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Cite this: Chem. Commun., 2012, 48, 9831–9833

COMMUNICATION
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CH4 storage and CO2 capture in highly porous zirconium oxide based
metal–organic frameworkswz
Qingyuan Yang,ab Vincent Guillerm,c Florence Ragon,c Andrew D. Wiersum,d
Philip L. Llewellyn,d Chongli Zhong,a Thomas Devic,c Christian Serrec and
Guillaume Maurin*b
Received 2nd July 2012, Accepted 14th August 2012
DOI: 10.1039/c2cc34714h

A series of porous Zr oxoclusters-based MOFs was computationally Through a judicious choice of these organic and inorganic moieties,
explored for their gas storage/capture performances. The highly many MOFs were designed with ultra-high porosity, including
porous UiO-67(Zr) and UiO-68(Zr) solids show exceptionally high MIL-101,5a MOF-177,5b MOF-205,3a PCN-14,5c UMCM-2,5d that
CH4 and CO2 adsorption capacities under operating conditions that have further shown high CO2 and/or CH4 uptakes.3a,5c,6 However,
make these thermal, water and mechanical resistant materials very the majority of these promising materials suffers either from a
promising for physisorption-based processes. relatively poor stability under humidity or would require a high
energy cost for regeneration that are both severe drawbacks for
The anthropogenic emission of CO2 from fossil fuel burning in practical applications.3c,d Indeed, tailoring more stable, chemically-
power plants and automobile transport is a growing environ- resistant MOF frameworks combined with high adsorption perfor-
mental and economic issue. CH4 is another strategic gas of mance is still nowadays a great challenge for the MOF community.
considerable interest. Apart from its negative greenhouse Here, we focus on an emerging class of zirconium-based
effect, this latter species, which is the main component of the MOFs derived from the UiO-66(Zr) topology. This isoreticular
natural gas, is also considered as a cleaner energy carrier than series includes the existing UiO-67(Zr),7a UiO-68(Zr)7a and
petroleum oil because of its higher hydrogen-to-carbon ratio Zr-AzoBDC7b solids where 4,4 0 -BPDC, TPDC and AzoBDC
and a resulting much lower carbon emission.1 Indeed, the ligands substitute the parent BDC organic node of UiO-66(Zr),
search for safe and high-capacity CH4 storage and CO2 respectively, that are completed by a newly synthesized
capture systems has been a long-standing challenge that has Zr-MOF involving Cl2AzoBDC as a linker (Fig. 1). The
triggered tremendous studies with the aim to improve the hydroxylated forms of these analogue materials are built up
existing related technologies. It is well established that the from the inorganic block Zr6-octahedra [Zr6O4(OH)4] bounded
physisorption-based processes involving porous solids offer an to twelve organic linkers, leading to a three dimensional periodic
efficient storage/capture alternative with the ability to release structure in which each centric octahedral cage (Fig. 1a) is
the adsorbed gases easily.2 Among this class of materials, connected to eight corner tetrahedral cages (Fig. 1b) through
porous metal–organic frameworks (MOFs) have attracted triangular windows. The parent UiO-66(Zr) has been recently
substantial attention during the past decades in the field of shown to be stable up to 450 1C under air, unaltered upon water
gas adsorption/separation both experimentally3 and theoreti- adsorption8a and mechanical pressure,7a easily regenerable8a,b
cally.4 Such an intriguing family of coordination materials and selective for the CO2–CH4 mixture with a high working
corresponds to crystalline hybrid media built up from inorganic capacity.8c The four other analogues are also porous MOFs (see
metal-ion subunits connected by polytopic organic ligands. the structural features provided in Table S3 in the ESIz). The
solvothermal synthesis of the UiO-67(Zr), Zr6-AzoBDC and its
a
State Key Laboratory of Organic-Inorganic Composites, 3,3 0 ,4,40 -Cl2AzoBDC functionalized analogue have been carried
Beijing University of Chemical Technology, Beijing 100029, China
b
Institut Charles Gerhardt Montpellier, UMR CNRS 5253, UM2,
Place E. Bataillon, 34095 Montpellier Cedex 05, France.
E-mail: [email protected]
c
Institut Lavoisier, UMR CNRS 8180-Universite´ de Versailles
StQuentin-enYvelines, 45 avenue des Etats-Unis, 78035 Versailles,
France
d
Madirel UMR CNRS 7246, Universite´s Aix-Marseille - CNRS,
Centre de Saint Je´rôme, 13013 Marseille, France
w This article is part of the ChemComm ‘Metal-organic frameworks’ Fig. 1 Illustration of the Zr-MOFs crystalline structure: (a) octahedral
web themed issue.
cage, (b) tetrahedral cages. H atoms were omitted for clarity. The large
z Electronic supplementary information (ESI) available: Details of
experiments and molecular simulations. CCDC 889529–889533. For spheres represent the void regions inside the cages (Zr polyhedra: red for
ESI and crystallographic data in CIF or other electronic format see octahedral cage, green for tetrahedral cages; C, gray; O, red). The extended
DOI: 10.1039/c2cc34714h organic linkers are also presented.

This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 9831–9833 9831
 out and the resulting solids activated and characterized. As a
further step, their thermal, water and mechanical stabilities have
been assessed (see ESIz), revealing that this class of solids is stable
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up to 450 1C, in water at room temperature overnight and exhibits

a fair mechanical stability upon application of uniaxial pressure.
In light of such favourable porosities and properties, a step
further consisted of exploring via a predictive approach the
adsorption capacities of this extended series of Zr-MOFs for
CH4 and CO2 under industrially relevant conditions. This Fig. 2 Simulated adsorption isotherms for (a) CH4 and (b) CO2 in the
modelling effort is based on a preliminary computational five Zr-MOFs at 303 K. The experimental data are also provided for
assisted structure determination strategy conducted in tandem UiO-66(Zr) as a comparison.
with X-ray powder diffraction (XRPD) experiments to propose MOFs, activated carbons and zeolites. As indicated in this
plausible structure candidates for each investigated Zr-MOF. table, among these Zr-MOFs, UiO-67(Zr) shows the highest
Indeed, starting with the parent UiO-66(Zr), the crystallographic storage capacity for CH4 (146 cm3 (STP) cm3) at 35 bar. It
structure for each Zr-MOF analogue was first built using a should be noted that the target set by the U.S. department of
ligand replacement strategy9 based on the unit cell parameters Energy (DOE) for such an application is 180 cm3 (STP’) cm3
deduced from XRPD experiments. The resulting structures were where STP’ denotes 1 bar and 298 K.11 To match the current
further refined using a density functional theory (DFT) geometry IUPAC definition used in this work, this objective corresponds
optimization procedure (details of the computational method- to a value of 167 cm3 (STP) cm3.11a Together with the results
ology are described in the ESIz). The geometry optimized shown in Fig. 2, one can argue that the storage capacities of
structures and their corresponding structural features are both UiO-67(Zr) and Zr6-Cl2AzoBDC are only slightly below the
provided in Fig. S8 and Table S3 (see ESIz). The theoretical DOE requirement. Further, Table 1 emphasizes that UiO-67(Zr)
accessible surface areas and pore volumes vary from 1020 to outperforms most of the well-known MOFs reported so far except
4240 m2 g1 (0.45 cm3 g1 to 1.82 cm3 g1) when one goes the Cu(II)-paddlewheel based Cu-BTC, UTSA-20 and PCN-14,
from UiO-66(Zr) to UiO-68(Zr) and further decrease for and the CPO-27(Ni) containing Ni(II) coordinatively unsaturated
Zr6-AzoBDC (3640 m2 g1 and 1.38 cm3 g1) and Zr6-Cl2AzoBDC sites (cus).
(2885 m2 g1 and 1.13 cm3 g1). Except from the parent Indeed, while these three last MOFs show the best performances,
UiO-66(Zr) where a very good agreement is obtained between the their structures are known to be dramatically altered upon water
experimental and predicted geometric features, some discrepancy adsorption3c,12 in contrast to what have been demonstrated
can be noticed for the other solids (see ESIz) mainly due to the
presence of residual Zr oxide and/or incomplete activation of the Table 1 Adsorption uptakes for CH4 (35 bar)–CO2 (40 bar) and
sample. This observation strongly suggests that the optimal adsorp- working capacity predicted in the Zr-MOFs at ambient temperature
vs. the values in other adsorbents including MOFs, zeolites and
tion performances of these Zr-MOFs can be only achieved via a
activated carbons
computational approach. This information will further orientate
the synthesis effort to be deployed for optimizing the activation Vadsorption uptake Vworking capacitya
procedure of the most promising solids. (cm3 (STP) cm3) (cm3 (STP) cm3)
Grand Canonical Monte Carlo simulations (see ESIz) were Materials T/K CH4 CO2 CH4 CO2
performed to predict the optimal adsorption uptakes for CH4 UiO-66(Zr) 303 127 205 105 116
and CO2 in this series of Zr-MOFs for a wide range of pressure at UiO-67(Zr) 303 146 301 138 266
303 K. For gas uptake and delivery purpose, the total adsorbed UiO-68(Zr) 303 123 333 118 313
amount is a more relevant quantity compared to the excess one.4b Zr6-AzoBDC 303 124 223 122 209
Zr6-Cl2AzoBDC 303 135 293 127 267
Further from an application standpoint, it is more meaningful to Mesoporous MOFs
6a
express the adsorption uptakes of different materials in terms of MIL-101(Cr) 303 103 340 64 197
volume than mass as the densities of the adsorbents vary.10 For this MOF-2003a 298 61 267 59 263
MOF-2053a 298 114 310 111 305
reason, the adsorbed amounts were converted into cm3 (STP) cm3 UMCM-2 303 128 357 123 346
(STP defined by IUPAC: 1 bar and 273 K) using the crystallo- PCN-6814a 298 117 281 112 264
graphic density of each MOF. Primarily, UiO-66(Zr) was selected NU-1004b 298 –– 327 –– 310
as a model material since its experimental and simulated geometric Microporous MOFs
MOF-53a,6b 298 126 326/293 124 312/283
features concur very well (see Table S1, ESIz). MOF-1773a,6b 298 124 357/332 122 349/328
14b,e
Fig. 2 shows a very good agreement between the adsorption MIL-47(V) 303 145 250b 132 214
isotherms simulated for this material and the corresponding Cu-BTC14c 298 180 278 153 200
PCN-145c 290 230 –– 210 ––
experimental data obtained by gravimetry measurements (see 14d
CPO-27(Ni) 298 214 331 160 142
ESIz). Such a validation step allowed us to confidently carry UTSA-20 14f
300 195 323c 173 226
out further explorations for the whole series of Zr-MOFs. Fig. 2 Other conventional adsorbents
thus also reports the absolute adsorption isotherms for CH4 AC Maxsorb13a 298 74 166 64 147
Zeolite 13X13b 298 128 185d 112 69
and CO2 in the remaining four Zr-MOFs. Table 1 summarizes
a
the predicted adsorption capacities at the pressures considered Calculated from the difference of the adsorption amounts adsorbed
in MOFs at 1 and 10 bar for CH4 and at 1 and 40 bar for CO2.
in practical applications (CH4: 35 bar,5c CO2: 40 bar4b) that are b
Measured at 20 bar. c Measured at 35 bar. d Measured at 32 bar.
compared with the performances of other adsorbents including

9832 Chem. Commun., 2012, 48, 9831–9833 This journal is c The Royal Society of Chemistry 2012
 above for UiO-67(Zr). In addition, this Zr-MOF shows a support of the Beijing Nova (2008B15), ‘‘Hubert Curien Cai
storage capacity for CH4 which is much higher than other Yuanpei’’ (24038XC) programs and Natural Science Foundation
conventional adsorbents such as the activated carbon (AC) (21136001) is also greatly appreciated.
Published on 15 August 2012. Downloaded by Universidad de Valladolid Biblioteca on 11/24/2022 4:57:21 PM.

Maxsorb13a and the zeolite 13X,13b thus UiO-67(Zr) is particularly

promising for such an application. Notes and references
The situation slightly differs for the CO2 capture with UiO-68(Zr)
1 S. Ma and H.-C. Zhou, Chem. Commun., 2010, 46, 44.
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This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 9831–9833 9833