UiO-67-type Metal-Organic Frameworks with Enhanced Water Stability and Methane Adsorption Capacity

Article abstract of DOI:10.1021/acs.inorgchem.5b02257

The structure and properties of two new UiO-67-type metal-organic frameworks, along with their linker synthesis and powder and single crystal synthesis, are presented. The new MOFs, UiO-67-Me and UiO-67-BN, are based on 3,3′-dimethylbiphenyl and 1,1′-binaphthyl linker scaffolds, and show a much higher stability to water than the thoroughly investigated UiO-67, which is based on the biphenyl scaffold. On the basis of structure models obtained from single crystal X-ray diffraction, it is seen that these linkers are partly shielding the Zr cluster. The new materials have higher density than UiO-67, but show a higher volumetric adsorption capacity for methane. UiO-67-BN exhibits excellent reversible water sorption properties, and enhanced stability to aqueous solutions over a wide pH range; it is to the best of our knowledge the most stable Zr-MOF that is isostructural to UiO-67 in aqueous solutions.

Full text of DOI:10.1021/acs.inorgchem.5b02257

Article
pubs.acs.org/IC
UiO-67-type Metal−Organic Frameworks with Enhanced Water
Stability and Methane Adsorption Capacity
†
†
†
†
‡
Sigurd Øien-Ødegaard, Boris Bouchevreau, Knut Hylland, Lianpao Wu, Richard Blom,
‡
†
†
,†
Carlos Grande, Unni Olsbye, Mats Tilset, and Karl P. Lillerud*
†Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0371 Oslo, Norway
‡SINTEF, P.O. Box. 124, Blindern, N-0314 Oslo, Norway
*
S Supporting Information
ABSTRACT: The structure and properties of two new UiO-67-type
metal−organic frameworks, along with their linker synthesis and powder
and single crystal synthesis, are presented. The new MOFs, UiO-67-Me
and UiO-67-BN, are based on 3,3′-dimethylbiphenyl and 1,1′-binaphthyl
linker scaffolds, and show a much higher stability to water than the
thoroughly investigated UiO-67, which is based on the biphenyl scaffold.
On the basis of structure models obtained from single crystal X-ray
diffraction, it is seen that these linkers are partly shielding the Zr cluster.
The new materials have higher density than UiO-67, but show a higher
volumetric adsorption capacity for methane. UiO-67-BN exhibits excellent
reversible water sorption properties, and enhanced stability to aqueous
solutions over a wide pH range; it is to the best of our knowledge the
most stable Zr-MOF that is isostructural to UiO-67 in aqueous solutions.
1
0,11
INTRODUCTION
crystallizing in several topologies,
and some varieties have
■
been reported to have excellent properties with respect to water
Although incorporation of bulky
linkers into methane adsorbing Zr-MOFs is somewhat
Porous metal−organic framework materials (MOFs) are
currently under investigation as gas separation and storage
media because of their excellent gas adsorption properties. This
versatile class of materials features exceptionally high internal
surface areas and ability to adsorb large amounts of gas at
relatively low pressures, making them ideally suited as filling
12,13
adsorption and catalysis.
discouraged by Snurr et al., who found that methane packs
1
4
efficiently around the Zr cluster, it was not clear how the
described effects would impact the material properties.
1
During the work, it became apparent that the newly
synthesized MOFs were much more stable toward water than
other UiO-67 analogues. Further investigations showed that
UiO-67-BN was also stable during repeated water adsorption/
desorption cycles. There have been several accounts on the
water stability of UiO-67, and whereas it seems to be stable in
water, it tends to undergo structural collapse when water is
removed from an aqueous suspension. Although adding
hydrophobic groups to the linker has been demonstrated to
increase MOF stability in certain cases, this has not yet been
investigated for UiO-67.
media to reduce the operating pressure of gas tanks. With
increasing worldwide consumption of natural gas, there is a
growing interest for safe gas separation, storage, and trans-
2
portation.
Composed of connected inorganic clusters and organic cross-
linking molecules, the materials have an intrinsic potential for
diverse chemistry; the organic part (linker) can be function-
alized in almost any conceivable way while the backbone
remains intact. To optimize a MOF for methane storage, one
15
16
strategy is to increase the heat of adsorption (Q ) by inclusion
St
of stronger interacting sites between methane and the
3
−5
adsorbent.
Large aromatic groups on the MOF linkers,
like naphthalene or anthracene, have been found to have this
effect and could increase gas loading albeit inevitably also
decreasing the free pore volume.
The work presented herein was initially aimed at increasing
the methane storage capacity of the Zr-MOF UiO-67 by
increasing QSt following the aforementioned strategy using
linkers based on 3,3′-dimethylbiphenyl and 1,1′-binaphthyl
linker scaffolds instead of the parent biphenyl. MOFs based on
EXPERIMENTAL SECTION
■
Synthesis. 3,3′-Dimethylbiphenyl-4,4′-dicarboxylic acid was syn-
6
,7
1
7
thesized according to our recently published method. 1,1′-
Binaphthyl-4,4′-dicarboxylic acid was synthesized using a multistep
procedure described in the Supporting Information, and characterized
by NMR and single crystal X-ray diffraction.
Solvothermal synthesis, based on previously reported methods in
which the reagents are dissolved in DMF and heated under static
the Zr -oxocluster are among the most chemically and
6
8
thermally stable of the commonly investigated MOFs. They
Received: October 1, 2015
9
have been synthesized with a wide variety of linkers,
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.5b02257
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Inorganic Chemistry
Article
conditions, was used to obtain powders and single crystals of MOFs 1,
water is exchanged with THF prior to solvent removal. MOFs 1
and 2 undergo structural collapse upon drying from aqueous
suspension, as is expected for UiO-67, but no decomposition of
18,19
2, and 3.
To produce single crystals of sufficient size for single
crystal X-ray diffraction, benzoic acid (for UiO-67 and UiO-67-Me)
and 4-nitrobenzoic acid (for UiO-67-BN) were used as growth rate
3
was observed, even after repeated dispersion and drying from
20
limiting additives, or “modulators”. Powders were synthesized using
less modulator, but otherwise, the conditions were similar. Both
powders and single crystals were washed repeatedly with dry DMF and
subsequently dry THF after synthesis. A complete description can be
found in the Supporting Information.
liquid water. Solutions with pH ranging from 1 to 12 did not
affect the crystallinity of 3, but the material dissolved in
stronger aqueous base.
BET surface areas of 1, 2, and 3 were obtained from
2
3
Stability Testing. Powders of 1, 2, and 3 were subjected to several
chemical stability tests: suspended in aqueous solutions of pH 1, 2, 4,
measured N isotherms using established consistency criteria,
2
2
−1
and were found to be 2583, 1978, and 1416 m g ,
respectively. These are in good agreement with previously
reported BET surface areas for UiO-67 and with geometrical
calculations (see Supporting Information). N2 isotherms
acquired after activation from water confirm the decomposition
of 1 and 2; following only one cycle of activation from water,
1
0, 11, 12, 13, and 14 for 30 min (HCl(aq) and NaOH(aq),
respectively); suspended in a large excess of water overnight both at 25
C and in a sealed Teflon lined autoclave at 150 °C. Thermogravi-
°
metric analysis (TGA) was also performed on each powder sample,
both as synthesized and after high temperature water treatment.
PXRD patterns were measured for the MOFs as synthesized, and
following the tests. It has been reported that Zr-MOFs are prone to
decompose upon evacuation of water, so PXRD measurement was
performed on each sample both when dried directly from water/
aqueous solution, and after solvent exchange (with THF) followed by
drying. The powders were dried simply by heating in air at 200 °C, as
this is sufficient to empty the pores of water, DMF, and lower boiling
solvents.
2
−1
sample 1 loses its porosity (s (BET) < 5 m g ), and the
surface area of 2 was reduced to 1112 m g . For 3, however,
only a slight increase was observed, to 1452 m g . After
repeated syntheses and measurements of 3 only slight
deviations in sA (BET) between as-synthesized and water-
activated samples have been observed.
A
2
−1
2
−1
The newly synthesized MOFs 2 and 3 were found to be
slightly less thermally stable than 1, and started to decompose
around 400 °C (see Supporting Information for TGA).
Single Crystal Structure Analysis. The structures of the
two linkers, 1,1′-binaphthyl-4,4′-dicarboxylic acid (as a DMF
solvate) and biphenyl-4,4′-dicarboxylic acid (crystal structure
previously unreported of the pure compound), and MOFs 2
and 3 were characterized by single crystal X-ray diffraction. In
the structure of 2 and 3, two positions of the carboxylate
Single Crystal X-ray Diffraction. Crystals of 2 and 3 were dried
at 200 °C in air before measurement at −173 °C at the MX Beamline
21
at the MAX2 synchrotron. Resolution of 0.73 Å was obtained for all
2
2
samples, and the structures were refined with SHELX-2015.
Following the same procedure as recently reported by us for a single
19
crystal investigation, the diffuse electron density of the pores was
modeled with partially occupied light (dummy) atoms, which led to
very good refinement indicators.
Sorption. Adsorption/desorption isotherms of N , CO , CH , and
2
2
4
H O were performed on THF washed dry powders of 1, 2, and 3. N2
2
oxygen were observed and allocated to missing linkers, in
adsorption isotherms were also measured after high temperature water
treatment and subsequent drying in air.
19,24,25
accordance with previous literature reports.
TGA
measurements also indicate the presence of missing linker
defects in the powder samples. The SC-XRD refinement
statistics are summarized in Table 1.
RESULTS AND DISCUSSION
■
Initial Characterization and Water Stability Test. From
PXRD measurements, it is clear that MOFs 1, 2, and 3 share
the same crystalline phase, and similar unit cell parameters
Table 1. Summary of Crystallographic Data for MOFs 2 and
3
(
Figure 1). All three MOFs remain structurally unchanged after
UiO-67-Me (2)
Fm3
UiO-67-BN (3)
Fm3
dispersion in water (both at room temperature and 150 °C), if
space group
a/Å
V/Å3
̅
̅
m
26.8690(3)
26.8167(2)
19284.8(4)
19397.9(6)
radiation
synchrotron (λ = 0.750)
5.306−60.836
10 712
2Θ range/deg
6.99−61.784
10 300
reflns
indep reflns
1290 [Rint = 0.0161,
Rσ = 0.0099]
1314 [Rint = 0.0400,
Rσ = 0.0275]
data/restraints/params
GOF on F2
1290/0/63
1.146
1314/0/78
1.178
final R indexes
R1 = 0.0349,
wR2 = 0.1507
R1 = 0.0323,
wR2 = 0.0953
[
I ≥ 2σ(I)]
final R indexes [all data] R1 = 0.0354,
R1 = 0.0338,
wR2 = 0.0965
wR2 = 0.1515
largest diff
0.74/−0.56
0.64/−0.50
peak/hole/e Å‑
3
The crystal structures provide insight into how the
carboxylate groups, and the strong adsorption sites in proximity
to the Zr clusters, are influenced by the different linkers (Figure
2
). In 2, the methyl group occupies the corner of the large
octahedral cage, and provides steric shielding for the
carboxylate group. Its position deviates from the plane span
out by the carboxylate groups (Miller plane (100)) by 18°, thus
Figure 1. PXRD patterns of as-synthesized MOFs 1, 2, and 3 (dark);
after water treatment at 150 °C followed by THF exchange (medium);
after direct activation from water slurry (light).
B
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Water Adsorption Cycles. All four cycles of water
adsorption measured on 3 at 30 °C exhibit remarkable type
IV adsorption isotherms, featuring a well-defined hysteresis
loop with two virtually vertical and nearly parallel branches
(
Figure 3). This is generally associated with porous materials
Figure 3. Water adsorption/desorption isotherms of 3 at 30 °C. Inlay:
The low pressure part of the adsorption isotherms magnified to show a
high initial affinity to water.
Figure 2. Views of the Zr -oxocluster environment from the [100],
6
having a narrow pore-size distribution. At relative humidity of
[
111], and [110] directions reveal that the linkers sterically shield the
5
3% (at 30 °C) it approaches full loading of water. Although a
carboxylate groups and adsorption sites on the cluster.
small decrease of adsorption capacity between each cycle is
observed, this is remarkable for a UiO-67-type MOF. While the
cause of this decrease in capacity is unknown, it is likely
connected to missing linker defects, as this has been shown to
slightly affecting the corner of the tetrahedral cage. For 3, the
effect is more pronounced: With a deviation of 30° from the
25,27,28
have a significant impact on Zr MOF stability,
and is
(
100) plane, the naphthyl groups are protecting both the
3
present in the measured sample of UiO-67-BN. It may also be
affected by the harsh regeneration between each cycle, heating
the powder at 250 °C overnight in vacuum. Further
investigations of the synthesis and measurement conditions
will clarify whether this is indeed the case.
carboxylate group and the μ -O(H) group from interaction
with adsorbates. At the same time, the pore volume is greatly
reduced.
It is still unclear which of these structural features contribute
most to the increased stability to water. While numerous
12,26
The adsorption isotherm has three distinct parts; before,
functionalized UiO-67 derivatives have been reported,
all of
during, and after the water condensation. Initially (p/p = 0.0−
these will naturally provide some steric shielding of the cluster,
and reduced pore volume. It has been observed that both
0
0
0
.4), it exhibits a non-negligible rise in adsorption (for p/p =
0
12
.0−0.02), followed by a linear segment (for p/p = 0.02−0.4).
hydrophilic (OH functionalized UiO-67, MOF-806 ) and
hydrophobic (this work) groups give enhanced stability, and
thus, it can be assumed that the chemical properties of the
functional group are of limited importance. However, the
decomposition only occurs during the evacuation of water from
the MOF, which indicates that hydrolysis of the metal−linker
bond is not the primary pathway of framework collapse. As
previously found by Farha et al. for other Zr-MOFs, it seems
the decomposition is mechanical, from capillary-like forces
acting on the framework during water removal. When dried
from solvents with less intermolecular interaction (i.e., less
polar solvents) the framework remains intact.
0
If we consider the crystal density of 0.937 for this material, the
initial amount of water adsorbed (n ) corresponds to 0.645
0
−3
mmol cm , or to about 7.5 water molecules per unit cell,
which is in good agreement with the 8 water molecules (2 per
Zr -cluster) expected to undergo chemisorption upon rehy-
6
8
,29
droxylation of the cluster.
equation, more than 90% of the rehydroxylation is completed at
a relative partial pressure as low as p/p = 0.015.
According to the Langmuir
0
The linear behavior (observed at p/p = 0.02−0.4) of the
0
adsorption indicates low surface coverage where the amount of
adsorbate is proportional to the partial pressure, and may thus
be modeled by Henry’s adsorption equation. However, in order
to also include the initial steep water uptake, a second
contribution in the form of a Langmuir isotherm has here been
added:
The naphthyl groups of 3 sterically interact with each other,
both intra- and intermolecularly, and it can be assumed they do
not rotate freely. They seem however to have a significant
rocking about their axis of connection, resulting in elongated
thermal displacement ellipsoids. Distinction between static and
dynamic conformational disorder has not yet been achieved.
In all structures, excess electron density is observed in the
bp
1 + bp
n = n0
+ kHp
3
tetrahedral cage corners directly facing the μ -O(H) group.
Although the crystals are activated before measurement, they
are exposed to ambient atmosphere for a few minutes before
immobilization in the cryostream, during which they
presumably adsorb water onto the strongest adsorption sites.
Here, n signifies the amount adsorbed at given relative pressure
p, n the maximum adsorption for the Langmuir-type isotherm
0
contribution, b the Langmuir equilibrium constant (propor-
tional to the ratio of the adsorption and desorption rate
C
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Article
constants), and kH the Henry’s constant characterizing the
explicit shift in pressure for the main desorption step (parallel
linear behavior of adsorption. The global fit over the p/p range
to the adsorption one) occurring at p/p = 0.47. The excess of
0
0
0
.0−0.4 of all four isotherms gives quite satisfactory results,
water that is not desorbed at low pressure amounts to about 7−
10 water molecules per unit cell and is possibly due to strong
hydrogen bonding between those water molecules and the
2
with a coefficient of determination R = 0.997. Fitted
parameters were single values for n and b and four individual
kH values (see Table 2).
0
capping μ -O(H) groups of the cluster or hydroxyl groups
3
resulting from linker deficiency. To prevent any bias in the
measurement of the ulterior adsorption isotherms, a necessary
outgassing for several hours under vacuum (at p < 0.1 Pa) at
Table 2. Parameters Derived from the Fitting of the Low
Pressure Part of the Water Adsorption Isotherms of 3 at 30
2
50 °C was performed between each cycle.
°C
In a comparison to those of 1 or 2, both effective pore and
adsorption cycle n (mmol g−1)
b
kH (mol g−1 Pa−1
)
0
log(kH)
−6.44
−6.42
−6.35
−6.32
window sizes are reduced in 3, owing to the dimension of the
extended binaphthyl linker. This gives rise to a confinement
7
1
2
3
4
0.688
0.688
0.688
0.688
590
590
590
590
3.63 × 10−
−
7
7
7
34
3.84 × 10
effect, facilitating the water adsorption and thus leading to a
4.43 × 10−
4.78 × 10−
lowering of the pore filling pressure α. This effect could also be
strengthened by the larger hydrophobicity of the pore walls,
promoting the formation of hydrogen bonding between water
molecules in such confined spaces. The pore filling pressure α
of UiO-67 determined from the isotherm reported by No et al.
has a value of 0.56, which seems to contradict the previous
assumption. However, the isotherms of the present work have
been measured at 30 °C, whereas those of No et al. were
measured at 25 °C. It is then worth mentioning that, as the
water adsorption shifts to higher pressures with increasing
temperatures, the value of pore filling pressure can change by
The low k value of 3 (average log(k ) of −6.4, see Table 2)
H
H
suggests a hydrophobic behavior and thus limited adsorption at
moderate partial water pressure (p/p < 0.4). The values
reported by Canivet et al. for the parent UiO-66 and its amino-
0
functionalized derivative have log(k ) values of −3.5 and −2.4,
H
30
3
1
and 4 orders of magnitude higher, respectively. Among the
5 MOFs investigated by these authors, very few exhibit similar
hydrophobic features; 3 is actually only comparable to the very
31
32
35
hydrophobic ZIF-8 and to In-MIL-68 with log(k ) values of
several hundred Pascal with a 5 °C temperature variation,
H
−
6.2 and −6.6, respectively.
eventually leading to a value of α equal to or higher than 0.63 as
expected at 30 °C.
The second part of the adsorption isotherm consists of a
water condensation phenomenon which occurs at p/p = 0.53
The first water adsorption/desorption isotherms of both 1
and 2 were ill-defined, and few conclusions can be made with
the existing data. For instance, it was not possible to determine
the water adsorption capacity of the pristine materials. Whereas
1 is completely decomposed after the first cycle, 2 undergoes
partial decomposition during desorption, as can be seen by a
critical loss in water capacity during cycling. Yet some
information, such as the adsorption capacity during cycles 3
and 4, could be extracted (see Table 3, and Figure S9 in the
Supporting Information).
0
with a significant rise in water adsorption equivalent to 92% of
the total water adsorption capacity. This large uptake is
followed by the third part, a linear increase that could originate
from further ordering of adsorbed water molecules into
additional layer(s) with higher pressure, thus increasing the
density in the larger pores and allowing some additional
adsorption. The total water uptake finally reaches 27.4 mmol/g
3
(
0.495 cm /g) at p/p = 0.90 (see Table 3).
0
Table 3. Water Capacity Data Derived from Water
Adsorption Isotherms at 30 °C
With the assumption that confined water has a density close
to that of liquid, less than 30% of the pore volume of the
3
pristine UiO-67 (ca. 0.98 cm /g) is filled, considering the total
3
‑1
MOF/ads cycle
CH2O* (cm g )
no. of water molecules per unit cell
3
uptake of about 16 mmol/g (0.288 cm /g) reported by
3
6−38
UiO-67-BN/1
UiO-67-BN/2
UiO-67-BN/3
UiO-67-BN/4
UiO-67-Me/3
UiO-67-Me/4
0.495
0.481
0.461
0.432
0.338
0.167
299
291
279
261
172
85
others.
(
On the contrary, for 3, 90% of the pore volume
3
3
0.548 cm /g) is filled (total uptake of 0.495 cm H O per
2
(l)
gram at p/p = 0.9). Despite the expected larger hydrophobicity
0
of the framework, the pore filling is here much more efficient.
As already suggested for example by Cmarik et al. for the
dimethoxy-functionalized UiO-66 MOF (UiO-66-2,5-
39
(
OMe)2), in certain cases the linker is likely to be acting as
At p/p = 0.50, just before the water condensation starts, the
a “directing agent”, implying a much more efficient packing of
the water molecules.
0
physisorbed water loadings range from 10 to 16 water
molecules per unit cell between cycle 1 and cycle 4. At low
pressure, the most favorable sites for water adsorption are at the
CH
and CO Adsorption. Cavka et al. reported high
4
2
pressure CH and CO isotherms for 1 up to 80 and 30 bar,
4
2
corners of the tetrahedral cages where the capping μ -O(H)
respectively, at 25, 40, and 70 °C. Analogous data for 2 and 3
are reported here (except at 70 °C for 2). To better correlate
the effects of linker functionalization on the gas adsorption,
isotherms are also reported with volumetric uptakes (rescaled
using the crystal density of the materials).
3
groups are pointing. This means that, before the steep uptake
arises, there are no more than 1−2 water molecules per
tetrahedral cage on average. Although this loading is relatively
small, these molecules still could take part in the formation of
water microclusters around primary adsorption sites, which is
generally widely accepted as the prior step to micropore filling
The CH4 adsorption capacity (Table 4), derived from
isotherms at 25 °C (Figure 4), is moderate for all three MOFs,
33
40
in hydrophobic porous materials.
and below the best performing MOFs. Despite the steric
The desorption branch exhibits a very similar behavior, with
a slight hysteresis in water uptake all over the isotherm and an
shielding of the cluster corners (which are the preferred gas
adsorption sites) and above all the reduction of porosity (by
14
D
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Article
Table 4. Adsorption Uptakes of CH and Working
MOF displays type IV hysteresis in water adsorption/
desorption, typically associated with capillary condensation in
narrow uniform pores in mesoporous materials. UiO-67-BN
retains its structure when dried from an aqueous suspension,
conditions in which UiO-67 collapses. From single crystal
structure determination, it has been observed that the
functional linkers partially shield the strongest adsorption
sites of the MOFs. This steric shielding, along with reduction in
4
Capacities (Considering Desorption at 5 bar) at Room
a
Temperature for 1, 2, and 3
P = 35 bar
P = 65 bar
uptake
working capacity
uptake
working capacity
UiO-67
102
113
124
72
75
72
127
135
147
104
104
104
UiO-67-Me
UiO-67-BN
pore volume, may account for the enhanced stability. CH heat
4
a
3
−3
Volumes are given in cm (STP) cm .
of adsorption increases when the linker is functionalized, and
UiO-67-BN has a higher volumetric loading than UiO-67,
despite the greatly reduced pore volume.
ASSOCIATED CONTENT
Supporting Information
■
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.5b02257. The crystal structures are submitted to The
Cambridge Crystallographic Data Centre with identifiers
CCDC 1422388−1422393 and can be obtained free of charge
from http://www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi. See DOI:
Figure 4. Adsorption isotherms acquired at 25 °C, showing the
1
0.1039/x0xx00000x.
volumetric loading. Left: CH . Right: CO .
4
2
Crystal details for biphenyl-4,4'-dicarboxylic acid (CIF)
Crystal details for UiO-67-BN (CIF)
2
6% in the case of 3), the volumetric capacity of 3 is 147
3
−3
cm (STP) cm at 65 bar, whereas it is 127 for 1 and 135 for 2.
This observation seems to encourage the adopted strategy of
functionalizing the linker with pending methyl or aryl groups to
enhance the interaction with the framework and thus the
methane adsorption capacity.
However, in our case, the isosteric heat of adsorption (at zero
coverage, see Table 5) increases as well with the functionaliza-
Crystal details for UiO-67-BN (SQUEEZE) (CIF)
Crystal details for 1,1'-binaphthyl-4,4'-dicarboxylic acid
(CIF)
Synthesis and NMR characterization of 1,1′-binaphthyl-
4,4′-dicarboxylic acid; single crystal characterization of
linkers; MOF synthesis details; summary on MOF single
crystal X-ray diffraction; thermogravimetric analysis
(
TGA); surface area calculations; N adsorption; high
2
−
1
Table 5. Heats of Adsorption (kJ mol ) Calculated by
Extrapolation of the Low Pressure Data of the Virial
pressure CO and CH sorption methods (PDF)
Crystal details for UiO-67-Me (CIF)
Crystal details for UiO-67-Me (SQUEEZE) (CIF)
2 4
41
Isotherms (n vs ln(p/n)) for 1 and 3 at 25, 40, and 70 °C
CH4
CO2
AUTHOR INFORMATION
Corresponding Author
E-mail: k.p.lillerud@kjemi.uio.no.
UiO-67
15.2
20.3
23.6
20.6
■
UiO-67-BN
*
Author Contributions
tion of the linker, leading to a non-negligible uptake at low
pressure, thus rather limiting the working capacity (considering
that the first 5 bar of methane pressure cannot be used in
current vehicle applications). One should yet notice that the
improved adsorption efficiency compensates very elegantly for
the loss of pore volume over this MOF series since the working
capacity at both 35 and 65 bar is surprisingly similar for the
three MOFs investigated.
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare the following competing financial
interest(s): K.P. Lillerud and U. Olsbye have a financial
interest in the start-up company ProfMOF A/S, which is
seeking to commercialize metal−organic frameworks.
The volumetric isotherms of CO adsorption (Figure 4)
2
show as expected a significant decrease of the uptake through
the MOF series, in line with the reduction of the pore volume.
By physical volume only, an even more pronounced decrease in
adsorption capacity would have been expected for 3 compared
to 1 and 2. On the contrary, it exhibits a behavior very similar
to 2 at moderate and high pressures. Thus, the packing of CO2
molecules is improved in this more confined space, as was the
case for water adsorption.
ACKNOWLEDGMENTS
■
This work is part of CLIMIT and FutureFeedstock, which
receives financial support from the Research Council of
Norway under Contracts 215735 and 228157, respectively.
The authors would like to thank the staff at beamline I911-3 at
MaxLAB for their support at the beamline.
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CONCLUSIONS
■
It has been found that UiO-67-BN shows exceptional stability
to aqueous solutions over a wide pH range, and to water vapor
in repeated adsorption/desorption cycles. This microporous
E
DOI: 10.1021/acs.inorgchem.5b02257
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