MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc -MOF for CH4, O2, and CO2 Storage

Article abstract of DOI:10.1021/jacs.5b07053

The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly porous and stable, aluminum-based metal-organic frameworks with soc topology. From this platform, three compounds were experimentally isolat

Full text of DOI:10.1021/jacs.5b07053

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Article
MOF Crystal Chemistry Paving the Way to Gas Storage Needs:
Aluminum Based soc-MOF for CH4, O2 and CO2 Storage
Dalal Alezi, Youssef Belmabkhout, Mikhail Suetin, Prashant M. Bhatt, Lukasz Jan Weselinski, Vera Solovyeva,
Karim Adil, Ioannis Spanopoulos, Pantelis N. Trikalitis, Abdul-Hamid Emwas, and Mohamed Eddaoudi
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b07053 • Publication Date (Web): 14 Sep 2015
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MOF Crystal Chemistry Paving the Way to Gas Storage
Needs: Aluminum Based soc-MOF for CH4, O2 and CO2
Storage
Dalal Alezi,† Youssef Belmabkhout,† Mikhail Suyetin,† Prashant M. Bhatt,† Łukasz J. Weseliński,†
Vera Solovyeva,† Karim Adil,† Ioannis Spanopoulos,§ Pantelis N. Trikalitis,§ AbdulꢀHamid Emwas,‡
Mohamed Eddaoudi*,†
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†
Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous
Materials Center, Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology
(KAUST), Thuwal 23955ꢀ6900, Kingdom of Saudi Arabia, Eꢀmail: mohamed.eddaoudi@kaust.edu.sa
10 ‡Imaging and Characterization Core Lab, King Abdullah University of Science and Technology (KAUST)
§Department of Chemistry, University of Crete, Voutes 71003, Heraklion, Greece
Supporting Information Placeholder
ABSTRACT: The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly
porous and stable, aluminum based MetalꢀOrganic Frameworks with soc topology. From this platform, three compounds were
15 experimentally isolated and fully characterized, namely, the parent AlꢀsocꢀMOFꢀ1 and its naphthalene and anthracene analogues.
AlꢀsocꢀMOFꢀ1 exhibits outstanding gravimetric methane uptake (total and working capacity). It is shown experimentally, for the
first time, that the AlꢀsocꢀMOF platform can address the challenging Department of Energy dual target of 0.5 g/g (gravimetric)
and 264 cm3 (STP)/cm3 (volumetric) methane storage. Furthermore, AlꢀsocꢀMOF exhibited the highest total gravimetric and
volumetric uptake for carbon dioxide and the utmost total and deliverable uptake for oxygen at relatively high pressures among all
20 microporous MOFs. In order to correlate the MOF pore structure and functionality to the gas storage properties, to better
understand the structureꢀproperties relationship, we performed a molecular simulation study and evaluated the methane storage
performance of AlꢀsocꢀMOF platform using diverse organic linkers. It was found that shortening the parent AlꢀsocꢀMOFꢀ1 linker
resulted in a noticeable enhancement in the working volumetric capacity at specific temperatures and pressures with amply
conserved gravimetric uptake/working capacity. In contrast, further expansion of the organic linker (branches and/or core) led to
25 isostructural AlꢀsocꢀMOFs with enhanced gravimetric uptake but noticeably lower volumetric capacity. The collective
experimental and simulation studies indicated that the parent AlꢀsocꢀMOFꢀ1 exhibits the best compromise between the volumetric
and gravimetric total and working uptakes in a wide range of pressure and temperature conditions.
INTRODUCTION
Gas storage in porous materials is a desirable technology that
30 has been significantly developed in recent years, owing to its
potential to address numerous persisting challenges in a
number of industrial applications related to energy,
environment, and health care sectors.1 In the context of clean
energy, there is an amplified willingness to reduce greenhouse
35 gas emissions, caused by energy production processes, as
evident by the considerable ongoing research in academia and
industry alike aiming to develop practical solutions to mitigate
this problem. Correspondingly, appropriate studies have been
conducted in order to practically deploy a relatively cleaner
40 alternative fuels such as methane (CH4), a primary component
of natural gas (NG) and biogas. CH4 is of great interest as a
fuel for stationary and mobile applications due to (i) its high H
to C ratio in comparison to other fossil fuels, resulting in a
relatively lower CO and CO2 emissions,2 and (iii) its lower
45 sulfur and nitrogen contents leading to a lessen SOx and NOx
emissions. The aforementioned attributes position CH4 as an
appreciably cleaner fuel than gasoline and diesel.3 Nonetheless,
the main drawback of CH4, as compared to liquid fossil fuels,
is its low volumetric energy density. Therefore development of
50 suitable and sustainable onꢀboard vehicle methane storage
solutions, close to room temperature, is vital to the successful
deployment of methane as a conventional fuel for transport
applications.4
Highly porous materials represent an interesting category of
55 adsorbents that display distinct structural advantages for CH4
storage. The appropriate combination of a high surface area
associated to a considerable pore volume with a suitable pore
shape and functionality, in a given porous material, is crucial to
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achieve the desired enhanced CH4 storage uptake and a
In this context and considering the aforementioned requisites,
65 we identified the MOF platform based on the soc topology
(squareꢀoctahedral) as promising platform to access
practical working capacity at a set pressure and temperature.5 It
is to note that the volumetric working capacity is an essential
parameter to assess the material’s performance towards CH4
storage. The working capacity represents the usable amount of
CH4 derived by subtracting the unused adsorbed CH4,
corresponding to the uptake at the delivery pressure (5 bar),
from the uptake at the maximum adsorption pressure (35 bar or
higher).6 Prominently, one of the pathways to enhance the
a
isoreticular MOF materials for potential use in gas storage and
separation applications. The socꢀMOF platform offers
interesting structural features where the pore system comprised
70 of cavities and channels can be fineꢀtuned in the micropore
domain by the judiciously fineꢀtuning the square building unit
(the tetraꢀcarboxylate ligand).14 It is to note, that the first
reported socꢀMOF materials (In, Ga, and Fe based socꢀMOF)
revealed an exceptionally high gas storage density for H2 and
75 CH411h, 15 albeit their associated moderate surface area and pore
volume when compared to the best storage MOF materials.6a, 16
Congruently, we found it compelling to target socꢀMOFs with
relatively larger surface areas and pore volumes, via
isoreticular chemistry where the expansion strategy is
80 employed to construct isoreticular socꢀMOFs based on
selected/compatible and expanded organic MBBs, and
subsequently evaluate their performance for storage of valuable
commodities such as CH4, H2, CO2 and O2.
5
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10 methane working capacity of a given porous material is to
regulate its methane uptake at relatively low pressures and
subsequently reduce the unused CH4 uptake up to the 5 bar
threshold.
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Relatedly, the storage of other gases such as nitric oxide (NO)
15 and carbon dioxide (CO2) has been previously studied and
explored for various relevant applications.1a, 7,8 On the contrary,
studies pertaining to high pressure oxygen (O2) storage are still
scarce.9 The availability of high amounts of O2 is of prime
importance in health care domain, particularly in the treatment
20 of respiratory insufficiencies and in hyperbaric oxygen changes
for the treatment of carbon monoxide poisoning.
Correspondingly, large amount of oxygen is used to enrich air
during catalysts regeneration in the catalytic cracking units.10
Markedly, there is a significant need in developing efficient
25 pathways to store O2 for various industrial needs.
Markedly, the construction of a highly microporous MOF with
85 a soc topology requires the judicious selection of an expanded
rectangular organic linker that facilitates the in situ formation
of the targeted inorganic oxoꢀcentered trinuclear M(III) cluster
[M3(µ3ꢀO)(O2C–)6], (M3+= In, Al, Fe, etc.). Specifically,
targeting MOFs based on the trinuclear aluminum(III) cluster
90 will permit the development of a relatively low cost material
with tailored properties for gas storage applications.17 It is
important to note that MOFs based on trinuclear Al(III) cluster
[Al3(µ3ꢀO)(O2C–)6], 6ꢀconnected MBB, are scarce with only
few examples reported in the literature due to challenges in
95 isolating reaction conditions that allow the in situ formation of
the said inorganic MBB.18
Metal Organic Frameworks (MOFs), a special class of solidꢀ
state materials, emerged as modular and functional porous
materials that can offer potential to address many enduring
challenges pertaining to energy and environmental
30 sustainability.11 Principally, advances in MOF chemistry have
permitted the successful implementation of reticular chemistry,
predesigned building blocks were directed to assemble into a
preset network topology. Namely, the Molecular Building
Block (MBB) approach is deployed to construct targeted
35 functional MOFs, where desired structural and geometrical
attributes are incorporated into the MBBs prior to the assembly
process. In effect, isolating reaction conditions that consistently
permit in situ formation of the requisite inorganic MBBs, in the
presence of a suitable organic linker, is essential for the
40 successful implementation of the MBB approach and the
subsequent formation of the targeted MOF with desired
network topology.12
In this work, we report the synthesis and the singleꢀcrystal
structure, based on singleꢀcrystal Xꢀray diffraction (SCXRD)
studies, of the first aluminum MOF with the soc topology and
100 possessing an exceptional porosity. Importantly, this is the first
report disclosing the assembly of the oxoꢀcentered trinuclear
aluminum(III) cluster (oxoꢀcentered aluminum(III) trimer),
[Al3(µ3ꢀO)(O2C–)6], with a quadrangular ligand into a given
MOF, namely a highly microporous socꢀMOF with more than 2
105 cm3/g pore volume and 6000 m2/g apparent Langmuir surface
area. Furthermore, the use of similar reaction conditions, that
afforded the synthesis of the parent AlꢀsocꢀMOFꢀ1, in the
presence of functionalized tetracarboxylate linkers (with
naphthalene or anthracene replacing the phenyl core in the
110 parent ligand) resulted in two new isoreticular structures,
namely naphthalene Alꢀsoc-MOFꢀ2 and anthracene Alꢀsoc-
MOFꢀ3. Extensive gas adsorption studies were carried out on
these isoreticular socꢀMOFs with different gases (N2, CO2,
CH4, O2) at low pressures (cryogenic temperatures) and at high
115 pressures. In particular, CH4 and O2 adsorption isotherms were
investigated experimentally at different temperatures and in a
wide range of pressures up to 85 and 120 bar, respectively. It
was found that AlꢀsocꢀMOFꢀ1 have one of the highest ever
total and working gravimetric CH4 uptake at 35 bar and higher
120 pressures at any given temperature. In the contrast to all other
best MOFs reported to date in the open literature for CH4
storage, the parent AlꢀsocꢀMOFꢀ1 sorption studies revealed an
enhancement in the volumetric CH4 storage working capacity
when the temperature was decreased. Particularly, at 258 K and
125 80 bar, the AlꢀsocꢀMOFꢀ1 fulfilled the Department of Energy
(DOE) targets (both gravimetric and volumetric) and exhibited
the highest working volumetric capacity of 264 (cm3STP/cm3).
Advantageously, the MBB approach permits the rational
assembly of targeted MOFs and their subsequent structural
45 fineꢀtuning using isoreticular chemistry.2b The deliberate
alteration of a MOF dimensionality and functionality without
changing its underlying topology, isoreticular chemistry, is
regarded as a powerful pathway for the development of new
functional materials with distinctive properties.
50 Evidently, the selection of an appropriate MOF platform, with
desired topological attributes for the logical practice of
isoreticular chemistry, offers potential to readily access porous
materials suitable to address the ongoing gas storage
13
challenges.11a,
Practically, several key requisites are
55 considered and targeted in order to facilitate the attainment of a
high storage MOF media: i) inorganic MBBs based on light
and abundant elements, ii) organic MBBs amenable to size,
shape and functionality adjustments via expansion and
decoration, iii) an elect MOF platform that permits access to
60 isoreticular MOFs with concomitant high surface area, large
pore volume and fineꢀtuned pores in the micropore domain, and
iv) a MOF platform based on an underlying topology that
prohibits interpenetration upon MOF expansion.
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Correspondingly, to the best of our knowledge, AlꢀsocꢀMOFꢀ1
25 reactions between H4L1 and AlCl3·6H2O in acidic solution
showed the highest gravimetric total capacity for CO2 and O2
among microporous MOFs. Furthermore molecular simulation
studies supported and confirmed our experimental results for
CH4 storage and thus encouraged us to explore various
plausible theoretical isoreticular AlꢀsocꢀMOFs, based on
expanded and/or functionalized tetracarboxylate organic
building blocks, for CH4 storage. This study permitted to i)
pinpoint various prospective AlꢀsocꢀMOFs with similar
10 outstanding CH4 storage capabilities as the parent Alꢀsocꢀ
MOFꢀ1, confirming the superior storage capabilities of the
parent AlꢀsocꢀMOFꢀ1 both volumetric and gravimetric, ii) gain
a better understanding of the structureꢀproperties relationship,
deriving a better correlation between the socꢀMOF gas storage
15 properties and the makeꢀup of the socꢀMOF porous system
(pore shape and size, ligand dimensions and functionalities).
containing the mixture of N,Nˋꢀdimethylformamide (DMF) and
acetonitrile (CH3CN) afforded colorless homogeneous crystals
with a cubeꢀshaped morphology, characterized and formulated
by SCXRD as [Al3O(TCPT)1.5(H2O)3]·|Clꢀ| (1). Compound 1
30 crystallizes in the cubic Pmꢀ3n space group. The crystal
structure of 1 reveals a 3ꢀperiodic framework built up from µ3ꢀ
oxoꢀcentered trinuclear Al(III) inorganic MBB (oxoꢀcentered
Al(III) trimer), [Al3(µ3ꢀO)(H2O)3(O2C–)6]. Each aluminum
cation (Al3+) displays an octahedral coordination environment
35 and coordinates to six oxygen atoms, namely, four bisꢀ
monodentate deprotonated carboxylate oxygen atoms from four
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independent TCPT4ꢀ ligands, one
µ3ꢀoxo anion and the
coordination sphere is completed by a terminal aqua ligand.
The trinuclear Al(III) MBBs are bridged by six independent
40 TCPT4ꢀ ligands resulting in the formation of a 3ꢀperiodic
cationic framework, AlꢀsocꢀMOFꢀ1 (Figure 1). The charge
balance is provided by the presence of chloride ions, which is
confirmed by the Xꢀray photoelectron spectroscopy (XPS)
RESULTS AND DISSCUSION
In our effort to isolate the first aluminum based socꢀMOF,
numerous attempts have been carried out to isolate reaction
20 conditions that consistently allow the formation in situ of the
desired trinuclear aluminum(III) MBB, [Al3(µ3ꢀO)(O2C–)6].
Accordingly, we designed and synthesized 3,3'',5,5''ꢀtetrakis(4ꢀ
carboxyphenyl)ꢀpꢀterphenyl (H4TCPT) tetratopic ligand
(H4L1)19 that can act as a rectangular MBB. Successfully,
50
experiment
(Figure
S11,
Supporting
Information).
45 Crystallographic analysis affirms that the chloride ions are
disordered over six positions around the trinuclear Al(III)
cluster with equal probability. This analysis was also supported
by 27Al solid state NMR spectroscopy experiment (Figure S12,
Supporting Information).
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Figure 1. Crystal structure of 1 showing the assembly of the trinuclear aluminum(III) MBB, [Al3(µ3ꢀO)(H2O)3(O2C–)6], with organic ligand, H4TCPT
(middle). Topological analysis of 1, where the 6ꢀconnected trinuclear Al(III) MBB can be viewed as trigonal prismatic SBU, while the organic ligand can
be rationalized as a 4ꢀconnected building unit to give (4,6)ꢀc socꢀnet (left), or can be viewed as 3ꢀc SBUs resulting in a (3,6)ꢀc derived net edq (right).
5
Topological analysis reveals that 1 has the anticipated edge
transitive (4,6)ꢀconnected net with the soc underlying topology.
The trinuclear Al(III) MBB, [Al3(µ3ꢀO)(O2C–)6], can be regarded
a trigonal prism secondary building unit (SBU) with the six
points of extension corresponding to the carbon of the
10 carboxylate moieties match the vertex figure of the 6ꢀc node in
the soc net. The 6ꢀc inorganic MBBs are joined by the
rectangular organic ligand, 4ꢀc node, into a primitive cubic
system arrangement (Figure 1).20 Alternatively from topological
perspective, the 4ꢀc rectangular ligand can be regarded as
15 comprised of two interconnected 3ꢀc triangular SBUs that are
further linked through the 6ꢀc trigonal prismatic SBUs to afford a
MOF related to a (3,6)ꢀc derived net edq, with transitivity 2 2
(Figures 1, Figures S25 and S26, Supporting Information).20b,21
However, in this paper, the reported AlꢀMOFs will be referred to
20 as AlꢀsocꢀMOFs.
diphenylanthracene (TCDPA) (H4L3), respectively (Figure 2a).19
As anticipated, under similar reaction conditions, which were
used to isolate the AlꢀsocꢀMOFꢀ1, cubeꢀshaped crystals were
30 obtained and characterized using SCXRD and powder Xꢀray
diffraction (PXRD) studies (Figure 2b), revealing the
construction of two isoreticular AlꢀsocꢀMOF compounds,
naphthalene AlꢀsocꢀMOFꢀ2 (2) and anthracene AlꢀsocꢀMOFꢀ3 (3)
with the following formula [Al3O(Ligand)1.5(H2O)3]·|Clꢀ|.
35 The phase purity of AlꢀsocꢀMOF compounds, 1, 2 and 3, were
confirmed by Whole Profile Pattern Matching using Le Bail
method (Figures S13, S14 and S15, Supporting Information).22
AlꢀsocꢀMOFꢀ1 structure encloses cubic shaped cages with 14.3Å
in diameter delimited by six TCPT4ꢀ ligands, which occupy the
40 faces of the cage, and eight inorganic trinuclear Al(III) clusters
located on the vertices of the cuboidal cage. The cage is
accessible through apertures of approximately 5.6 × 8.4Å taking
van der Waals (vdW) radius into consideration. The structure also
encloses two wellꢀdefined 1D infinite channels with estimated
45 dimensions of 14Å (vdW), which is approximately at the border
of microporous materials. (Figures S23 and S24, Supporting
Information).
In order to isolate other isoreticular analogs of AlꢀsocꢀMOFꢀ1,
the phenyl ring located in the core of TCPT ligand was
substituted by 1,4ꢀnaphthalenyl and 9,10ꢀanthracenyl cores to
give the naphthalene and anthracene functionalized ligands,
25 3',3'',5',5''ꢀtetrakis(4ꢀcarboxyphenyl)ꢀ1,4ꢀdiphenylnaphthalene
(TCDPN) (H4L2) and 3',3'',5',5''ꢀtetrakis(4ꢀcarboxyphenyl)ꢀ9,10ꢀ
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The corresponding solvent accessible free volumes for 1, 2 and 3
were estimated to be 80.5 %, 79 % and 75 %, respectively, by
summing voxels more than 1.2 Å away from the framework using
PLATON software.23
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Table 1. Selected porosity data for Al-socꢀMOFs compounds. ABET, ALang
are the experimental BET and Langmuir specific surface areas. PVtheo
,
and PVexp are the calculated pore volume from crystal structures and the
experimentally measured pore volume, respectively
8
9
ABET
m2/g
5585
5162
4849
ALang
m2/g
6530
5976
5212
Density
g/cm3
0.34
PVtheo
cm3/g
2.3
PVexp
cm3/g
2.3
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Compound
Al-soc-MOF-1
Al-soc-MOF-2
Al-soc-MOF-3
0.36
2.2
2.1
0.38
1.9
1.8
10
In light of the extraordinarily pure microporous architecture
exhibited by 1, 2 and 3, optimization of the conventional
activation conditions (drying under vacuum and heating) showed
that the guest solvent in the pores could be easily removed using
15 traditional approach (vacuum and heating) without altering their
microporosity. Nitrogen (N2) adsorption measurements at 77 K
were carried out on the acetonitrile exchanged samples, showing
fully reversible typeꢀI isotherm representative of porous materials
with permanent microporosity (Figure 2c).
20 The Langmuir and BET specific surface area, in the pressure
range (0.015ꢀ0.0269 p/p0), were estimated and found to be ca.
(6530, 5585 cm3/g) for 1, (5976, 5161 cm3/g) for 2, and (5212,
4849 cm3/g) for 3 (Table 1). It is to note that the resultant high
microporosity (surface area and pore volume) is exceptional and
25 yet to be observed, prior to this work, using traditional activation
method that often causes pore collapse in the case of highly
porous MOFs.24 Such a unique feature is of prime importance for
the implementation and deployment of 1, 2 and 3 as a gas storage
media for onboard or stationary gas storage applications.
30
Figure 2. (a) Representation of the organic MBBs used to construct
isoreticular AlꢀsocꢀMOFs. (b) PXRD patterns for the isoreticular Alꢀsocꢀ
MOFs. (c) Nitrogen isotherms at 77K for the isoreticular AlꢀsocꢀMOFs.
35 The successful use of the conventional activation method was
confirmed by the excellent agreement between the experimental
and the optimal theoretical pore volumes (PVexp= 2.3, 2.1 and 1.8
cm3/g, PVtheo= 2.3, 2.2 and 1.9 cm3/g for 1, 2, and 3,
respectively). Furthermore, AlꢀsocꢀMOF structures preserved
40 their optimal porosity after heating up to 340 °C under vacuum
(Figures S27b, S34b and S36b, Supporting Information), another
essential feature that is rarely observed for highly porous MOFs.
The high thermal stability was also confirmed using variable
temperature PXRD studies and thermal gravimetric analysis
45 (Figures S17ꢀ S22, Supporting Information).
Methane Storage Studies.
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Interestingly, the extremely open structure, exclusively concerted
in the microporous range, combined with the distinctive structural
features (presence of cages and channels) place AlꢀsocꢀMOFs as
ideal adsorbent candidates for gas storage studies. Accordingly, 35 between 80 bar (adsorption) and 5 bar (desorption). This
volumetric CH4 storage working capacity for 1 increased from
201 cm3(STP)/cm3 to 264 cm3(STP)/cm3 when the temperature
was decreased from 298 K to 258 K at working pressures
5
CH4 adsorption on 1, 2 and 3 was extensively studied
experimentally at variable temperatures and up to 80 bar as well
as at low pressure and 112 K (boiling point of CH4).
attribute, unique to AlꢀsocꢀMOFꢀ1, is unprecedented as all
available CH4 storage data for MOFs showed the conventional
decrease in the volumetric CH4 storage working capacity with the
decrease in temperature as illustrated in Figure 4 and Table S3 for
40 UTSAꢀ76,26 HKUSTꢀ1,16, 27 NiꢀMOFꢀ74,16, 27b, 28 , NUꢀ11129 and
PCNꢀ14.16, 27b, 30 It is to note that MOFꢀ5196a was not included in
this comparative assessment as the associated data at low
temperatures were not available for this highly CH4 adsorbing
MOF.
5
6
7
8
The methane adsorption isotherms at 112 K for 1, 2 and 3
revealed remarkable CH4 uptakes near saturation pressures, e.g.
9
10 1336, 1205 and 1055 cm3 (STP)/g at p/p0 = 0.95, respectively
(Figures S28a, S35a and S37a, Supporting Information).
Importantly, high pressure CH4 adsorption isotherms at variable
temperatures, depicted in Figure 3, showed that 1 has one of the
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highest ever reported CH4 gravimetric uptakes (ca. 361 45 A comprehensive comparison of absolute CH4 uptakes and
15 cm3(STP)/g) for any microporous MOF materials at the disclosed
DOE operational storage conditions (298 K and 35 bar).
Mesoporous MOFꢀ21024b and DUTꢀ4925 displayed an uptake
around 210 and 364 cm3(STP)/g at the same conditions.
working capacities for AlꢀsocꢀMOFꢀ1 (1) with various best MOF
materials reported so far at different temperature and pressure
conditions is presented in Figures 5 and Figure S38, Supporting
Information. Interestingly, although the total volumetric CH4
Interestingly, the DOE CH4 gravimetric uptake target of 700 cm3 50 uptake for 1 is relatively lower than some of the highly adsorbing
20 (STP)/g (0.5 g/g) was addressed and reached for relatively high
pressures at temperatures below 288 K, e.g. 50 bar at 258 K and
85 bar at 288 K (Figure 3).
MOFs, 1 displayed mutually high volumetric and gravimetric
working capacities at different working temperatures and
pressures. This notable and rare compromise between the
gravimetric and the volumetric capacities for 1 is a result of the
55 reduced unused CH4 uptake below 5 bar and the linear trend of
the CH4 isotherms at relatively high pressures, a desirable
attribute for an appropriate gas storage media. In contrast to the
best MOFs reported so far for CH4 storage, 1 exhibits relatively
low CH4 heat of adsorption (11 kJ/mol at low loading) in the
60 relatively low CH4 loading region, only slightly higher than the
CH4 latent heat of evaporation (Figure S30, Supporting
Information). Markedly, the comparatively favorable methane
adsorption at relatively high pressures can be attributed to
enhanced CH4ꢀCH4 interactions regulated by the appropriate pore
65 size of the AlꢀsocꢀMOFꢀ1. Therefore, the combination of both
aforementioned effects, governing the CH4 adsorption at low and
high pressures, in a single material afforded the exceptional CH4
working capacities observed for the AlꢀsocꢀMOFꢀ1, especially at
relatively low temperatures. It is to note that 1 exhibits the second
70 highest CH4 volumetric working capacity at 298 K and 5ꢀ80 bar
working pressure range, namely 201 cm3 (STP) /cm3 vs. 230 cm3
(STP)/cm3 for the recently reported MOFꢀ519. Noticeably, the
two synthesized isoreticular AlꢀsocꢀMOFs (2 and 3) exhibited
also high gravimetric and volumetric total and working CH4
75 uptakes that were only slightly lower than the uptake values
derived for 1. The experimental results for 2 and 3 are
summarized in Figure S41 and Table S4, Supporting Information.
25 Figure 3. Single component gas adsorption isotherms for CH4 at different
temperatures for AlꢀsocꢀMOFꢀ1, showing total CH4 gravimetric uptakes
surpassing the DOE target at particular pressures and temperatures.
Additionally, analysis of the volumetric CH4 adsorption
isotherms, using the AlꢀsocꢀMOFꢀ1 crystal density, revealed an
30 enhancement in the volumetric CH4 storage working capacity
when the temperature was decreased (Figure 4). Specifically, the
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Figure 4. Comparison of the CH4 volumetric working capacities (5ꢀ80 bar and 5ꢀ65 bar) at different temperatures (258, 273 and 298K) for AlꢀsocꢀMOFꢀ1
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with the best microporous MOF materials reported to date.
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Figure 5. Total (a, b, c, d) at 65 and 80 bar and 5ꢀ65, 5ꢀ80 bar working (e, f, g , h) CH4 gravimetric and volumetric uptakes for AlꢀsocꢀMOFꢀ1 (1) as
compared to the best MOF materials reported to date at 298, 270 and 240 K. The data for the AlꢀsocꢀMOFꢀ1 (1) were collected at 298, 273 and 258 K.
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Molecular Simulation Study for Methane Storage.
With the aim to gain a better understanding of the structureꢀ 55 relatively very low simulated unused methane uptake at 5 bar
properties relationship governing the resultant high methane
storage capacities in the AlꢀsocꢀMOFs, we assessed theoretically
the plausible CH4 storage capacity of various plausible theoretical
isoreticular AlꢀsocꢀMOFs, based on expanded and/or
functionalized tetracarboxylate organic building blocks.
(both gravimetric and volumetric) for P-P equivalent to 1, at 5
bar, was confirmed by performing adsorption isotherms at
different temperatures, namely at 298, 295, 273 and 258 K
(Figure S45, Supporting Information). This is reflected in the
60 observed nonꢀpreferential positions of CH4 molecules in the
framework of P-P (Figure 7b), .i.e. no specific preferential
adsorption sites at 5 bar.
5
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10 storage properties and the makeꢀup of the socꢀMOF porous
system (pore shape and size, ligand dimensions and
functionalities), a comprehensive molecular simulation study was
carried out on various hypothetical/isoreticular AlꢀsocꢀMOFs
constructed using hypothetical organic building blocks. Firstly,
15 we envisioned to validate our molecular simulation methodology
on the parent 1 (Alꢀsoc-MOFꢀ1) and corroborate the mechanistic
of CH4 adsorption at 5 bar and at higher pressures, resulting on
the outstanding CH4 working capacity. Secondly, simulate and
evaluate the absolute and working CH4 uptakes for various
20 hypothetical isoreticular socꢀMOFs, constructed using different
optimized (i) elongated, (ii) functionalized and (iii) contracted
organic MBBs. In effect, the simulated isoreticular AlꢀsocꢀMOFs
were assembled using both experimentally synthesized and
hypothetically designed linkers obtained by modifying the arms
25 and/or the core of the AlꢀsocꢀMOFꢀ1 ligand as shown in Figure 6,
Figure S47 and Scheme S2, Supporting Information. Figures 6
depicts the naming scheme employed to label the hypothetical
AlꢀsocꢀMOF linkers. For example, the original linker is shown in
Figure 6 (left), where P-P means phenyl – phenyl: both arm and
30 core have one phenyl group. While PP-APA stands for phenyl –
phenyl for arm and acetylene – phenyl –acetylene for core as
shown in Figure 6 (right). A total of 18 theoretical analogues
were hypothetically assembled and their associated CH4
adsorption isotherms were simulated. For clarity the new
35 simulated AlꢀsocꢀMOF structures will be named and referred to
using the linker name.
40 Figure 6. Scheme illustrating the adapted naming for the employed
hypothetical organic ligands and associated hypothetical AlꢀsocꢀMOFs.
Initially, the Grand Canonical Monte Carlo (GCMC) simulations
of methane adsorption were performed for the parent compound 1
45 in order to compare first the resulting simulated results with
available experimental adsorption data and subsequently validate
the simulation approach adopted in this study (Figure 7a and
Figure S44, Supporting Information). More details about the
employed simulation method is described in the Supporting
50 Information. As shown, the theoretical CH4 adsorption isotherm
for the P-P is in a good agreement with the experimental data (1).
The corresponding screenshots of methane adsorption at different
relevant pressures, i.e. 5 bar (limiting desorption pressure) and
35, 65 and 80 (storage pressures) are shown in Figure 7b. The
Figure 7. (a) Methane sorption in AlꢀsocꢀMOFꢀ1 at 298 K: simulation
65 (red filled circles) vs. experiment (black filled squares). (b) Screenshots of
methane adsorption in P-P (equivalent to AlꢀsocꢀMOFꢀ1) at 298 K at
different pressure: 5, 35, 65 and 80 bar. The purple spheres surrounding
the framework represent the methane molecules.
70 Delightfully, the simulated CH4 adsorption isotherms on the
optimized structure, based on molecular mechanics simulation
approach (details in the Supporting Information.), of the parent 1
(P-P), is in a good agreement with the corresponding CH4
adsorption isotherms simulated on the experimental structure
75 (Figure S46, Supporting Information). Accordingly, the same
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molecular mechanics optimization procedure was employed to
5
The simulated absolute volumetric and gravimetric CH4
adsorption isotherms for P-P (1) and the other isoreticular Alꢀ
socꢀMOFs were simulated at various temperatures and up to 80
construct 18 hypothetical isoreticular AlꢀsocꢀMOFs and
subsequently simulate their associated total and working CH4
uptakes using the GCMC approach.
bar total pressure (Figures S76ꢀS84, Supporting Information).
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10 Figure 8. Total (a) at 35 bar and 5ꢀ35 bar working (b) CH4 gravimetric and volumetric uptakes for PꢀP and AꢀP simulated structures as compared to the
best MOF materials reported to date at 298 K. Theoretical total (left, c and e) and working (right, d and f) gravimetric vs. volumetric capacity for selected
hypothetical isoreticular AlꢀsocꢀMOFs in a wide range of pressures (35, 65 and 80 bar) at different temperatures (298 and 258 K) as compared to Alꢀsocꢀ
MOF (1). The purple area represent the desired range of the best compromise between gravimetric and volumetric total and working uptakes.
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Interestingly, these results showed that the use of (i) elongated, 65 indicated that 1 exhibits a relatively low O2 heat of adsorption (10
(ii) functionalized and (iii) contracted linkers resulted in three
distinguished AlꢀsocꢀMOF groups in terms of gravimetricꢀ
volumetric uptake tradeꢀoff. In fact, the use of (i) elongated arms
and/or cores, such as PP-PP, led to an increase in the gravimetric
uptake at the expense of the volumetric uptake at any pressure
and temperature conditions evaluated in this study. (ii)
Functionalizing the phenyl core of the linker led generally to
lower gravimetric uptake but still with good gravimetricꢀ
10 volumetric uptake tradeꢀoff at any pressure and temperature
conditions explored here. In a particular case, strategies for
functionalization of the phenyl cores with different functional
groups, such as CF3 and Br led to relatively good working
volumetric uptake (due to the relatively higher framework
15 density), albeit with much lower working gravimetric uptake.
Interestingly, (iii) contraction of the arms and/or the core, for
kJ/mol at low loading) in the whole O2 loading range, slightly
higher than the O2 latent heat of evaporation (Figure S33,
Supporting Information).
5
Additionally, the CO2 adsorption studies revealed that Alꢀsocꢀ
70 MOFꢀ1 exhibits an exceptional absolute gravimetric CO2 uptake
at 40 bar of 2 g/g (1020 cm3 (STP)/g) vs. 1.5 g/g for MOFꢀ177, a
setting a new record among microporous MOFs (Figure S39,
Supporting Information). Consequently, AlꢀsocꢀMOFꢀ1 displays
the uppermost working capacity between 1 bar and 40 bar of 1.90
75 g/g (967 cm3 (STP)/g) vs 1.46 g/g (742 cm3 (STP)/g) for MOFꢀ
177.24b The analysis of variable temperature CO2 adsorption data
showed that AlꢀsocꢀMOFꢀ1 exhibits a relatively low CO2 heat of
adsorption (17 kJ/mol at low loading) in the whole CO2 loading
range (Figure S31b, Supporting Information). It is important to
80 note that the mesoporous MOFꢀ21024b exhibits the highest
absolute gravimetric CO2 uptake at 50 bar (2.8 g/g).
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instance A-P structure, offer potential for
a collective
improvement (ideal compromise) of the gravimetric and
volumetric uptakes as compared to 1 at any temperature,
20 particularly at intermediate pressures of 35 bar (Figure 8).
Principally, in terms of CH4 working (5ꢀ35 bar) volumetric and
gravimetric capacity tradeꢀoff, contraction of the arms showed a
notable improvement in the absolute CH4 uptake at 298 K. This
unique compromise can be attributed to the enhanced CH4
25 adsorption uptake at relatively high pressures below 35 bar, due
to the reduced channel dimensions in the A-P structure as
compared to the parent AlꢀsocꢀMOFꢀ1 (9.3 Å x 10.0 Å vs 14.0 Å
x 14.2 Å). It is important to note that the AlꢀsocꢀMOFꢀ1 (P-P)
still exhibits both enhanced volumetric and gravimetric tradeꢀoff
30 for 5ꢀ65 bar and 5ꢀ80 bar working pressures at any temperature
(Figure 8).
Finally, it is worth noting that AlꢀsocꢀMOFꢀ1 exhibits also an
excellent H2 storage capacity at 77 K (ca. 11 wt %) (Figure S40,
Supporting Information) at high pressure (30 bar) in comparison
85 to other highly porous materials.
A summary of the theoretical results in terms of CH4 absolute and
working capacities, volumetric and gravimetric, at 298, 273 and
258 K in a wide range of pressures are presented in Figures S48ꢀ
35 S66, Supporting Information.
O2 and CO2 Storage Studies
The exceptional methane storage capabilities of AlꢀsocꢀMOFꢀ1
have inspired us to extend this study to other important
40 commodities, namely O2 and CO2. Accordingly, we recorded
various O2 and CO2 adsorption isotherms for AlꢀsocꢀMOFꢀ1.
Noticeably, the amounts of O2 and CO2 adsorbed in AlꢀsocꢀMOFꢀ
1 near saturation pressures (0.95 p/p0), derived from adsorption
isotherms at 90.2 K and 195.15 K for O2 and CO2 respectively,
45 were found to be remarkably high (1757 cm3 (STP)/g and 1236
cm3 (STP)/g, respectively) (Figure S29, Supporting Information).
Markedly, the combination of experimentally accessible low
pressure (at 90.2 K) and high pressure O2 adsorption data up to
115 bar (at 298 K) (combined with Toth model) revealed that Alꢀ
50 socꢀMOFꢀ1 exhibits a record of 29 mmol/g absolute gravimetric
O2 uptake at 140 bar that is much higher than HKUSTꢀ1 (13.2
mmol/g) and NUꢀ125 (17.4 mmol/g)31, reference materials for the
application (Figure 9).15 Additionally, AlꢀsocꢀMOFꢀ1 displayed a
record deliverable capacity between 5 and 140 bar of 27.5
55 mmol/g vs 11.8 and 15.4 mmol/g for HKUSTꢀ1 and NUꢀ125
respectively (Figure 9a). Consequently by neglecting the effect of
packing density and the void space occupied by the material, a 1
L cylinder filled with AlꢀsocꢀMOFꢀ1 will potentially enhance the
volumetric O2 storage capacity (172 cm3/cm3) by 70% at 100 bar
60 as compared to a conventional empty cylinder32 (Figure 9b). It is
to note that if we assume a prospective 25% loss associated to
packing density, the AlꢀsocꢀMOFꢀ1 volumetric O2 storage
capacity still offers a 25% enhancement over an empty cylinder.
Analysis of the O2 adsorption recorded at variable temperatures
Figure 9. (a) Single component gravimetric gas adsorption isotherm for
O2 at 298 K showing that 1 exhibits the highest deliverable uptake
90 reported so far. (b) Volumetric O2 adsorption isotherm compared to the
storage capacity in pressurized container.32
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Similarly, O2 and CO2 adsorption studies were performed for the
two isoreticular AlꢀsocꢀMOFs (2 and 3) and revealed that the
naphthalene and anthracene analogues exhibit only a slightly
lower O2 and CO2 adsorption uptakes under the same condition as 65 automated Autosorbꢀ1C gas sorption analyzer (Quantachrome
performed under a continuous N2 flow and recorded on a TA
Instruments hiꢀres TGAQ500 thermogravimetric analyzer. Low
pressure gas sorption measurements were performed on a fully
5
compared to 1 (Figures S42, S43 and Table S4, Supporting
Information).
Instruments). High pressure gas sorption studies were performed
on a magnetic suspension balance marketed by Rubotherm
(Germany).
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CONCLUSIONS
Synthesis of Al-soc-MOF-1: A solution of AlCl3.6H2O (29 mg,
70 0.015 mmol), H4L1 (7.1 mg, 0.01 mmol), in N,Nꢀ
dimethylformamide (DMF) (1 ml), acetonitrile (CH3CN) (1 ml)
and nitric acid (3.5 M, 0.5 ml) was prepared in a 20ꢀml
scintillation vial and subsequently placed into preheated oven at
130˚C for 12 h to give pure small colorless cubeꢀshaped crystals.
75 Suitable single crystals were obtained using the same synthetic
procedure, but with increasing the amount of HNO3 to l ml.
Crystals of AlꢀsocꢀMOFꢀ1 were harvested, washed with CH3CN
and airꢀdried. FTꢀIR (4000 ꢀ 650 cmꢀ1): 3349 (br), 1605 (s), 1592
(s), 1423 (s), 1387 (vs), 1312 (w), 1243 (w), 1100 (w), 1018 (w),
80 854 (w), 830 (w), 783 (s), 771 (s).701(s).
9
In summary, we successfully employed the molecular building
block approach to synthesize the first aluminum socꢀMOF
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10 isoreticular materials. Specifically, reaction conditions that
consistently permit the inꢀsitu generation of the [Al3(μ3ꢀ
O)(H2O)6(O2C−)6] MBB were isolated and used for the
construction of a highly porous (4,6)ꢀconnected aluminum based
socꢀMOF, AlꢀsocꢀMOFꢀ1 , with more than 6000 m2/g Langmuir
15 specific surface area.
Importantly, the tedious activation using dry supercritical CO2 is
not required in order to activate the AlꢀsocꢀMOFꢀ1 and its
naphthalene and anthracene analogues. Particularly, the
conventional activation technique, i.e. simple combination of
20 heating and vacuum (or N2 flush), is sufficient for the full
activation prior gas loadingꢀunloading cycles.
Synthesis of Al-soc-MOF-2: A solution of AlCl3.6H2O (29 mg,
0.015 mmol), H4L2 (7.6 mg, 0.01 mmol), in N,Nꢀ
dimethylformamide (DMF) (1 ml), acetonitrile (CH3CN) (1 ml)
and nitric acid (3.5 M, 0.5 ml) was prepared in a 20ꢀml
85 scintillation vial and subsequently placed into preheated oven at
130˚C for 12 h to give pure small colorless cubeꢀshaped crystals.
Suitable single crystals were obtained using the same synthetic
procedure, but with increasing the amount of HNO3 to l ml.
Crystals of AlꢀsocꢀMOFꢀ2 were harvested, washed with CH3CN
90 and airꢀdried. FTꢀIR (4000 ꢀ 650 cmꢀ1): 3349 (br), 1606 (s), 1545
(m), 1422 (s), 1384 (s), 1241 (w), 1100 (w), 1015 (w), 851 (w),
851 (w), 771 (s).705(m).
Extensive gas adsorption studies were carried out on the Alꢀsocꢀ
MOF platform with different gases (N2, CO2, CH4, O2, etc.).
Methane adsorption isotherms were completed at different
25 temperatures and in a wide range of pressures up to 85 bar.
Interestingly, it was found that AlꢀsocꢀMOFꢀ1 exhibits one of the
highest total and working gravimetric CH4 uptakes at 35 bar. In
contrast to other reported best MOFs for CH4 storage, Alꢀsocꢀ
MOFꢀ1 showed enhanced CH4 storage working capacity as the
30 temperature is decreased. Particularly, at 258 K and 80 bar, the
AlꢀsocꢀMOFꢀ1 fulfils the DOE target and exhibits the highest
working volumetric capacity of 264 cm3(STP)/cm3. To the best of
our knowledge, this is the first time that a porous material fulfills
both the challenging gravimetric and volumetric targets for the
35 CH4 working capacity. The collective experimental and GCMC
simulation studies indicated that the parent AlꢀsocꢀMOFꢀ1, in
contrast to various hypothetical isoreticular AlꢀsocꢀMOFs based
on contracted, elongated and functionalized ligands, exhibits the
best compromise between the volumetric and gravimetric total
40 and working uptakes in a wide range of pressure and temperature
conditions.
Synthesis of Al-soc-MOF-3: A solution of AlCl3.6H2O (29 mg,
0.015 mmol), H4L3 (8.1 mg, 0.01 mmol), in N,Nꢀ
95 dimethylformamide (DMF) (1 ml), acetonitrile (CH3CN) (1 ml)
and nitric acid (3.5 M, 0.3 ml) was prepared in a 20ꢀml
scintillation vial and subsequently placed into preheated oven at
130˚C for 12 h to give pure microcrystalline yellow powder.
Suitable single crystals were obtained using the same synthetic
100 procedure, but with increasing the amount of HNO3 to l ml.
Crystals of AlꢀsocꢀMOFꢀ3 were harvested, washed with CH3CN
and airꢀdried. FTꢀIR (4000 ꢀ 650 cmꢀ1): 3349 (br), 1606 (s), 1547
(s), 1442 (s), 1387 (s), 1312 (w), 1241 (w), 1181 (w), 1016 (w),
852 (m), 771 (s), 706 (s).
EXPERIMENTAL SECTION
105 ASSOCIATED CONTENT
Materials and methods. Details on the synthesis of the organic
ligands used in this study, 3,3'',5,5''ꢀtetrakis(4ꢀcarboxyphenyl)ꢀpꢀ
45 terphenyl (H4TCPT), 3',3'',5',5''ꢀtetrakis(4ꢀcarboxyphenyl)ꢀ1,4ꢀ
diphenylnaphthalene (TCDPN) and 3',3'',5',5''ꢀtetrakis(4ꢀ
Supporting Information
Synthesis of organic ligands, PXRD, additional structural
figures, sorption, and singleꢀcrystal Xꢀray diffraction data
(CIF). This material is available free of charge via the Internet
110 at http://pubs.acs.org
carboxyphenyl)ꢀ9,10ꢀdiphenylanthracene
provided in the Supporting Information.
(TCDPA)19
are
Singleꢀcrystal diffraction data were collected at beamline I19,
50 Diamond Light Source, Didcot, UK using a wavelength λ =
1.0402 Å at 250 K. Fourierꢀtransform infrared (FTꢀIR) spectra
(4000−600 cm−1) were collected in the solid state on a Nicolet
700 FTꢀIR spectrometer. The peak intensities are described in
each of the spectra as very strong (vs), strong (s), medium (m),
55 weak (w), broad (br) and shoulder (sh). Powder Xꢀray diffraction
(PXRD) measurements were performed on a PANalytical MPD
X’Pert PRO Xꢀray diffractometer at 45 kV, 40 mA for Cu Kα (λ
= 1.5418 Å) equipped with a variableꢀtemperature stage, with a
scan speed of 20/min. The sample was held at the designated
60 temperature for at least 10 min between each scan. High
resolution dynamic thermal gravimetric analysis (TGA) were
AUTHOR INFORMATION
Corresponding Author
mohamed.eddaoudi@kaust.edu.sa
Notes
115 The authors declare no competing financial interests.
ACKNOWLEDGMENT
Research reported in this publication was supported by King
Abdullah University of Science and Technology (KAUST).
The authors thank Diamond Light Source for access to
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M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319ꢀ330. (f) Xue, D.ꢀX.;
beamline I19 (MT10189) that contributed to the results
presented here and also D. Allan and H. Nowell for their
assistance during the measurements.
Cairns, A. J.; Belmabkhout, Y.; Wojtas, L.; Liu, Y.; Alkordi, M. H.;
65 Eddaoudi, M. J. Am. Chem. Soc. 2013, 135, 7660ꢀ7667.
(13) Chae, H. K.; SiberioꢀPerez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.;
Matzger, A. J.; O'Keeffe, M.; Yaghi, O. M. Nature 2004, 427, 523ꢀ527.
(14) (a) Liu, Y.; Eubank, J. F.; Cairns, A. J.; Eckert, J.; Kravtsov, V. C.;
Luebke, R.; Eddaoudi, M. Angew. Chem., Int. Ed. 2007, 46, 3278ꢀ3283.
70 (b) Pang, M.; Cairns, A. J.; Liu, Y.; Belmabkhout, Y.; Zeng, H. C.;
Eddaoudi, M. J. Am. Chem. Soc. 2012, 134, 13176ꢀ13179.
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