Colloids and Surfaces A 561 (2019) 128–135

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Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

Adsorption of gases and vapours in silica based xerogels T

a a,b c,d c,d
Joana Fernandes , Ana C. Fernandes , Jesús C. Echeverría , Paula Moriones ,
Julián J. Garridoc,d, João Piresa,
⁎

a
Departamento de Química e Bioquímica, Faculdade de Ciências, CQB and CQE, Universidade de Lisboa, Campo Grande, 1749-016, Lisboa, Portugal
b
CICECO, Universidade de Aveiro, Aveiro, Portugal
c
Departamento de Química Aplicada, Universidad Pública de Navarra Campus Arrosadía, 31006, Pamplona, Spain
d
Institute for Advanced Materials, Edif. Jerónimo de Ayanz, Universidad Pública de Navarra, Campus Arrosadía, 31006, Pamplona, Spain

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: In spite of the outstanding adsorption properties of microporous silica and hybrid silica xerogels, the selectivity
Xerogel of these materials towards gases and vapours has been studied to a little extent. In this work we studied selected
Adsorbents silica and hybrid xerogels of microporous nature to evaluate their adsorption properties for the following mo-
Ethane lecular separations: carbon dioxide / methane; ethane/ethylene; and hexane isomers. For the carbon dioxide /
Ethylene
methane system a microporous silica xerogel synthesized at pH 2.5 showed the most favourable results, ad-
Hexane isomers
sorbing 1.8 mmol/g of CO2. In the case of the ethane/ethylene system it was possible to obtain materials with
reverse selectivity, that is, while silica xerogels adsorbed preferentially ethylene, some hybrid xerogels adsorbed
preferentially ethane. Considering the adsorption of hexane isomers (n-hexane, 3-methyl pentane and 2,2-di-
methylbutane), both silica and hybrid xerogels, but particularly the latter, were able to differentiate between the
adsorption of the mono and the di-branched isomers.

1. Introduction
Energy is the primary ‘fuel’ for social and economic development,
but energy and energy-related activities also have significant impacts
on other areas such as the environment and technology [1]. It is
interesting to note that while the world population between 1993 and
2020 will increase from 5.5 to 8.1 billion (a nearly 50% increase), the
energy consumption in the same period, either from oil, coal or natural
gas, will proportionally grow more since it almost doubles [1].
Chemistry is obviously related to the more (but sometimes less)

⁎
Corresponding author.
E-mail address: jpsilva@ciencias.ulisboa.pt (J. Pires).

https://doi.org/10.1016/j.colsurfa.2018.10.063
Received 28 May 2018; Received in revised form 16 October 2018; Accepted 23 October 2018
Available online 23 October 2018
0927-7757/ © 2018 Elsevier B.V. All rights reserved.
J. Fernandes et al. Colloids and Surfaces A 561 (2019) 128–135

efficient use of energy, and nanoporous materials [2] are key for this
efficiency in various energy-related processes, particularly those related
with molecular separations. There are several examples, as is the case of
the alkene/alkane separation which is one of the most energy-intensive
single distillations practiced commercially [3–5]. Another example is
the separation of the linear, mono and di-branched hexane isomers. In
fact, while zeolitic materials are already in use for this, the isomers
separation is not complete since a significant proportion of mono-
branched molecules is still present in the final mixture, which lowers
the Research Octane Number (RON) [6–11]. A third example is related
with the separation of methane from biogas [12] or landfill gas [13],
from which the major contaminant is carbon dioxide, to upgraded
biogas and produce high quality fuel.
Various series of materials have been studied for the above men-
tioned separations, each one with their advantages and drawbacks as
discussed in the literature [3,6,14–17]. However, the number of studies
involving those separations in microporous xerogels is rather limited.
Nevertheless, sol–gel chemistry offers a flexible approach to obtain a
diverse range of materials. It allows differing chemistries to be achieved
as well as offering the ability to produce a wide range of nano / micro-
structures. To obtain silica based materials, sol–gel methods typically
involve the use of tetraethoxysilane (TEOS) as a principal network
forming agent. TEOS allows the formation of robust networks, and a
high degree of synthesis control is afforded through variations in the
experimental conditions such as pH, temperature, and additives [18]. In
contrast to zeolites and Metal-Organic Frameworks (MOFs), which are
crystalline materials, silica based xerogels are amorphous. Even if this
does not necessarily hamper their adsorption possibilities it surely
hinders the prediction of the adsorption properties for instance by
molecular simulation. Therefore, laboratory experiments are manda-
tory to ascertain the adsorption properties of xerogels.
In recent years, some of us have been synthetizing and character-
ising silica and hybrid silica-organic xerogels [17,19–23]. Within the
later, various organic moieties were studied such as methyl [20], ethyl
[21], propyl [24] or phenyl [17] groups. With the objective of selecting
some of these materials for studying their adsorption properties, some
rationalization of their characteristics, although not straightforward,
needs to be made. For instance, in the case of the hybrid xerogels values
higher than 30% of the organic groups (in relation to TEOS) usually
produce materials with low specific surface areas, and hence, low ad-
sorption capacities. Other relevant issue is the thermal stability, for
instance, the hybrid materials prepared with phenyltriethoxysilane
(PhTEOS) present the highest thermal stability of the series studied, in
some cases they were stable at temperatures around 700 K [24].
Therefore, to the present work we selected three silica xerogels pre-
pared with from TEOS and four hybrid xerogels prepared from TEOS/
PhTEOS series (Table 1) that present different types of porosity and/or
composition. Sample XG00-2.5 is an ultramicroporous silica xerogel
that adsorbs CO2 at 273 K but not N2 at 77 K, which denotes activated
adsorption and that it might act as a molecular sieve. Because the pH of
synthesis was 2.5, the surface has silanol groups ^Si]OH. Xerogel
XG00-4.5 was synthesized at pH 4.5 with the same concentrations of
TEOS, ethanol and water as XG00-2.5. It has a well-developed porous
texture that includes micro and mesoporos. Sample XG00-4.5a was also
synthesized at pH 4.5 but with lower molar ratios for ethanol and water
than the other silica xerogels. Incorporation of phenyl groups into the
silica structure reduce the amount of silanol groups on the surface of
hybrid materials, but the phenyl group has a hydrophobic aromatic ring
that modifies the interaction forces with adsorbibles. We chose four
hybrid samples to compare the effect of the synthesis pH (4.5 and 10),
the amount of PhTEOS (20, 25, and 30%), and the addition of ammo-
nium fluoride to reduce the double layer of the colloids that, in turn,
favours gelation. The skeleton density of xerogels was ∼1.9 g cm−3 for
xerogels prepared from TEOS and between 1.61 and 1.67 g cm−3 for
hybrid xerogels. These values are in line with the density of amorphous
silica and the decreasing intensity when organic groups incorporate to
the inorganic matrix. The bulk density, estimated by taking into ac-
count the specific volume from the skeleton density and the volume of
macropores was ∼1.4 g cm−3 for xerogels and hybrid xerogels syn-
thesized at acid pH, and ∼1.3 g cm−3 for hybrid xerogels synthesized
at pH 10
The goal of this research was to investigate the adsorption of gases
and vapours by silica xerogels and hybrid phenyl-silica xerogels. The
specific goals were the following: (a) to obtain the high-pressure ad-
sorption isotherms at 298 K; (b) to obtain the adsorption isotherms of n-
hexane, and branched isomers; and (c) to assess the selectivity of the
adsorbents towards carbon dioxide/methane, ethane/ethylene, and
hexane isomers.
2. Experimental
2.1. Synthesis
Silica sources were tetraethoxysilane (TEOS) and phenyltriethox-
ysilane (PhTEOS) (Fluka, 98%). Absolute ethanol, hydrochloric acid
and aqueous ammonia for analysis were from Merck. The water used
was of MilliQ quality. The xerogels were synthesised at pH 2.5, 4.5 and
10 at 333 K. The PhTEOS molar percentagein the siliceous mixture was
set to 20, 25 or 30% (Table 1). The required amount of precursors and
ethanol were mixed with a magnetic stirrer in a 30-mL glass container.
Under constant stirring, the required amount of water was added
dropwise. The sample containers were closed, stirred in an orbital

Table 1
Textural properties of silica xerogels made from TEOS and hybrid xerogels made from TEOS-PhTEOS mixtures. Specific surface areas were evaluated by BET (N2
adsorption at 77 K) and DR methods (CO2 adsorption at 273 K). The nomenclature of the samples includes XG for xerogels from TEOS and HXG for hybrid xerogels,
the first two figures refer to the molar percentage of PhTEOS in the initial mixture of precursor (0, 20, 25 and 30), and the final figures indicate the pH (2.5, 4.5 or
10).
Precursor (molar percentage, %) pH Molar ratios Specific surface area (m2 g−1) V micro (cm3 g−1)

Sample TEOS PhTEOS Ethanol:precursor Water:precursor as(BET) aDR(CO2) N2 CO2

XG00-2.5 100 0 2.5 4.75 5.50 N.D. 478 N.D. 0.192

XG00-4.5 100 0 4.5 4.75 5.50 648 395 0.240 0.158
XG00-4.5a 100 0 4.5 2.25 2.50 674 303 0.231 0.122
HXG20-4.5 80 20 4.5 4.75 5.50 203 242 0.085 0.097
HXG25-4.5 75 25 4.5 4.75 5.50 ND 213 0.002 0.085
HXG30-10 70 30 10 6.00 6.00 245 147 0.097 0.059
HXG30-10ba 70 30 10 6.00 6.00 421 234 0.168 0.094

a
Ammonium fluoride was added to facilitate gelling.

129
J. Fernandes et al.
Fig. 1. Micropore size distributions (CO2 adsorption at 273 K by the
Dubinin–Radushkevich–Stoeckli equation) for: (a) the silica xerogels; and, (b)
hybrid xerogels.
shaker and allowed to stand until gelation was achieved. The gels were
covered with 5 mL of ethanol and aged for seven days. The alcogels
were dried at 295 ± 2 K and atmospheric pressure. A more detailed
description of the synthesis method can be found elsewhere [24].
2.2. Characterisation
Adsorption of Nitrogen at 77 K and CO2 at 273 K was determined in
a Micrometrics ASAP 2010 adsorption analyser. The samples (∼
100 mg) were outgassed at 423 K, for at least 15 h, at a residual vacuum
of 7 × 10−1 Pa. The specific surface area was calculated from the N2
adsorption data (molecular cross section 0.162 nm2) according to the
Brunauer–Emmett–Teller (BET) method [2], and by applying the Du-
binin–Radushkevich (DR) method to CO2 adsorption at 273 K (mole-
cular cross-section of 0.170 nm2 [25]. Micropore size distributions were
obtained from the CO2 adsorption isotherms at 273 K by the Dubi-
nin–Radushkevich–Stoeckli equation by a methodology discussed
elsewhere [26]. As described in previous studies [17,24], the samples
were characterised by helium pycnometry (Micromeritics Accupyc
1330); Fourier-transformed infrared -FTIR spectroscopy (Nicolet Avatar
360 FTIR spectrometer); simultaneous thermogravimetry and differ-
ential scanning calorimetry (TGA–DSC) using a SETARAM, Mod. Setsys
Evolution 1600, and by 29Si NMR (Bruker AV-400 MHz spectrometer).
2.3. Adsorption of ethane, ethylene, carbon dioxide and methane
The adsorption isotherms of ethane (Air Liquide, 99.995%),
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Colloids and Surfaces A 561 (2019) 128–135
ethylene (Matheson, 99.995%), carbon dioxide (Air Liquide, 99.99%),
and methane (Air Liquide, 99.99%) were measured up to pressures of
750 kPa at 298 ± 0.1 K. The experiments were carried out in a volu-
metric apparatus made in stainless steel, equipped with a pressure
transducer (Pfeiffer Vacuum, APR 266) and a vacuum system, which
allowed a vacuum better than 10−2 Pa. The adsorption temperature
was maintained with a water bath (Grant Instrument, GD-120). Each
sample was degassed for 3 h at 523 K before the experiments. For the
calculations of the amounts adsorbed, gas non-ideality was considered
by using the second virial coefficient. Reproducibility of the adsorbed
amounts is between 2%, for pressures below 200 kPa and up to 5% for
pressures up to 800 kPa
2.4. Adsorption of hexane isomers
For the determination of the adsorption isotherms of n-hexane
(Merck, 99.0%), 3-methylpentane (Sigma-Aldrich, ≥99%), and 2,2
dimethylbutane (analytical standard) a vacuum microbalance
(C.I.Electronics), which allowed a precision of 10 μg was used. The
pressure was measured by a pressure transducer (Pfeiffer Vacuum CMR
262) and the samples were outgassed for 3 h at 523 K under high va-
cuum before experiments. The lowest sensitivity of the pressure sensor
was 10−1 Pa. However, to ensure high quality data, only pressure
readings higher than 10 Pa were recorded (that is, 100 times higher the
lowest sensor sensitivity). The adsorption temperature was maintained
by a thermostatic water bath as above. The hydrocarbons were purified
by conducting freezing-vacuum-thawing cycles. Tables S1 and S2 in
Supporting Information collected various physical characteristics of the
adsorptive molecules used.
3. Results and discussion
3.1. Characterisation
Table 1 summarizes the textural properties of the xerogels (XG00-
2.5, XG00-4.5, and XG00-4.5a), and the hybrid xerogels (HXG20-4.5,
HXG25-4.5, HXG30-10 and HXG30-10b). Xerogels synthesized from
TEOS had larger specific surface areas than hybrid xerogels from TEOS-
PhTEOS mixtures. Hybrid xerogels synthesized at pH 10 had larger
surface areas than those synthesized at pH 4.5. The addition of am-
monium fluoride to decrease the double layer of colloids and favour the
gelation resulted in the largest specific area and pore volume of hybrid
xerogels. The sample XG00-2.5 is ultramicroporous (< 0.7 nm), it ad-
sorbed CO2 at 273 K but not N2 at 77 K.
The micropore size distributions for the various samples were ob-
tained from the CO2 adsorption isotherms at 273 K by the
Dubinin–Radushkevich–Stoeckli equation by a methodology discussed
elsewhere [27], which relates the characteristic energy of the DR
equation (E0) with the micropore width (L). The results are shown in
Fig. 1 for silica and hybrid xerogels, respectively.
As can be seen in Fig. 1.a, the material XG00-2.5 is an ultra-
microporous sample, the micropore widths are lower than 0.45 nm
while the samples XG00-4.5 and XG00-4.5a show a wide range of mi-
cropore widths. The fact that the xerogel synthesis at a pH of 2.5
(Table 1) leads to samples with very small pore openings was already
reported and discussed in the literature [23]. The introduction of the
organic moieties in the hydrid xerogels (Fig. 1.b) resulted in materials
with porosity better defined, that is, with narrower micropore size
distributions, particularly when comparing with XG00-4.5 and XG00-
4.5a.
3.2. Adsorption of ethane, ethylene, carbon dioxide and methane
High pressure adsorption isotherms of carbon dioxide, ethylene,
ethane, and methane at 298 K in silica (XG00-2.5, XG00-4.5, XG00-4.5a)
and the hybrid xerogels (HXG20-4.5, HXG25-4.5, HXG30-10, HXG30-
J. Fernandes et al.
Fig. 2. Adsorption isotherms of carbon dioxide, ethylene, ethane, and methane
at 298 K in the silica xerogels: XG00-2.5, XG00-4.5, and XG00-4.5a.
10b) are shown in Figs. 2 and 3, respectively. Xerogels from TEOS ad-
sorbed larger amounts of CO2, ethylene, ethane and methane than hybrid
xerogels synthesized from PhTEOS-TEOS mixtures, which can be related
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Colloids and Surfaces A 561 (2019) 128–135
to the contribution of silanol groups on the surface of xerogels and higher
pore volumes. It should be noticed that the kinetic diameters for carbon
dioxide, methane, ethane and ethylene (in nm) are 0.33, 0.38, 0.38 and
039 [28], respectively, Therefore, according to the micropore size dis-
tributions in Fig. 1, molecular sieving on a basis of pore dimensions and
molecule dimensions are not expected. For xerogels, the amount ad-
sorbed followed the trend CO2 > ethylene > ethane > methane. The
fact that xerogels adsorbed larger amounts of CO2 and C2H4 than C2H6
and CH4 points out the role of some dipole-dipole attraction between π-
bonds and silanol groups (or quadrupole-dipole in the case of carbon
dioxide). For phenyl silica xerogels, the trend was CO2 ≥ ethylene ≥
ethane > methane. Because xerogels and hybrid xerogels adsorbed
more C2H6 than CH4, it rules out the presence of molecular sieve effects.
In the case of the ethane/ethylene pair, the xerogel (XG) samples
always adsorbed higher amounts of ethylene than ethane. This is the
most general behaviour found in literature for instance for zeolites
[29,30] or silicas [31], and it is usually interpreted as resulting from the
favoured interactions between the cations or OH groups of the material
with the ethylene double bond [29–31]. In the case of the hybrid xer-
ogels, whereas HXG20-4.5 and HXG30-10b favoured the adsorption of
ethylene over ethane, HXG30-10 adsorbed more ethane than ethylene
over all the pressure range, and HXG25-4.5 adsorbed more ethane than
ethylene up to 3 bar. According to these results, silanol groups, proto-
nated silanol groups and the presence of ammonia cation as counterion
in sample HXG30-10b will enhance the interaction with carbon dioxide
and ethene. When the concentration of silanol groups decreases either
by including PhTEOS as precursor or by synthesizing the materials at
pH 10 the selectivity of the samples toward CO2 and C2H4 diminished,
in line with was already discussed in literature about the interactions of
surface groups and the ethane and ethylene molecules [4].
Most of the known adsorbents display preferential adsorption of
ethylene over ethane as for instance zeolites [32], mesoporous silicas
[33], clay based adsorbents [34], or various types of metal-organic
frameworks (MOFs) [35,36]. However for industrial application this
implies an additional desorption step, normally using an inert gas or
applying vacuum, to obtain high-purity ethylene which complicates the
technology of the process, making its implementation difficult due to
economic reasons [37,5]. Therefore, if the ethane is preferentially ad-
sorbed, that is if the adsorbent gives reversed selectivity for the ethane/
ethylene mixture [5], pure ethylene is directly obtained during the
adsorption step, and the separation becomes much cost effective [38].
As mentioned, the number of materials that display favoured adsorp-
tion of ethane over ethylene is not very high but examples exist in the
literature, particularly for some MOFs [37,39]. This type of selectivity
was interpreted in terms of the interactions between the organic moiety
of material and the ethane molecule being stronger due to dispersion
forces that are developed with the ethane molecule, which is more
voluminous than ethylene [39]. Apparently, the same explanation can
also be applied to the results of the hybrid xerogels HXG25-4.5 and
HXG30-10, which present higher proportion of organic moiety. How-
ever for sample HXG30-10b, the adsorption of ethylene is now fa-
voured. Using NH4F as catalysts reduces the gelification time and, most
probably in this situation, the NH4+ cation remains as a counter ion on
the surface and enhaces the adsorption of carbon dioxide and ethene.
To quantify the CO2/CH4 and ethane/ethylene separations in the
various materials, selectivity (or separation factor) – S1,2 - values were
estimated by a methodology proposed by Myers [40] based on the ideal
adsorbed solution theory (IAST) and detailed in the Supporting In-
formation. For this, the adsorption isotherm must be described by an
analytical expression and in the present work, as also used previously in
the literature [39,40], the virial equation was used. The fittings of the
virial equation are presented in the Supplementary material, Section
2.2. The selectivity values are shown in Fig. 4 where all values are
higher than 1 for the sake of improving comparison of the results.
Therefore, Fig. 4(c) plots the selectivity for C2H6/C2H4 for samples
HXG25-4.5 and HXG30-10. In general, Fig. 4 shows that the selectivity
J. Fernandes et al.
Fig. 3. Adsorption isotherms of ethane, ethylene, carbon dioxide and methane at 298 K in the hybrid xerogels HXG20-4.5, HXG25-4.5, HXG30-10 and HXG30-10b.
values are always higher for the xerogels made only of silica than for
the hybrid xerogels.
Considering the CO2/CH4 separation the sample XG00-2.5, which
has the narrowest micropore widths (Fig. 1.a) shows the highest se-
lectivity value. This value can be considered high even when compared
with the literature (Table S3 – Supporting Information), although the
total amounts adsorbed are relatively low. Sample HXG30-10b shows
the more favourable selectivity values amongst the hybrid xerogels. For
the ethane/ethylene pair, silica xerogels again show the highest values.
However, it is interesting the case of the samples HXG25-4.5 and
HXG30-10 that show reversed selectivity and so ethane is more ad-
sorbed than ethylene (Fig. 4(c). Particularly for sample HXG30-10 the
selectivity values are near 2 for a wide range of pressures, which is near,
or sometimes better, than what can be found in the literature (Table S4
– Supporting Information).
Since the samples XG00-2.5 and HXG30-10b showed the more fa-
vourable results within each series concerning amounts adsorbed and
selectivity values, these materials were studied for their cyclic re-
generation under vacuum at ambient temperature (298 K), for the ad-
sorption of the most adsorbed molecules of each system (CO2 and
ethylene). The results (Fig. 5) show that CO2 can be entirely removed
from both samples, pointing out the reversible adsorption of carbon
dioxide in these samples but, for the hybrid xerogel, a slight decrease in
the adsorption capacity for ethylene is noticed.
3.3. Adsorption of hexane isomers
The adsorption isotherms of n-hexane, 3-methyl pentane and 2,2-
dimethylbutane at 298 K are shown in Figs. 6 and 7. For the silica
xerogels (Fig. 6), the sample XG00-2.5 did not adsorb the n-hexane
isomers in line with its narrow microporosity.
132
Colloids and Surfaces A 561 (2019) 128–135
The sample XG00-4.5a did not adsorb the di-branched molecule
which, at the first sight, could be a positive indication regarding the
separation of the di-branched isomer from the linear and mono-bran-
ched. However, the adsorbed amounts in this material are very low. In
the case of the hybrid xerogels (Fig. 7), the behaviour is relatively
general amongst the samples, that is, they adsorb the three isomers and
its adsorption is well differentiated. Sample HXG30-10 presents the
lowest amounts adsorbed of the series which is most probably related to
its lowest microporous volume.
The modelling of the adsorption isotherms of the hexane isomers by
equations that are often applied to the adsorption of hydrocarbon va-
pours in microporous materials, such as the Tóth or
Dubinin − Astakhov (DA) equations [41–43], was not satisfactory in
the case of the silica xerogels. For the hybrid xerogels, only the DA
equation gave acceptable fittings, whose parameters are given in Sup-
porting Information – Table S5, together with the average percent de-
viations and the degree of dispersion of the fittings. In Table S3 the
characteristic energy (E) of the DA equation is a parameter related to
the adsorption energy, and has been compared with the heats of ad-
sorption [44]. It is interesting to notice that E values are highest for the
bulkiest di-branched isomer, reflecting the existence of stronger inter-
actions between these molecules and the studied hydrogels, when
comparing to the linear and mono-branched isomers.
To compare the potentialities of the materials for the hexane iso-
mers separation, and also because the evaluation of selectivity values
from the adsorption isotherms in the case of vapours adsorption is not
straightforward and there are not many values in the literature to
compare, the comparison with the literature was made considering the
ratio of the adsorbed amounts at a given pressure for various types of
materials – Table S6, Supporting information. The comparison was
made with the more favourable materials from this work (XG00-4.5 and
J. Fernandes et al. Colloids and Surfaces A 561 (2019) 128–135

Fig. 5. Adsorption isotherms of carbon dioxide and ethylene at 298 K before

(run 1) and after (run 2) regeneration under vacuum in the indicated materials.

HXG30-10b). As can be seen in this Table the adsorbed amounts in the

xerogels prepared in this work are amongst the highest reported in the
literature for comparable temperatures. Considering the ratios of the
adsorbed amounts (we considered at 75 Torr to uniformize with data
available in the literature) and bearing in mind the more relevant se-
paration, that would be between the mono-branched and the di-bran-
ched isomers, it can be notice that the values for sample HXG30-10b are
near the highest values found in the literature.

4. Conclusions

Adsorption properties of microporous silica and hybrid organic-si-

Fig. 4. Selectivity values for the systems (a) carbon dioxide / methane, and (b)
ethylene / ethane, and (c) ethane / ethylene.
lica xerogels demonstrate that they can be considered for the separation
of gases and vapours. The high pressure adsorption isotherms of ethane,
ethylene, carbon dioxide and methane at 298 K in silica (XG00-2.5,
XG00-4.5, and XG00-4.5b) and the hybrid xerogels (HXG20-4.5,
HXG25-4.5, HXG30-10, and HXG30-10b) showed that the adsorbed
amounts are in general higher for the silica xerogels than for the hybrid
materials, which can be related to higher pore volume and larger sur-
face density on silanol groups. Considering the CO2/CH4 separation, the
sample XG00-2.5, which as the narrowest micropore widths, shows the
highest selectivity value which is high even when compared with the
literature. For the ethane/ethylene case, silica xerogels again showed
the higher selectivities values than hybrid xerogels. However, it is in-
teresting the case of the hybrid xerogels HXG25-4.5 and HXG30-10 that

133
J. Fernandes et al. Colloids and Surfaces A 561 (2019) 128–135

Fig. 6. Adsorption isotherms of n-hexane isomers at 298 K in the indicated si-

lica xerogels.

showed reversed selectivity and ethane was more adsorbed than ethene,
particularly for sample HXG30-10 the selectivity values are near 2 for a
wide range of pressures. In the case of the adsorption of hexane isomers,
some samples (XG00-4.5 and GHXG30-10b) showed that the adsorbed
amounts and their ratio for each pair of isomers are amongst the more
favourable reported in the literature. The experimental results obtained
in this research highlight the potential and versatility of the sol-gel
methodology for synthesizing xero- and hybrid xerogel for adsorption
de gases and vapours. The sol-gel is a powerful tool to tune the porous
texture and surface chemistry of adsorbents.

Acknowledgments
Fig. 7. Adsorption isotherms of n-hexane isomers at 298 K in the indicated
The authors thank the Foundation for Science and Technology for hybrid xerogels.
funding CQB (UID/MULTI/00612/2013). This work was supported by
“Ministerio de Economía, Industria y Competitividad” (MAT2016-
78155-C2-2-R). Paula Moriones is thankful to the “Departamento de Appendix A. Supplementary data
Industria y Tecnología, Comercio y Trabajo” of Navarre Government for
a fellowship. Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.colsurfa.2018.10.063.

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