Volume 48 Number 16 28 April 2019 Pages 5093–5460

Dalton
Transactions
An international journal of inorganic chemistry
rsc.li/dalton

ISSN 1477-9226

PAPER
Ana Martínez, Rubicelia Vargas, Ilich A. Ibarra et al.
CO2 capture enhancement for InOF-1: confinement of
2-propanol
Dalton
Transactions
PAPER

CO2 capture enhancement for InOF-1: confine-

Cite this: Dalton Trans., 2019, 48,
ment of 2-propanol†
5176
Jonathan E. Sánchez-Bautista,‡a Bruno Landeros-Rivera,‡b
Tamara Jurado-Vázquez,a Ana Martínez,*§b,c Eduardo González-Zamora, b

Jorge Balmaseda, c Rubicelia Vargas *b and Ilich A. Ibarra *a

Received 28th January 2019,
Accepted 5th March 2019
DOI: 10.1039/c9dt00384c
rsc.li/dalton
The 2-propanol (i-PrOH) adsorption properties of InOF-1 are investigated along with the confinement of
small amounts of this alcohol to enhance the CO2 capture for i-PrOH@InOF-1 (1.25-fold improvement
compared to pristine InOF-1). InOF-1 exhibited a high affinity towards i-PrOH, experimentally quantified
by ΔHads (−55 kJ mol−1), and DFT geometry optimisations showed strong hydrogen bonding between
O(i-PrOH) and H(µ2-OH). Quantum chemical models demonstrated that the CO2 capture increase for
i-PrOH@InOF-1 was due to a decrease in the void surface of InOF-1 (bottleneck effect), and the formation of
essential hydrogen bonds of CO2 with i-PrOH and with the hydroxo functional group (µ2-OH) of InOF-1.

Introduction Among the vast group of porous materials, a subgroup that

In recent years, a considerable amount of studies has been
conducted in order to demonstrate the effect of confined sol-
vents on the gas oversolubility inside porous materials. Such a
described effect is an enhancement in the gas solubility in
comparison with Henry’s law (given a known concentration of
a dissolved gas, this will be equal to a certain partial pressure
of such a gas above the chosen solvent).1 In other words,
current studies propose an oversolubility of the proposed gas
in the presence of confined solvents, leading to the alteration
of some physicochemical properties of such solvents, e.g., vis-
cosity, specific heat, density and dielectric constant.2 For
example, the work of Garcia-Garibay et al.3 demonstrates the
increase of the dynamic viscosity of DMF within the material
UCLA-R3 by 4 orders of magnitude.
a with n-hexane.
Laboratorio de Fisicoquímica y Reactividad de Superficies (LaFReS), Instituto de
Investigaciones en Materiales, Universidad Nacional Autónoma de México,
Circuito Exterior s/n, CU, Del. Coyoacán, 04510 Ciudad de México, Mexico.
E-mail: argel@unam.mx
b
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa,
San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, C. P. 09340 Ciudad de México,
Mexico
c
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de
México, Circuito Exterior s/n, CU, Del. Coyoacán, 04510 Ciudad de México, Mexico
† Electronic supplementary information (ESI) available: Materials and measure-
ments; CO2 adsorption experiments; powder X-ray diffraction patterns of InOF-1;
derivation of the isosteric enthalpy of adsorption for i-PrOH; molecular calcu-
lations and periodical calculations. See DOI: 10.1039/c9dt00384c
‡ These authors contributed equally to this work.
§ Sabbatical leave.
has shown promising results in gas capture applications is the
one formed by metal–organic frameworks (MOFs). MOFs can
be defined as crystalline materials consisting of metal ions
and organic bridging ligands with potential voids.4 In particu-
lar, MOFs are known to exhibit high adsorption capacities,
structural stability and moderate regeneration conditions
regarding CO2 capture and separation.5 Also, with the help of
small quantities of different solvents, MOFs can enhance their
gas capture properties.6
Some of the first pieces of evidence of enhanced gas
capture properties and gas oversolubility have been observed
in mesoporous materials. One representative study was pre-
sented by Pera-Titus and co-workers1,7 who demonstrated that
the confinement of different solvents, e.g., EtOH, H2O, CHCl3
and n-C6H14, improved the solubility of H2 within mesostruc-
tured materials. Regarding mesoporous MOFs, Farrusseng8
showed a remarkable enhancement of a 22-fold increase in H2
uptake by confining 60% of the pore volume of MIL-101(Cr)
As mentioned above, the oversolubility effect has been
observed only in mesoporous materials. In fact, to properly
refer to gas oversolubility, it is necessary to confine high
amounts of solvents before any gas adsorption. If the same
condition is applied to microporous MOFs, their CO2 adsorp-
tion properties cannot be enhanced, as it has been demon-
strated for NOTT-400,9 NOTT-401,10 UiO-6611 and InOF-1.12
Nevertheless, an efficient CO2 capture enhancement has been
achieved by only confining small amounts of solvents13 within
microporous MOFs.
Our research group has focused on the relevance of confin-
ing small quantities of polar solvents, to enhance the CO2

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Dalton Transactions
capture properties of microporous MOFs. We have studied the
confinement of solvents within microporous MOF materials
such as H2O,14 MeOH,15 EtOH,16 DMF17 and n-PrOH,18 with
satisfactory CO2 capture results.14–18 In particular, the confine-
ment of DMF17 and EtOH16 inside the pores of InOF-1 has
demonstrated an outstanding enhancement in CO2 capture. In
addition, the interactions of these polar solvents were observed
and carefully described with the help of single crystal X-ray
diffraction.
As the progress of CO2 capture technologies moves
forward,5,19 new hybrid MOF materials have been developed in
order to contribute with the “Twelve Principles of CO2
Chemistry”, which were enunciated by Poliakoff.20 In the
present study, our research group presents a new hybrid
material (i-PrOH@InOF-1) based on InOF-1 with 2-propanol,
also known as isopropanol (i-PrOH), confined in small quan-
tities. Thus, the CO2 capture properties of the hybrid material
i-PrOH@InOF-1 were investigated along with computational
calculations to increase fundamental insights into the mecha-
nisms responsible for the observed CO2 capture enhancement.
Experimental section
Synthesis and activation of InOF-1
The synthesis of InOF-1 was based on a methodology pre-
viously reported by Hong et al.21 For this procedure, 156 mg of
In(NO3)3·5H2O and 33 mg of H4BPTC (H4BPTC: biphenyl-
3,3′,5,5′-tetracarboxylic acid) were dissolved in 5 mL of DMF
(N,N-dimethylformamide), 5 mL of MeCN (acetonitrile) and
0.2 mL of HNO3 (nitric acid), 65 wt%, sealed in a pressure tube
and heated up to 85 °C for 72 hours. Once the synthesis was
completed, the structure of the microporous MOF material
was determined by bulk powder X-ray diffraction (PXRD).
Before activation of the material, samples of InOF-1 were
acetone-exchanged to remove any confined solvent used
during the solvothermal process (e.g. DMF). The activation of
the acetone-exchanged samples was carried out at 453 K for
two hours under a constant flow of dry N2.
PXRD experiments
Powder X-ray diffraction (PXRD) patterns were obtained in a
Bruker AXS D8 Advance system (Cu Kα radiation). PXRD pat-
terns were recorded from 5 to 45° (2θ) in 0.013° per step, at a
scan rate of 0.8° min−1. These patterns were obtained before
and after the CO2 capture experiments (Fig. S2, ESI†).
Adsorption isotherms for i-PrOH
A DVS Advantage 1 instrument, from Surface Measurement
Systems, was used to record i-PrOH sorption isotherms, at 303
and 293 K, using ultrapure grade (99.9995%) N2 gas (Praxair)
as a vapour carrier. A preheat method was carried out on the
DVS controllers in order to activate the sample (453 K), fol-
lowed by a partial pressure method, which consisted of con-
trolled step changes of partial pressure inside the sample
chamber of the instrument at a constant temperature. The
This journal is © The Royal Society of Chemistry 2019
Paper
adsorption phase consisted of 28 steps, consisting of a vari-
ation of 1% for the first 19 steps and of 5% for the following 9
steps. The desorption phase consisted of 13 steps with vari-
ations of 5 and 10%, until reaching 0% P/P0.
CO2 capture experiments
For the CO2 capture studies, the same instrument from
Surface Measurement Systems (vide supra) was used. The
experiments were carried out on fully activated acetone-
exchanged samples of InOF-1 and i-PrOH@InOF-1 samples at
303 K. Different values of partial pressure (2.26, 2.46, 2.68 and
2.76% P/P0) were selected to achieve the desired weight percen-
tages of the confined alcohol. After that, a flow of CO2 was
allowed inside the sample chamber until the mass remained
constant.
Computational calculations
Single point calculations of the model reported in Fig. 4 were
performed using Gaussian 09 implementation22 at the B3LYP
level of theory23–25 using LANL2DZ basis sets for metal atoms
and D5DV basis sets for light atoms [5–7].26–28 The quantum
theory of atoms in molecules (QTAIM) analysis29 was per-
formed using the GPUAM software.30
A partial geometry optimization of i-PrOH@InOF-1 under
periodical conditions was performed with the Crystal14 code31
at the B3LYP-D*/POB-TZVP level of theory. An isopropanol
molecule was introduced in the unit cell of InOF-1, which was
taken from previous experiments. The InOF-1 atomic positions
were taken from previous experiments and kept fixed, while
those of i-PrOH were relaxed. As a starting point, i-PrOH was
placed near the µ2-OH hydroxyl group to favour hydrogen
bond formation. An analysis of the electron densities of
InOF-1 and the optimized i-PrOH@InOF-1 was carried out in
order to determine the change in the void of the pores of the
MOF. The void volume was calculated using a program devel-
oped by our research group that is in a beta version of
GPUAM.30
Results and discussion
Isopropanol (i-PrOH) adsorption–desorption studies
Sorption experiments for isopropanol were carried out on
acetone-exchanged samples of InOF-1. These samples were
activated at 453 K for 2 hours under a flow of dry N2 gas. Once
full activation was achieved for InOF-1 and it was cooled down
to 303 K, an i-PrOH adsorption–desorption isotherm was
carried out from % P/P0 = 0 to 85 (Fig. 1). The i-PrOH uptake
increased rapidly from 0 to 10% P/P0, presumably, due to the
presence of favourable host–guest interactions, achieving an
i-PrOH uptake of almost 20 wt% (3.33 mmol g−1). From 10 to
85% P/P0, the alcohol uptake was slower but constant, having a
maximum uptake of approximately 26 wt% (4.33 mmol g−1).
A relatively strong hysteresis was observed during the de-
sorption phase, being noticeable at low pressure ranges (from
0 to 10% P/P0). Once the desorption phase was completed, a
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Fig. 1 i-PrOH adsorption isotherm at 303 K of InOF-1 from % P/P0 = 0
to 85. Solid circles show the adsorption phase. Open circles show the
desorption phase.
high amount of i-PrOH was still confined inside the pores of
InOF-1 (approximately 17 wt%, 2.83 mmol g−1). This suggests
a relatively strong affinity of InOF-1 to i-PrOH. The pore dimen-
sion of InOF-1 is approximately 7.50 Å,18 which is considerably
larger than the kinetic diameter of i-PrOH (4.7 Å).32 Thus, the
observed hysteresis suggests relatively strong host–guest inter-
actions between i-PrOH and InOF-1. The origin of these inter-
actions is, most likely, due to the formation of hydrogen bonds
between the hydroxo functional groups (µ2-OH) and the
i-PrOH molecules.
In order to experimentally investigate the strength of these
host–guest interactions (hydrogen bonds), another i-PrOH
adsorption isotherm was carried out, at 293 K (Fig. S3, ESI†),
to estimate the isosteric heat of adsorption (ΔHads) for i-PrOH.
This was calculated by fitting both adsorption isotherms to the
Clausius–Clapeyron equation (Fig. S4, ESI†). Thus, the ΔHads
value was ≈−55.15 kJ mol−1, which was higher than the molar
enthalpy of vaporisation for i-PrOH (45.24 kJ mol−1 at 298 K),
consistent with ΔHads values for other confined solvents
within InOF-1.16–18 In addition, this ΔHads value is in the same
range for previously reported i-PrOH: MIL-53(Al), another µ2-
OH containing the MOF material.15
CO2 adsorption properties
Isothermal and dynamical CO2 experiments were carried out
on InOF-1. First, an acetone-exchanged sample of InOF-1 was
activated as previously described (vide supra), and the total
CO2 capture, measured at 303 K, was equal to 5.21 wt% and it
was achieved after only 10 min (see Fig. 2). Later, in order to
investigate the effect of confining small quantities of i-PrOH
on the CO2 adsorption properties of InOF-1, different amounts
of this alcohol were pre-adsorbed into the pores of InOF-1 and
the CO2 adsorption properties were determined. The range of
i-PrOH weight percentages studied were 1.22, 2.05, 2.98 and
3.34 wt%, all of them in the low loading region as effectively
demonstrated in previous examples.12–18 Then, a partial
pressure of i-PrOH was selected (e.g., 2.46% P/P0), allowing the
vapour of i-PrOH (N2 as a carrier gas) to be pre-adsorbed
within the pores of InOF-1. When the sample mass increased
5178 | Dalton Trans., 2019, 48, 5176–5182
Dalton Transactions
Fig. 2 CO2 uptake experiments performed at 303 K under a CO2 flow
of 200 sccm in InOF-1 ( purple curve) and i-PrOH@InOF-1 (green curve);
CO2 error ±0.05 wt%.
to a value very close to the desired weight percentage (e.g.,
2.05 wt%), the partial pressure returned to 0% P/P0. Once the
mass remained constant, CO2 flow was allowed inside the
sample holder of the DVS instrument.
As shown in Fig. 3, when only 1.22 wt% of i-PrOH is pre-
adsorbed (confined), the CO2 capture (5.35 wt%) remained
similar to the CO2 capture by the pristine InOF-1. Once the
percentage of i-PrOH increased up to approximately 2 wt%, the
CO2 capture increased to 6.54 wt%. This is equivalent to a
1.25-fold increase in CO2 capture. Percentages of the confined
alcohol greater than 2.05 wt% showed a small decrease in the
capture of CO2 (see Fig. 3, also Fig. S1, ESI†). Thus, the best
amount of confined i-PrOH was found to be approximately
2 wt%, as previously observed for other alcohols (e.g.,
MeOH).33 This sample was then labelled as i-PrOH@InOF-1
and the isothermal and dynamical CO2 capture is shown in
Fig. 2.
Theoretical results
In order to investigate the role of confined i-PrOH, within
InOF-1, in CO2 capture enhancement, we used a coordination-
molecular model of the “reactive section” (μ2-OH functional
Fig. 3 Comparison of CO2 uptake experiments performed at 303 K in
InOF-1 and i-PrOH@InOF-1 with different weight percentages of the
solvent confined within the pores (1.22, 2.05, 2.98 and 3.34 wt%).
This journal is © The Royal Society of Chemistry 2019
Dalton Transactions
group) from InOF-1. This model was previously reported,16a
and the structure with isopropanol and CO2 is presented in
Fig. 4. Our calculations demonstrated that i-PrOH can estab-
lish a relatively strong hydrogen bond with the hydrogen atom
from the μ2-OH functional group (see Fig. 4). Then, when a
CO2 molecule is incorporated into this arrangement, this can
interact with i-PrOH via one hydrogen bond with the OH
group from the alcohol (i-PrOH). Thus, i-PrOH stabilises the
CO2 molecule and such stabilisation is partially responsible
for the enhanced CO2 adsorption capacity.
To describe and understand the characteristics of these
hydrogen bonds, we employed the analysis of bond critical
points (depicted by orange nodes which indicate connectivity,
Fig. 5) of the electron density within the QTAIM (quantum
theory of atoms in molecules) framework, which is a powerful
tool to characterise non-covalent interactions.34 An important
criterion to evaluate the strength of non-covalent interactions
(derived from QTAIM analysis)35 is the electron density value
taken at the bond critical point (ρBCP); the larger the value, the
stronger the interaction (see Table S1, ESI†).
According to the QTAIM analysis, the molecular graph of
the model is depicted in Fig. 5. Bond paths (depicted by
orange lines, see Fig. 5) connecting each guest (CO2 and
i-PrOH) with the coordination-molecular model and with each
other (CO2 and i-PrOH) were found, suggesting enhancement
in the CO2 adsorption on the InOF-1 surface. CO2 interactions
with InOF-1 were precisely identified: two non-canonical O⋯O
(one was found to be commonly weak and the other one sur-
passingly strong, vide infra) along with a characteristic weak C–
H⋯O hydrogen bond (see Table S1, ESI†). The abnormal O⋯O
interaction (large ρBCP) could be attributed to a short contact
(2.340 Å, see Fig. 5 and Table S1, ESI†), as shown by the
model. i-PrOH and InOF-1 are linked by O–H⋯O and C–H⋯O
hydrogen bonds. Interestingly, this C–H⋯O contact is the
strongest hydrogen bond (see Table S1, ESI†) estimated by our
model. Finally, CO2 is also trapped by a strong O–H⋯O hydro-
gen bond formed with the alcohol molecule (i-PrOH). The
occurrence of the latter interaction is postulated to be one of
those responsible for the increase in the CO2 capture ability of
i-PrOH@InOF-1.
Thus, this coordination-molecular model provided us
important insights concerning the enhancement in CO2
capture due to the confined isopropanol. Nevertheless, it is
Fig. 4 Optimized structure of the coordination-molecular model with
isopropanol and CO2.
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Paper
Fig. 5 Molecular graph of the model. BCPs and bond paths are drawn
in orange. Only intermolecular contacts are represented.
relatively limited to a local situation due to the restrictions of
the model itself. For this reason, periodical calculations on the
crystalline framework material can provide us valuable infor-
mation to complement our investigation. The partial opti-
mised geometry of i-PrOH@InOF-1 obtained under periodical
conditions is depicted in Fig. 6. As expected, a hydrogen bond
was formed between the hydroxyl of i-PrOH and the µ2-OH of
InOF-1 with an O–H⋯O distance of 1.932 Å (Fig. 6a), which is
consistent with the value found in MeOH@InOF-1 studied in a
previous study.33 Other geometrical parameters that are useful
for the characterisation of the hydrogen bond are the O⋯O
distance and the O–H⋯O angle, which were found to be
2.881 Å and 163.8°, respectively. According to the criteria pro-
posed by Desiraju,36 this hydrogen bond falls into the category
of strong. An interesting feature is that i-PrOH fits in the
“dent” around µ2-OH (Fig. 6b), as it was observed for the N,N-
dimethylformamide (DMF) molecule in a preceding study.17
These results denote that, along with the capacity of forming a
hydrogen bond with µ2-OH, any system should also have an
appropriate shape that allows its insertion in the InOF-1
“dent”. This selective property of InOF-1 needs to be con-
sidered when other solvents are tested to increase CO2 capture.
It is noticed that the carbon chain of i-PrOH reduces the
pore size (Fig. 6c). This fact advocates for the “bottleneck”
effect that was proposed by Jancik et al.,16a,17 which consists of
a reduction of the pore size generated by polar molecules (e.g.,
EtOH and DMF) bonded to the µ2-OH of InOF-1, which causes
CO2 to slow down, facilitating in this way its adsorption. In
order to confirm the presence of a bottleneck effect by the con-
finement of i-PrOH, the void volume of one pore contained in
the unit cell (there are two pores per unit cell) was estimated
by means of an electron density isosurface (ρ = 0.0003 a.u.),
following the model proposed by Turner et al.37 In Fig. 7, the
void channels of the empty InOF-1 and i-PrOH@InOF-1 are
shown. From this figure, a clear difference is observed; the
“lump” is found in the latter system at the i-PrOH position.
For our model, corresponding to a 2.48 wt% of i-PrOH, the
“empty space” of the pore (in the unit cell) is reduced by
13.8%, which is relatively large considering that only a single
alcohol molecule was placed in each unit cell. This outcome
can explain why, at i-PrOH weight percentages larger than
2.98 wt%, the CO2 adsorption starts to decrease because, as
was shown before,16a the saturation of the micropores makes
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Paper Dalton Transactions

Fig. 7 Solid (top) and transparent (bottom) isosurface of the electron

density (ρ = 0.0003 a.u.), denoting the voids of the empty InOF-1 (left)
and i-PrOH@InOF-1 (right).

Finally, in order to evaluate the regeneration properties and

the CO2 desorption process of i-PrOH@InOF-1, isothermal and
dynamical CO2 experiments (adsorption–desorption) were per-
formed at 303 K (Fig. 8). Each cycle involves an adsorption
step (15 minutes) and a desorption step (15 min), total cycling
time of 30 min, without the use of N2 purge or raising the
temperature (complete CO2 desorption). Thus, by only turning
off the CO2 flow (desorption step) at 303 K, the total regener-
ation of i-PrOH@InOF-1 was achieved. From the first cycle
(6.50 wt% CO2 capture) to the tenth cycle, a minimal reduction
in the CO2 total capacity of only 0.4 wt% (from 6.50 to
6.10 wt%) was observed. Even though there was a loss in the
total CO2 capture, this result is relevant since there is no need
to purge with N2 or re-activate the sample at higher tempera-

Fig. 6 (a) DFT-optimized geometry of i-PrOH@InOF-1. The inter-

molecular distance (dashed line) of the hydrogen bond formed between
the hydroxyl of i-PrOH and the µ2-OH of InOF-1 is reported in Å. (b) The
“dent” around the µ2-OH where i-PrOH is inserted. (c) View along the
100 crystallographic direction.

the inclusion of CO2 unfeasible. With the insertion of a

second i-PrOH molecule in the unit cell, leading to a
4.85 wt%, the void is reduced by more than 25%.
Consequently, the CO2 capture by i-PrOH@InOF-1 is a compro-
mise of several effects: the direct interaction between CO2 and
the µ2-OH functional group of InOF-1 and possible synergic
effects caused by the presence of CO2 and i-PrOH, as described
in our coordination-molecular model, both of which will be
enhanced by the bottleneck effect as long as saturation is not Fig. 8 Adsorption–desorption cycling for i-PrOH@InOF-1 showing
reached. reversible CO2 capture.

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Dalton Transactions
tures. Furthermore, according to our DFT computations, there
is more affinity of InOF-1 for i-PrOH than for CO2, as pre-
viously observed for MeOH.17 The displacement energy,
defined as the difference between the energy needed for releas-
ing i-PrOH molecules from InOF-1, and the interaction energy
of CO2 and InmOF-1, is approximately +18.9 kcal mol−1, which
indicates that this process is non-favourable. Therefore, a
stronger CO2 flow will be needed to provide sufficient
energy for i-PrOH molecules to be desorbed from the pores of
InOF-1.
Conclusions
The i-PrOH adsorption properties of InOF-1 were, to the best
of our knowledge, investigated for the first time. Fast i-PrOH
uptake and hysteresis at 293 and 303 K demonstrated a high
affinity towards i-PrOH. The i-PrOH affinity was experimentally
quantified by the evaluation of the isosteric heat of adsorption
(ΔHads ≈ −55 kJ mol−1). Also, DFT geometry optimisations
demonstrated that the hydrogen bond between O(i-PrOH) and
H(µ2-OH) is classified as strong, corroborating the relatively
high ΔHads for i-PrOH. Dynamical isotherm CO2 experiments
on i-PrOH@InOF-1, small amounts of i-PrOH confined within
the pores of InOF-1 (2.05 wt%), showed a CO2 capture of
6.54%, which corresponds to a 1.25-fold improvement com-
pared to fully-activated InOF-1 (5.23 wt%). Quantum chemical
models demonstrated that the increment in the CO2 capture
for i-PrOH@InOF-1, in comparison with the pristine InOF-1, is
a result of two effects: a decrease in the void surface of InOF-1,
which enhanced its capture via a bottleneck effect, and the for-
mation of essential hydrogen bonds (O–H⋯O and C–H⋯O) of
CO2 with isopropanol and with the hydroxo functional groups
(µ2-OH) of InOF-1.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors thank Dr A. Tejeda-Cruz ( powder X-ray;
IIM-UNAM) for analytical assistance. Thanks to U. Winnberg
(ITAM) for scientific discussions and language editing.
Financial support for this work was provided by PAPIIT UNAM
Mexico (IN101517), CONACyT under grants No. 1789 (I. A. I.),
CONTex 2018-36B (I. A. I.) and 236879 (E. G.-Z.). We are grate-
ful to the Laboratorio de Supercómputo y Visualización en
Paralelo at the Universidad Autónoma Metropolitana (UAM)
Iztapalapa for access to their computer facilities. J. E. S.-B.
thanks UNAM and all the people who supported him during
the writing of this article. B. L.-R. thanks UAM for a postdoc-
toral fellowship. Dr Raymundo Hernández-Esparza is acknowl-
edged for the development of the software used for the compu-
tation of the void properties.
This journal is © The Royal Society of Chemistry 2019
Paper
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