STP) cm3 for
rings by a polyyne chain leads to not only a boost of pore NOTT-100, 239 and 183 cm3 (STP) cm3 for NOTT-101, 237 and
volume but also a strong affinity toward gas molecules such as 192 cm3 (STP) cm3 for NOTT-102, 236 and 183 cm3 (STP) cm3 for
hydrogen and acetylene.153 The gravimetric excess methane NOTT-103, and 242 and 170 cm3 (STP) cm3 for NOTT-109, res-
uptake in PCN-46 reaches a saturation at 192 mg g1 at 298 K pectively. Under these conditions, the deliverable capacity of NOTT-
and 60 bar. At 298 K and 35 bar, the total volumetric methane 102 is comparable to that of HKUST-1 (190 cm3 (STP) cm3).
uptake in PCN-46 is 172 cm3 (STP) cm3. Ma et al. have synthesized a NbO-type MOF material called
Schröder et al. explored various aromatic rings as spacers PCN-14 exhibiting an impressive methane adsorption capacity
between two isophthalates, and constructed a variety of poly- of 230 cm3 (STP) cm3 at 290 K and 35 bar,49 which has been
phenyl tetracarboxylate linkers, which are incorporated into a widely cited as one world-record holding MOF material for
series of NbO-type frameworks.151,152,154 These desolvated frame- methane storage. PCN-14 is constructed by self-assembly of
works exhibit high H2 adsorption capacities. Considering the dicopper paddlewheel SBUs and the organic linker, 5,5 0 -(9,10-
fact that the different densities of open metal sites, and different anthracenediyl)diisophthalate. If the centers of dicopper paddle-
pore sizes and shapes in these resulting frameworks provide a wheel SBUs and the anthracenyl groups are all taken as vertices of
good chance to systematically investigate the effect of these factors polyhedra, the octahedral cage can be viewed as a squashed
cuboctahedral cage in which the anthracenyl rings are in close
contact, with the distance of 2.6 Å between a H atom and the
center of a phenyl ring from the adjacent anthracenyl group,
providing a strong van der Waals interaction for methane adsorp-
tion; whereas the cuboctahedral cage is regarded to consist of one
squashed cuboctahedral cage at the center and two small octa-
hedral cages on the top and bottom (Fig. 7a). A combination of
Fig. 7 (a) Cage structures and (b) high-pressure methane adsorption

Fig. 6 (a) The cage structures and (b) absolute gravimetric high-pressure isotherms in PCN-14. The orange color lines represent isotherms obtained
methane adsorption isotherms at 300 K for NOTT-100, 101, 102, 103, from He-cold volume with the sample inside while the other isotherms are
and 109. Inset: an enlargement of the low-pressure region of the sorption using empty-cell cold volumes. Reprinted with permission from ref. 29.
isotherms. Copyright 2013, American Chemical Society.
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these nanoscopic cages with the open metal sites contributes to its
high methane adsorption capacity. The absolute volumetric adsorp-
tion capacity of methane in PCN-14 is up to 230 cm3 (STP) cm3 at
290 K and 35 bar. Because of the importance of this benchmark
MOF, two groups have re-evaluated the methane adsorption prop-
erties of PCN-14 carefully over a wide range of pressures and
temperatures (Fig. 7b).8,29 The methane uptakes of PCN-14 were
found to be around 195–202 cm3 (STP) cm3 under 35 bar and

230–239 cm3 (STP) cm3 under 65 bar at 298 K, once again
confirming its high methane storage capacities. The differences
among these reports are attributed to slightly different activation
conditions, temperatures and framework densities utilized.
Fig. 9 Probability distributions of the centers of mass of methane in PCN-
Wu et al. applied several computational techniques includ- 14 at (a) 3500 kPa and 290 K and (b) 5 kPa and 150 K, viewed along the
ing DFT calculation and GCMC simulations to determine the [211] crystallographic direction. The circles show the probability distribu-
methane adsorption sites in PCN-14.147 As shown in Fig. 8, tions of the centers of mass of methane molecules in the region where
open copper sites, small cage window sites, small cage bottom sites, methane molecules are expected to be positioned to populate the
and small cage side window sites are the primary adsorption sites. open Cu site. Reprinted with permission from ref. 155. Copyright 2008,
American Chemical Society.
Full occupation of these sites would give 160 cm3 (STP) cm3 of
methane storage capacity. The remaining storage capacities would
be easily provided by the secondary adsorption sites such as large slightly better methane storage material than PCN-14.52,152
cage corner sites. Interestingly, another simulation study indicates a Absolute methane uptake capacity of NOTT-107 is predicted
temperature dependence of open metal site population for methane to be 213 cm3 (STP) cm3 at 298 K and 35 bar, but the
adsorption. Fig. 9 shows probability distributions of the centers of experimentally measured value is 8% lower than predicted.
mass of methane at 290 K and 150 K. It can be seen that open The authors attribute the discrepancy to incomplete pore
copper sites are heavily populated at low temperature, while less activation, reflected by the fact that the experimental surface
populated at room temperature. It was further suggested that there area is lower than the calculated one. The reason for a high
exists no energy barrier between weak and strong sites at room methane uptake in NOTT-107 is believed to be similar to the
temperature. Open metal sites might play a crucial role in direct- one behind PCN-14.49,147
ing methane molecules to other neighboring binding sites. By introducing the Lewis basic pyridyl sites into the frame-
Molecular simulation identified that a known NbO-type MOF, work, Rao et al. realized a NbO-type framework ZJU-5 exhibiting
NOTT-107, based on 5,5 0 -(2,3,5,6-tetramethylbenzene-1,4-diyl)- not only a high acetylene storage capacity of 290 cm3 g1 at
diisophthalate linker and dicopper paddlewheel SBUs, is one 273 K and 1 bar, but also high methane storage capacities of
190 and 228 cm3 (STP) cm3 under 35 bar and 65 bar at 300 K,
respectively.57 ZJU-5 is formed by self-assembly of dicopper
paddlewheel SBUs and 5,50 -(pyridine-2,5-diyl)diisophthalic acid,
in which the isophthalate moieties are coordinated to Cu2+ ions to
form dicopper paddlewheel SBUs while the pyridyl sites remain
unbound. Compared with the analogous MOF NOTT-101,30,156
ZJU-5 exhibits a much higher acetylene uptake but a slightly lower
methane uptake, indicating that the Lewis basic pyridyl sites
might strengthen the interaction with acetylene through pyridyl
N H–CRC–H hydrogen bonding. The methane storage capacity
of ZJU-5 is still among those of the very few porous MOFs with
storage capacities higher than 190 cm3 (STP) cm3 at room
temperature and 35 bar, which is attributed to the interplay of
the open copper sites and suitable cage sizes. The same group also
synthesized another MOF compound ZJU-25 with a rare sty-a
framework topology,63 which is assembled from dicopper paddle-
wheel SBUs and a fluorene based diisophthalate, exhibiting a total
methane uptake of 180 and 229 cm3 (STP) cm3 under 35 bar and
63 bar at 300 K, respectively. The deliverable capacity of methane
from 63 to 5 bar at 300 K is 181 cm3 (STP) cm3, which is among
those of a few MOFs with the deliverable capacity of methane
Fig. 8 (a) The small cage window site and the small cage bottom site (top
and side views), (b) the small cage side window site, and (c) all four major
higher than 180 cm3 (STP) cm3 (Table 1).
adsorption sites, including the open copper sites in PCN-14. Reprinted Incorporation of the carborane moiety into the NbO-
with permission from ref. 147. Copyright 2010, Wiley. type framework generates a porous NbO-type MOF NU-135.58
View Article Online
Interestingly, compared with the analogous terphenyl-based

MOF compound NOTT-101,151,152 NU-135 has a slightly reduced
pore volume but significantly enhanced volumetric surface
area, presumably due to the unique geometrical character of
the carborane unit, despite the approximately equal length of
the linkers employed in two MOFs. Significantly, the interplay
between the volumetric surface area and the pore volume leads
to a high methane adsorption capacity. At 298 K, the total
methane storage capacities under 35 and 65 bar are 187 and
230 cm3 (STP) cm3, respectively. The deliverable amount of
methane from 65 to 5 bar at 298 K is 170 cm3 (STP) cm3. This
study highlights a novel strategy employing a carborane moiety
to greatly increase the volumetric surface area.
3.4.3 rht-type copper–hexacarboxylate frameworks. The
traditional strategy for obtaining higher surface area MOFs
has been to increase the length of the organic linkers based
on a known topology structure. However, extension of the
organic linker frequently undermines the framework stability.
Upon the removal of guest molecules, the frameworks tend to
collapse partially or completely, leading to less porous or even
nonporous frameworks. Furthermore, in some cases, undesired Fig. 10 (a–c) Three types of polyhedral cages in NU-111: truncated
framework interpenetration occurs, filling each other’s pores. tetrahedron (T-Td), the cuboctahedron (cub-Oh), and truncated octahedron
(T-Oh). (d) High-pressure methane adsorption isotherms of NU-111 at
Thus, construction of a more stable MOF framework in com-
various temperatures. Reprinted with permission from ref. 29 Copyright
bination with higher porosity is still a great challenge for the 2013, American Chemical Society.
MOF community. In this regard, using metal–organic poly-
hedra as supermolecular building blocks (SBBs) might be an
efficient strategy to construct robust highly porous MOFs. This Yuan et al. reported an isoreticular series of (3,24)-connected
is because the nano-scale SBBs have intrinsic porosities and rht-type MOFs PCN-6x (x = 1, 6, and 8) made from C3-symmetrical
higher connectivity compared to the simple SBUs. One widely hexatopic ligands incorporating three isophthalates.157 As
used SBB is a cuboctahedron, owing to the chemical accessibility of expected, the ligand extension enlarges the size of T-Oh and
1201-angular-dicarboxyalte ligands, which is assembled from T-Td but does not change the size of cub-Oh. These MOFs
12 dinuclear paddlewheel SBUs and 24 isophthalate moieties. exhibit impressive surface areas and pore volumes. Because
Connecting the 24 edges of a cuboctahedron with C3-symmetrical the gas uptake capacity at low loadings is mainly controlled by
hexacarboxylate linkers affords a large number of highly porous the gas affinity towards the framework, as aforementioned,
(3,24)-connected rht-type frameworks.61,62,67,103,157–165 Notable PCN-61 shows the highest methane uptake capacity in the
examples include NOTT-112,159 PCN-61,157 PCN-66,157 PCN-68157/ medium pressure range (o20 bar), which is likely caused by
NOTT-116,161 PCN-6997/NOTT-119,103 NU-100,166 NU-111160 and its small pore spaces and the high concentration of accessible
NU-125.61 This type of topology was pioneered by the Eddaoudi copper sites. When the pressure goes to high range, the effect of
group,167 and thereafter extensively explored by several other surface area and pore volume starts to dominate, making PCN-68
research groups. The use of this type of topology can effectively the one with the highest methane uptake capacity. The saturated
avoid framework interpenetration, create hierarchical pore cages gravimetric methane adsorption capacities correlate well with
and generate open metal sites upon desolvation. These features are their gravimetric surface areas/pore volumes. However, the volu-
obviously favorable for high-pressure gas storage. metric capacity does not follow the trend due to different frame-
The structure of these (3,24)-connected rht-type MOFs can be work densities. To achieve high volumetric methane uptake
viewed as the packing of three different types of polyhedral capacity, other factors such as framework density and pore size,
cages, as illustrated in Fig. 10, using NU-111 as an example. The in addition to framework porosity, should be equally taken into
smallest cage is a cuboctahedron (cub-Oh) composed of 24 account. At 298 K and 35 bar, the volumetric methane uptakes of
isophthalate moieties and 12 dicopper paddlewheel SBUs. The PCN-61, PCN-66 and PCN-68 are 171, 136, and 128 cm3 (STP) cm3,
second cage is a truncated tetrahedron (T-Td) formed by 4 linkers respectively. At 298 K and 65 bar, the adsorption and deliverable
and 12 dicopper paddlewheel units. The largest cage is a capacities of methane are 219 and 174 cm3 (STP) cm3 for PCN-61,
truncated octahedron (T-Oh) composed of 8 ligands and 187 and 152 cm3 (STP) cm3 for PCN-66, and 187 and
24 dicopper paddlewheel units. One truncated tetrahedron is 157 cm3 (STP) cm3 for PCN-68, respectively. Up to 85% of
connected to 4 cuboctahedra, while one truncated octahedron the storage amount can be delivered, which might be attributed
is connected to 6 cuboctahedra, by sharing the triangular and to the hierarchical cage structures.
square windows of the cuboctahedron, respectively, leading to a Hupp and co-workers synthesized a highly porous (3,24)-
highly porous framework. connected MOF denoted as NU-111 made from a C3-symmetrical
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organic linker whose arms each contain two CRC triple bond
spacers.160 NU-111 has a BET surface area of 5000 m2 g1, signifi-
cantly higher than that of PCN-69/NOTT-119 (3989–4118 m2 g1)
constructed from a C3-symmetrical organic linker whose arms
each contain two phenyl ring spacers,97,103 meaning that repla-
cing two phenyl rings in each arm with two triple bonds can
greatly boost the molecule-accessible surface area. Based on

this strategy, the two MOF materials NU-109 and NU-110 have
recently been realized, displaying the highest experimental
BET surface area of any porous materials reported to date
(B7000 m2 g1).168 The most striking feature is that NU-111
exhibits equally high volumetric and gravimetric methane uptake
values (Fig. 10d). The total gravimetric and volumetric uptakes at
298 K and 65 bar reach 0.36 g g1 and 205 cm3 (STP) cm3,
respectively, which are only 25% lower than the new DOE targets.
The deliverable capacity of methane at 298 K from 65 to 5 bar is
177 cm3 (STP) cm3.
In choosing MOF materials for methane storage, the scale-up
synthesis plays equally important roles. Many MOFs do not scale
well under the present synthetic pathways, with their purity
decreasing at larger reaction sizes. The same group synthesized
in a gram scale the other two (3,24)-connected rht-type frame-
works NU-125 and NU-140 based on C3-symmetrical triazole-
based hexacarboxylate linkers, which were easily synthesized via
click reaction.61,84 At 298 K and 65 bar, the volumetric methane
adsorption and deliverable capacities are, respectively, 232 and Fig. 11 (a) Two types of 1D channels in UTSA-20, with open metal sites
183 cm3 (STP) cm3 for NU-125, and 200 and 170 cm3 (STP) cm3 pointing to the pores and (b) high pressure methane adsorption isotherms
for NU-140. of UTSA-20. Reprinted with permission from ref. 53. Copyright 2011, Wiley.
Zhao et al. reported three isostructural (3,24)-connected rht-
type MOFs (SDU-6–8) based on C3-symmetrical organosilicon-
which is equivalent to the density of compressed methane at
based hexacarboxylates.67 Interestingly, although three isophthalate
300 K and 340 bar. The methane storage capacity can reach
units on the organic linkers are noncoplanar, the (3,24)-connected
230 cm3 (STP) cm3 at 298 K and 65 bar.
rht-type network is still formed. More importantly, by changing the
Furthermore, GCMC simulation reveals that besides the open
functional groups on the central silicon atom of the organic linker,
copper sites, the channel site is also one primary adsorption site
the cage size of T-Oh can be systematically tuned, while the sizes of
(Fig. 12). Methane binding at linker channel sites is even stronger
cub-Oh and T-Td are almost unchanged, thus providing a good
chance to see the effect of the functional groups on the gas
adsorption capacity. At 298 K and 35 bar, the total volumetric
methane uptake capacities of SDU-6–8 are 172, 159, and
147 cm3 (STP) cm3, respectively. The higher methane adsorp-
tion capacity in SDU-6 is attributed to its higher surface area
and polar hydroxyl groups.
3.4.4 UTSA-20. By immobilizing the high density of open
metal sites and constructing a suitable pore space within a MOF,
we realized a porous MOF material UTSA-20 for high-density
methane storage.53 UTSA-20 was obtained by a solvothermal
assembly of dicopper paddlewheel SBUs and the organic linker
H6bhb (5,5 0 ,500 -(benzene-1,3,5-triyl)tris-1,3-benzenedicarboxylic
acid). There exist 1D rectangular pores of about 3.4 4.8 Å and Fig. 12 (a) Probability distribution of the CH4 center of mass in UTSA-20
1D cylinders of 8.5 Å diameter along the c axis, with open metal ([001] view), obtained from GCMC simulation at 298 K and 10 bar. The red
sites pointing to the pores for binding guest molecules (Fig. 11a). regions represent the places where methane molecules are heavily popu-
The interplay of the high density of open copper sites and lated in the MOF structure. Note that the open Cu site is preoccupied with
CH4 molecules. (b) The pore surface of the interconnected channel pores
optimal pore spaces enables UTSA-20 to be a promising material
in UTSA-20 with adsorbed methane at the linker channel site. The channel
for methane storage. The overall volumetric methane storage width along the c axis matches well with the size of the adsorbed methane
capacity is 195 cm3 (STP) cm3 at 300 K and 35 bar (Fig. 11b). molecules, leading to an enhanced van der Waals interaction. Reprinted
The methane storage density in micropores is 0.222 g cm3, with permission from ref. 53. Copyright 2011, Wiley.
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than that at open metal sites because the methane molecule is Under practical conditions (303 K and 35 bar), UiO-67(Zr)
well sandwiched between two bhb linker potential surfaces. shows the highest storage capacity of 146 cm3 (STP) cm3.
Full saturation of these two primary sites will generate a Despite the methane storage capacity is lower than the best
methane uptake of 162 cm3 (STP) cm3, which is approximately performing MOFs such as HKUST-1, PCN-14, and UTSA-20, the
85% of the total methane uptake measured experimentally at high stability against water makes it more attractive for prac-
300 K and 35 bar. The remaining 15% of the storage capacity tical methane storage application.
can be readily provided by other secondary binding sites, which The high degree of connectivity of Zr6O4(OH)4(COO)12 gives
exhibit a weak interaction with methane. rise to the high stability but at the same time limits the pore
window size and thus negatively affects the availability of pores.
3.5 MIL series Under the premise of ensuring structural stability, reducing the
Férey et al. synthesized two zeolite-type mesoporous frame- ability of a cluster to coordinate multifunctional linker mole-
works, MIL-100(Cr)169 and MIL-101(Cr),170 which were built cules has two beneficial effects: (1) boosting the porosity of the
up from trimeric chromium(III) octahedral clusters and trime- MOF material and (2) creating more open metal sites after
sate and terephthalate, respectively. In frameworks, two types removal of terminal solvent molecules. Bon et al. reported such
of mesoporous cages were connected through microporous an example. A porous MOF DUT-51(Zr) was made from a bent
windows. Because of high porosity and stability, these two thiophene dicarboxylate linker, namely dithieno[3,2-b;2 0 ,3 0 -d]-
MOFs were tested for methane adsorption storage, adsorbing thiophene-2,6-dicarboxylate, using a modulator approach.93
a large amount of methane gravimetrically.80 The Zr-based cluster is 8-connected instead of 12-conneced as
MIL-53 (M = Cr and Al) is a 3D microporous framework reported. The terminal position of the cluster is occupied by
containing 1D diamond-shaped channels, which is built from solvent molecules and modulator molecules, and the terminal
infinite chains of corner sharing M4(OH)2 octahedra, intercon- solvents can be removed, thus creating open metal sites for
nected by benzenedicarboxylate units.171 The striking feature is binding guest molecules. There exist two distinct types of cages
that MIL-53 exhibits a breathing phenomenon which is trig- in the framework, namely, octahedron and cuboctahedron,
gered by adsorption of polar molecules such as CO2. In con- which are connected via triangular windows. The maximum
trast, nonpolar molecules such as methane cannot induce the excess of methane adsorbed on DUT-51(Zr) is 0.12 g g1 at
structural transformation of the framework due to the lack of a 80 bar and 298 K. More importantly, DUT-51(Zr) exhibits high
strong specific interaction with the MIL-53 framework. For stability against hydrolysis. No significant loss of crystallinity
methane adsorption at or above ambient temperature, the large and porosity occurred when the dried sample was immersed in
pore structure of MIL-53 is thermodynamically favored over the water for 12 h. The high hydrolytic stability is certainly very
whole pressure range. The amount adsorbed at 304 K and 35 bar is important for the practical application of MOF materials as
about 155 cm3 (STP) cm3 for MIL-53(Al) and 165 cm3 (STP) cm3 natural gas adsorbent media in the near future.
for MIL-53(Cr), respectively.60 Rallapalli et al. reported an An interesting phenomenon observed in UiO-66(Zr) is that
enhanced methane storage capacity of 186 cm3 (STP) cm3 there exist missing linker defects, which have recently been
for MIL-53(Al) using a solvent extraction activation method.59 unambiguously confirmed by Zhou et al. using a high-
A Cu-based compound MIL-53(Cu) has also been synthesized resolution NPD technique.173 By varying the synthesis conditions
with a methane uptake of 191 cm3 (STP) g1 at 298 K and such as the concentration of the acetic acid modulator and the
35 bar, but the structure is still not clear.125 synthesis time, the linker defects can be tuned systematically.
With an increased defect concentration, gas uptake for methane,
3.6 Zr-based MOFs especially polar CO2, was enhanced at high pressure. Further-
Although some MOFs have exhibited storage capacities which more, it was found that although the hydrated sample has
potentially meet or exceed the old DOE target, there are also slightly smaller pore volume and surface area than the dehydrated
potential concerns about the stability of these MOFs against the form, the former performs better than the latter in gas adsorption,
moisture and pressure. Since the discovery of UiO-66 by Cavka which is certainly favorable for practical applications. Such an
et al.,172 an emerging class of Zr–carboxylate frameworks has enhancement effect is attributed to the Columbic interaction
attracted great attention of the MOF community because high between the gas molecules and polar OH groups.
inertness of Zr–carboxylate bonds endows the frameworks with
excellent thermal, chemical, and mechanical stability. Numerous
isoreticular MOFs such as UiO-67 and UiO-68 have been 4. Screening, rationalization and
reported. All these materials are built up from Zr6O4(OH)4 optimization of MOFs for methane
clusters linked by 12 dicarboxylate linkers to form a 12-connected storage
network with a fcu topology, in which each centric octahedral
cage is connected to 8 corner tetrahedral cages through triangular With more porous MOFs being synthesized and structurally
windows. characterized at labs, while reliable instruments for high
Yang et al. used a computational approach to predict pressure methane storage studies are kind of limited, there is
the methane adsorption in a series of isoreticular Zr–MOFs, a strong need to figure out the relationship between the
including UiO-67, UiO-68, Zr-AzoBDC, and Zr-Cl2AzoBDC solids.78 porosity (pore volume or BET surface area) and the methane
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storage capacity of the MOF materials. Thus, we can screen and

make the preliminary judgments on their potential for
methane storage before some of them can be examined in
detail. In this regard, some very promising results have been
realized.
He et al. examined a series of copper–tetracarboxylate
frameworks with similar structures whose porosities are

systematically varied for methane storage at room temperature
and 35 bar.30 The study reveals that under these methane
storage conditions (methane uptakes are still not saturated
yet), those porous MOFs with higher porosities (shown in both
their higher pore volumes and BET surface areas) have lower
methane storage pore occupancies. The pore occupancy, O,
under 35 bar and at room temperature, is defined as the excess
methane storage amount under 35 bar and at room tem-
perature, C, divided by the excess saturated methane storage
amount, Csat, which is determined at 150 K. This is reasonable,
because the pore spaces within MOFs of large pore volumes are
basically larger in dimension than those of small pore volumes,
so the larger spaces are less efficiently utilized for methane
storage under 35 bar and at room temperature. The fact that
both the pore occupancy and the excess saturated methane
uptake at 150 K are linearly correlated to their pore volume of
the porous MOF has enabled us to figure out an empirical
formula to predict the methane storage capacity (under 35 bar
and at room temperature) of a specific MOF: Cexcess = 126.7 Fig. 13 (a) Saturated excess gravimetric methane adsorption capacity at
Vp2 + 381.6 Vp 12.6; Ctotal = 126.7 Vp2 + 415.1 Vp 12.6. 150 K (cm3 (STP) g1) versus pore volume (cm3 g1) of the MOFs investi-
Here the units of C and Vp are cm3 (STP) g1 and cm3 g1 gated. (b) Pore occupancy versus pore volume (cm3 g1). Pore occupancy is
(Fig. 13). Supposing we know the framework densities from defined as the excess gravimetric methane uptake at 300 K and 35 bar
their X-ray crystal structures of the activated samples, we can divided by the saturated excess gravimetric methane uptake at 150 K. The
solid lines show the linear fitting results. 1: NOTT-100; 2: NOTT-109; 3:
predict their volumetric storage capacities as well. The calcu- NOTT-101; 4: NOTT-103; and 5: NOTT-102.
lated methane storage capacities from this empirical formula
match quite well with those experimentally determined ones,
which will enable us to make a quick judgment on a new and 65 bar, as well as (1/framework density) are well correlated
porous MOF for its potential application in methane storage with the BET surface area (Fig. 14b). From these correlations,
once we characterize its X-ray crystal structure and porosity. it can be deduced that (1) total methane storage capacity at
It can also help us to evaluate whether or not an optimized 65 bar and room temperature can be approximately calculated
activation has been fulfilled for methane storage. Such a simple based on the equation: Ctotal (cm3 (STP) g1) = 0.07958
equation can certainly facilitate our screening of porous MOFs BET (m2 g1) + 127.1; (2) a hypothetical MOF with a BET surface
for their methane storage. area of 7500 m2 g1, a pore volume of 3.2 cm3 g1 and a
Studies on a number of reported porous MOFs by Kong et al. framework density of 0.28 g cm3 can meet the DOE’s new
revealed that (1/framework density) is linearly correlated with gravimetric target of 0.5 g (CH4) g1 (adsorbent).
the pore volume of the MOFs, while the total methane uptake at Although the above mentioned empirical formula can facili-
60 bar and room temperature is linearly dependent on their tate our screening and target new promising porous MOFs for
BET surface area.64 Accordingly, the total methane storage capacity high methane storage, detailed studies through computational
at 60 bar and room temperature can be approximately calculated simulations, spectroscopic measurements and diffraction are
based on the following equation: Ctotal (cm3 (STP) g1) = very important to rationalize the factors and/or parameters and
147.2 + 0.06526 BET (m2 g1). strategies to optimize/maximize methane storage capacities.
Peng et al. compared the methane adsorption properties of Snurr et al. used high-throughput computational simulations
six promising MOFs (HKUST-1, NiMOF-74, PCN-14, UTSA-20, to predict the textural properties (surface area, pore volume and
NU-111, and NU-125) by measuring high pressure isotherms on pore size distribution) and methane uptakes at room tempera-
the same instrument and under the same conditions, leading ture and 35 bar in a large number of hypothetical MOFs, and
to reordering of MOF performance ranking.29 At 298 K and discovered some very useful structure–property relationships.52
65 bar, HKUST-1 and NU-111 exhibit the best results in terms For example, volumetric methane adsorption is proportional
of volumetric and gravimetric uptake, respectively (Fig. 14a). to the volumetric surface area. In terms of the widely used
Furthermore, the pore volume, the gravimetric uptake at 298 K gravimetric surface area, volumetric methane adsorption firstly
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modulated by the functional groups lead to different methane

adsorption capacities. The small and polar OH groups in SDU-6
enable it to adsorb much more methane at 35 bar. Wang et al.
investigated the effect of functional groups on methane adsorp-
tion properties in three isoreticular microporous MOFs.65 Their
studies reveal that introducing functional groups such as CH3
and Cl increases the heat of adsorption and thus the uptake

at low pressure, but also reduces the free volume and thus
negatively affects the gas adsorption properties at high pressure.
Summarizing, the gas sorption properties depend on the positive
effect of adsorbate–adsorbent interaction enhancement and the
negative effect of the surface area and pore volume reduction
upon introduction of functional groups into the framework.
Wu et al. determined the exact locations of the stored
methane in three MOFs, HKUST-1, PCN-11, and PCN-14, and
concluded that open metal sites and van der Waals potential
pocket sites are favorable structural features and dominate the
methane uptake.147 The open metal sites are coordinatively
unsaturated and can interact favorably with the adsorbate
methane through Coulomb interactions, while at the van der
Waals pocket sites, the methane molecules interact with multi-
ple surfaces, leading to an overall enhanced dispersive inter-
action. The design principle has well been demonstrated by
Guo et al.53 By immobilization of high density of open metal
Fig. 14 (a) A schematic diagram showing total gravimetric and volumetric sites and construction of suitable pores in microporous MOF
methane adsorption capacities at 298 K and 65 bar, and (b) total gravi- UTSA-20, this MOF exhibits high density methane storage
metric uptake at 298 K and 65 bar, pore volume, and (1/framework density)
capacity. In addition, it should be borne in mind that pursuing
as a function of BET surface area in six MOFs: HKUST-1, NiMOF-74, PCN-14,
NU-111, and NU-125. Reprinted with permission from ref. 29. Copyright MOFs with high open metal sites will not be a good strategy to
2013, American Chemical Society. target MOFs with high methane delivery.
The doping of MOFs with alkali or transition metals has
been used to improve the hydrogen sorption affinities, but this
increases and then begins to decrease when it surpasses the strategy is seldom extended to methane storage. Xiang et al.
optimal gravimetric surface area of 2500–3000 m2 g1. For showed that incorporation of CNTs into MOFs can enhance the
volumetric methane uptake, the optimal void fraction is around uptakes of CO2 and CH4 by MOFs.46 The CO2 and CH4 adsorption
0.8, and the optimal pore sizes are 4 and 8 Å, exactly big enough capacities are further improved by doping the CNT modified
for one or two methane molecules. These structure–property MOFs with Li+. It is believed that incorporation of CNT into MOFs
relationships provide clues and principles to rationally design increases the pore volume while doping MOFs with Li+ improves
MOFs for methane storage. the affinity towards gas molecules, thus achieving enhanced
Raman spectroscopic investigations of methane adsorption composite performance. As for Li doping, the Li+ content must
behavior in a series of IRMOFs at room temperature and high be maintained at a low concentration to achieve the enhance-
pressure have revealed that the methane adsorption is domi- ment. Also, Lan et al. showed theoretically that doping of COFs
nated by the organic linkers instead of the metal clusters.132 with Li+ ions can significantly enhance the methane uptake of
This result indicates that the linker functionalization may covalent–organic frameworks (COFs).174 However, Gong et al.
afford a better storage material. Due to the hydrophobic nature reported an anionic porous MOF.94 When Et2NH2+ counter-
of methane, the incorporation of hydrophobic groups such as cations were exchanged with Li+ ions, the methane adsorption
methyl and aromatic groups in the organic linkers might capacities decreased despite the higher pore volume and surface
increase methane uptake capacities. In fact, molecular simula- area in Li+ exchanged MOFs. Authors think this is due to the
tion by Snurr et al. has shown that MOFs with lipophilic higher affinity of Et2NH2+ towards methane than Li+ ions, which
functional groups such as methyl, ethyl and propyl groups is different from the aforementioned case.
dominate the best performers.52 In addition, incorporation of Obviously, methane storage capacities of porous MOFs are
these hydrophobic groups can improve the moisture stability of dependent on a number of factors. As demonstrated in the
the MOFs. empirical formula, the main factor for the gravimetric methane
As mentioned previously, Sun et al. synthesized three iso- storage amount is still the porosity, which is demonstrated by
reticular rht-type MOFs SDU-6–8 with different functional groups its pore volume and/or BET surface area. Porous MOFs for high
immobilized on the truncated octahedral cages.67 The different volumetric methane storage need to have a balanced porosity
size and surface chemistry of the truncated octahedral cages and framework density, so the pore space can be efficiently
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Methane storage in metal–organic frameworks

1. Introduction power plants and automobile transport is a growing environ-

Yabing He earned his PhD in Wei Zhou received his PhD in

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Guodong Qian was born in Banglin Chen was born in

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have been reported for methane storage. Significantly, several

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Methane adsorption capacity is not the sole property that has to

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Methane adsorption Methane adsorption

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Methane adsorption Methane adsorption

SDU-8 0.639 1.02 2516 147 105 298 35 67

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Methane adsorption Methane adsorption

Zn2(L6) 1.105 0.155 367 34b 298 35 121

Kim et al. investigated methane binding sites in the Zn based

Zn4O(COO)6 SBU is one very useful inorganic building block for

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loaded with diﬀerent amounts of CD4 revealed that methane

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trolled by the methane aﬃnity towards the framework. However,

Fig. 7 (a) Cage structures and (b) high-pressure methane adsorption

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found to be around 195–202 cm3 (STP) cm3 under 35 bar and

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Interestingly, compared with the analogous terphenyl-based

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greatly boost the molecule-accessible surface area. Based on

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storage capacity of the MOF materials. Thus, we can screen and

frameworks with similar structures whose porosities are

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modulated by the functional groups lead to different methane

and Cl increases the heat of adsorption and thus the uptake

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