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Journal of Chromatography A, xxx (2017) xxxxxx

Contents lists available at ScienceDirect

Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Behavior of macroporous vinyl silica and silica monolithic columns in

high pressure gas chromatography
Adrien Maniquet b , Nicolas Bruyer a , Guy Rafn a , Franck Baco-Antionali b ,
Claire Demesmay a , Vincent Dugas a , Jrme Randon a,
a
Univ Lyon, CNRS, Universit Claude Bernard Lyon 1, Ens de Lyon, Institut des Sciences Analytiques, UMR 5280, 5 rue de la Doua, F-69100 Villeurbanne,
France
b
IFP nergies nouvelles tablissement de Lyon, Exprimentation Procds, Rond-point de lchangeur de Solaize, BP3, 69360 Solaize, France

a r t i c l e i n f o a b s t r a c t

Article history: 80% vinyltrimethoxysilane-based hybrid silica monoliths (80-VTMS), which have been initially devel-
Received 12 April 2017 oped for separation in reversed-phase liquid chromatography, have been investigated in high pressure
Received in revised form 27 April 2017 gas chromatography separations (carrier gas pressure up to 60 bar) and compared to silica monolithic
Accepted 2 May 2017
columns. The behavior of both silica and 80-VTMS monolithic columns was investigated using helium,
Available online xxx
nitrogen and carbon dioxide as carrier gas. The efciency of 80-VTMS monolithic columns was shown to
vary differently than silica monolithic columns according to the temperature and the carrier gas used.
Keywords:
Carrier gas nature was a signicant parameter on the retention for both silica and vinyl columns in relation
Hybrid silica monoliths
Silica monoliths
to its adsorption onto the stationary phase in such high pressure conditions. The comparison of retention
Gas chromatography and selectivity between 80-VTMS monoliths and silica was performed under helium using the logarithm
High pressure of the retention factor according to the number of carbon atoms combined to Kovats indexes. The very
good performances of these columns were demonstrated, allowing the separation of 8 compounds in less
than 1 min.
2017 Elsevier B.V. All rights reserved.

1. Introduction surface chemistry required for a specic LC application [13], the

Monolithic capillary columns result of an in-situ synthesis of
porous material inside microchannels, and organic monoliths were
introduced in separation science in the 70s as an alternative to
packed column [1]. Such organic monoliths were characterized by
a relatively simple experimental design for each of the large set
of monomers used leading to a wide variety of surface chemistry.
If these columns based on an organic backbone can also be used
in GC for even samples containing a large amount of water, their
major drawbacks were related to their low thermal stability and
their low permeability [25]. On the other side, inorganic monoliths
can also be produced based on silica (SiO2 ) [6] or transition metal
oxides such as zirconium dioxide (ZrO2 ) [7,8], or titanium diox-
ide (TiO2 ) [9,10] for separation purpose. Silica monolithic columns
have been introduced by Tanaka group in the 90s for liquid chro-
matography [11], and in comparison with organic monoliths, they
are mechanically and thermally more resistant [12]. Even if the sur-
face properties can be tuned by several ways depending on the
Corresponding author.
E-mail address: randon@univ-lyon1.fr (J. Randon).
investigation of inorganic monolith in gas separation are really few,
mainly because it requires specic instrumentation to work with
high carrier gas pressure [3,14]. Light hydrocarbon mixtures from
C1 to C6 are the main targeted applications for inorganic monolithic
columns in relation to the adsorption mechanism involved in GC for
these compounds, but the inorganic surface chemistry available up
to now was limited to silica leading to only one specic selectivity.
A new type of hybrid monolithic columns (80-VTMS: 80%
vinyltrimethoxysilane-based hybrid silica monoliths) have been
developed and manufactured in our lab and have shown multi-
ple benets over their grafts counterparts when used in reverse
phase liquid chromatography [15,16]. These columns were made of
vinyltrimethoxysilane and showed better hydrophobic properties,
and higher chemical stability than silica columns with conven-
tional methyl groups. Moreover, among a wide range of hybrid
materials synthetized, vinyl groups are good candidates to be used
later as a generic platform for further specic modications [15,16].
The behavior of these columns has been studied in high pressure
gas chromatography and compared to conventional silica columns
already used in GC [17]. The inuence on the carrier gas nature,
pressure and column temperature has been studied on retention,

http://dx.doi.org/10.1016/j.chroma.2017.05.002
0021-9673/ 2017 Elsevier B.V. All rights reserved.

Please cite this article in press as: A. Maniquet, et al., Behavior of macroporous vinyl silica and silica monolithic columns in high pressure
gas chromatography, J. Chromatogr. A (2017), http://dx.doi.org/10.1016/j.chroma.2017.05.002
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Table 1
Summary of silica and 80-VTMS monolithic columns (geometry and performances).
Column number Internal diameter Pore diameter
(SEM)/m (SEM)/m
SiO2 (M1-1) 68 1.9
SiO2 (M3-1) 70 1.9
SiO2 (M3-2) 61 1.9
80-VTMS (L1-1) 65 2.0
80-VTMS (L2-1) 67 2.0
80-VTMS (L3-1) 67 2.0
efciency and selectivity of light hydrocarbons gases on the 80-
VTMS columns.
2. Materials and methods
2.1. Chemical and reagents
Fused-silica capillaries (75 m I.D., 375 m O.D.) were
obtained from Cluzeau (France). Tetramethoxysilane (TMOS),
vinyltrimethylsiloxane (VTMS), nitric acid, formamide, methanol,
ethanol, propanol, isopropanol, isooctane and decane were pur-
chased from SigmaAldrich (France), toluene and dichloromethane
from Fisher Chemical (France), pentane and undecane from Acros
Organics (France) and octane were from Prolabo (France). All
aqueous solutions were prepared using 18 M water (Millipore,
Molsheim, France). Nitrogen and carbon dioxide were from Air
Liquide (France). Helium and sample mixtures were from Messer
(France): mix A [methane (998 ppm), ethane (970 ppm), ethylene
(994 ppm), acetylene (1019 ppm), propane (987 ppm), cyclo-
propane (1016 ppm), n-butane (989 ppm), 1-butene (989 ppm),
carbon monoxide (996 ppm), carbon dioxide (1008 ppm), n-
pentane (100 ppm), n-hexane (100 ppm), hydrogen (98.6 ppm)
in nitrogen) and mix B [hydrogen (15 mol%), carbon monox-
ide (15 mol%), carbon dioxide (15 mol%), methane (15 mol%) and
ethane (15 mol%) in nitrogen]. Propene was obtained from IFPEN
Lyon (France).
2.2. Preparation of 80-VTMS silica capillary monolithic columns
Silica monolithic columns have been prepared by sol-gel process
from tetramethoxysilane [17] while 80-VTMS columns have been
prepared from a mixture of TMOS/VTMS (20:80, w/w) according to
the previously published protocol [13,14], briey reported here. A
total of 3.2 g of this mixture was added to 1.24 g of nitric acid (1 M)
and 2.8 g of formamide and stirred at 0 C for 5 min. Then, the mix-
ture was kept at 40 C for 48 h for gelation and ageing. The mixture
was then ushed into fused-silica capillaries by applying a con-
trolled pressure using a Micro Fluidic Control System (MFCS) from
Fluigent (France). The monoliths were washed for 12 h with water
under hydrodynamic ow and dried at 100 C for 12 h. A scanning
electron microscope (SEM) Neoscope JCM-5000 from JEOL (France)
was used to measure the internal diameter of the silica capillaries
and to estimate the pore size diameter of the monoliths.
2.3. 80-VTMS and silica capillary monolithic columns
Several columns were made from different batches and their
characteristics are reported in Table 1. Columns name are rep-
resented as follow: SiO2 (M [batch number-column number])
or 80-VTMS (L [batch number-column number]). Columns were
compared in terms of internal diameter, pore diameter, length,
permeability, relative retention time of C2 over C1 (at 75 C, car-
rier gas CO2 20 bar, from mixtures A and B) and Hmin (minimum
plate height). Results were very similar when comparing differ-
ent parts of the same column and inter batch columns. This set
Please cite this article in press as: A. Maniquet, et al., Behavior of macroporous vinyl silica and silica monolithic columns in high pressure
gas chromatography, J. Chromatogr. A (2017), http://dx.doi.org/10.1016/j.chroma.2017.05.002
Length/cm Permeability B0 (tRC2 /tRC1 ) 75 C, Hmin of C2 , 75 C,
(GC)/m2 20 bar, CO2 CO2 /m
16.4 3.1 1014 1.25 15
18.6 6.3 1014 1.22 14
22.8 6.4 1014 1.23 18
35.1 5.7 1013 1.33 81
59.5 7.4 1013 1.34 99
26 3.2 1013 1.32 86
of homogenous columns from different batches has been used in
order to be sure that the reported results were representative of
silica and 80-VTMS monolithic column behaviors. With an appar-
ent pore size around 2 m, the permeability was expected to be not
far from 1013 m2 which was the permeability range observed. For
capillary columns produced with the same material, permeability
values are rather similar (standard deviation 30%). Furthermore,
permeability in porous media is also related to geometrical charac-
teristics such as connectivity, tortosity and pore circularity which is
dependant on the synthesis protocol. As a consequence, 80-VTMS
columns were ten times more permeable, less efcient than silica in
the best conditions, and the difference in surface chemistries leads
to a shift in relative retention time of ethane compared to methane.
2.4. Gas chromatography
An Agilent Technologies 7820 gas chromatograph (GC) with a
split/splitless injector and a ame ionization detector (FID) was
lent by SRA Instruments (France), and gas injection valve and high
pressure regulators have been added to the GC. Valves, tubing, fer-
rules and nuts were in stainless steel 316L from Swagelok (France).
Pressure regulators were bought from Messer (France) and Air
Liquide (France). Pressures gauges were obtained from Keller AG
(Switzerland). The injection valve for gas samples was fromVICI
Valco (Switzerland): the model used has an internal sample loop
of 0.06 L and a pressure limit of 1000 psi (69 bar). Valve actuation
was performed with helium. Liquid samples were injected at 120 C
using an on-line liquid injector which could be use at elevated pres-
sure. Split injection was designed using open capillary tubing with
controlled ow resistance based on internal diameter and length
of the capillary. The system validation and hydrodynamic char-
acterization of the chromatographic device have been reported
in a previous paper. Analysis of light hydrocarbons mixtures in
gaseous samples were conducted with an oven temperature int
the range 25 C 120 C. Retention factors have been determined
using methane as hold up time marker above 75 C (below 75 C
methane appeared slightly retained) [17].
3. Results and discussion
3.1. Inuence of the temperature and the nature of the carrier gas
on 80-VTMS column efciency in comparison with silica monoliths
Van Deemters curves of ethane from mixture B have been mea-
sured for 80-VTMS and silica monolithic columns for each carrier
gas (He, N2 and CO2 ) for inlet pressure ranging from 10 to 50 bar
and for temperature ranging from 25 C to 120 C.
Fig. 1 shows the Van Deemters curves for helium (left) and car-
bon dioxide (right) on 80-VTMS column. These curves highlight
the temperature effect on efciency of 80-VTMS columns and its
dependence on the carrier gas. The temperature effect on column
efciency appeared to be much more important with helium than
with carbon dioxide. In this case, effect of temperature on column
efciency seems to be mainly related to a decrease of the mass
transfer resistance parameter on the stationary phase when tem-
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600 400
H / m H / m
25C 350
500 50C
300

400 75C
250 25C
50C
300 200 75C
100C
100C
150
200
100
100
50
80-VTMS under helium 80-VTMS under CO2
0 0
0 5 10 15 20 25 30 0 5 10 15 20
u / cm.s-1 u / cm.s-1

Fig. 1. Van Deemter plots of ethane from mixtureB (sample pressure at1.3 bar) for temperatures from 25 C to 120 C under helium (left) and carbon dioxide (right) on
80-VTMS (L2-1)monolithic column.

H50/H120 HHe/HCO2
3 5
A : Temperature inuence B : Carrier gas inuence
4.1
4
2.1
3.6 SiO2
2 SiO2 3.4
1.8 4
80-VTMS 80-VTMS
1.6 3
2
3
1.2 1.2
1.1 2.0
2
1 1.5 1.6
2

1
1

0 0
M1-1 M3-1 M3-1 L1-1 L2-1 L3-1 M1-1 M3-1 M3-2 L1-1 L2-1 L3-1
Column number Column number

Fig. 2. H50 C /H120 C under helium (left) andHHe /HCO2 at 75 C (right) for silica and 80-VTMS monolithic columns.

Table 2
Hmin and optimal velocity for 80-VTMS (L2-1) monolithic column under different carrier gases (He, N2 and CO2 ) for different temperatures: 25, 50, 75, 100 and 120 C

Carrier gas 25 C 50 C 75 C 100 C 120 C

/Temperature

Hmin /m uopt /cm s1 Hmin /m uopt /cm s1 Hmin /m uopt /cm s1 Hmin /m uopt /cm s1 Hmin /m uopt /cm s1

He 316 6 220 8 153 10 129 11 121 13

N2 226 6 152 6 117 6 96 8 90 8
CO2 174 7 110 7 99 8 87 8 82 8

perature increases. However, whatever the carrier gas (He, N2 or
CO2 ), the minimum height equivalent to a theoretical plate was
always obtained at high temperature, with the lower value (slightly
lower than 100 m) obtained with CO2 as carrier gas (Table 1).
The effect of temperature and carrier gas nature on minimum
height equivalent to a theoretical plate has also to be compared to
the one observed on silica monoliths, and was reported on Fig. 2.
The gain in efciency according to a temperature shift from 50 C
to 120 C was rst compared under helium (Fig. 2-A). Tempera-
ture has a signicant effect on the minimum height equivalent to
a theoretical plate with helium for 80-VTMS columns (gain factor
1,8 0,3), whereas temperature has no major effect on the ef-
ciency of silica columns (gain factor 1,1 0,1). So, high temperature
has to be used for 80-VTMS columns in order to reach the maximum
efciency of the column. The effect of the carrier gas nature on ef-
ciency was also studied for silica and 80-VTMS columns (Fig. 2-B)
at an intermediate temperature of 75 C and so the ratio of Hmin
values obtained with He/CO2 was compared for both silica and
80-VTMS columns (higher is this ratio, better is carbon dioxide
compared to helium). The effect of the nature of the carrier gas
led to a substantial gain of a factor 3,7 0,4 on the efciency of
silica monolithic columns and it was less pronounced with 80-
VTMS columns with only a factor 1,7 0,3. This difference could
be explained from a much higher micro/meso-porosity on silica
compared to 80-VTMS columns leading to a more signicant pore
obstruction of micro-pore by carbon dioxide on silica. This could

Please cite this article in press as: A. Maniquet, et al., Behavior of macroporous vinyl silica and silica monolithic columns in high pressure
gas chromatography, J. Chromatogr. A (2017), http://dx.doi.org/10.1016/j.chroma.2017.05.002
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kN2 or CO2/kHe
1 He

0.9 N2 - 120C

0.8

0.7 CO2 - 120C

0.6 N2 - 75C

0.5

0.4 CO2 - 75C

0.3

0.2

0.1
0 5 10 15 20 25 30 35

P / bar

Fig. 3. kN2 /kHe and kCO2 /kHe for ethane from mixture B (sample pressure 1 bar) versus P at 75 C and 120 C on column 80-VTMS (L3-1).

lead to a lower mass transfer resistance and as a consequence to Table 3

Kovats retention indexes for several compounds under helium on SiO2 (M3-1) and
a lower minimum height equivalent to a theoretical plate. Nitro-
80-VTMS (L3-1) columns at 120 C.
gen acts as an intermediary carrier gas between helium and carbon
dioxide on efciency as reported in Table 2 with Hmin and uopt for SiO2 (M3-1) 80-VTMS (L3-1)
80-VTMS monolithic column for different carrier gases and several Ethylene 210 200
temperatures. Propene 325 300
Silica based columns are very efcient (more than 10 000 plates 1-butene 436 400
Acetylene 300 200
per meter) compared to the value reported in literature and could
Cyclopropane 348 339
be appropriate stationary phases for the analysis of highly volatile Dichloromethane 638 555
compounds. Concerning 80-VTMS columns, they reach their max- Toluene 852 800
imum efciency at elevated temperature and so would be more Methanol 941 555
Ethanol 1026 651
appropriate for analysis of heavier compounds. For both silica and
80-VTMS columns, best efciencies are reach when carbon dioxide
is used as carrier gas, with a signicant inuence on silica columns
as highlighted in Fig. 2 leading to more than 60 000 plates per meter. due to a lower adsorption of carrier gas molecules on the monolithic
surface.

3.2. Inuence of the temperature and nature of the carrier gas on 3.3. Comparison of the retention and selectivity of monolithic
80-VTMS columns retention columns in silica and 80-VTMS

The inuence for various carrier gas on the retention and selec-
tivity was previously reported on several monolithic columns
[2,3,14,1726] in high pressure gas chromatography but appeared
to be stationary phase dependent. Such behavior was here inves-
tigated on 80-VTMS columns for C2 at different temperatures and
pressures using helium, nitrogen and carbon dioxide as carrier gas
(see ref 15 for silica columns). When helium was used as a carrier
gas, helium pressure had no inuence on retention factor what-
ever the temperature, so these retention factors can be used as
a reference for other carrier gases (nitrogen and carbon dioxide).
Relative retention factors were plotted on Fig. 3 where retention
factors using nitrogen and carbon dioxide were normalized over
the retention factor observed with helium at the same temper-
atures. Whatever the oven temperature, retention factor of light
hydrocarbons decreased when nitrogen or carbon dioxide pressure
increased. The molecules of the carrier gas being adsorbed on the
stationary phase surface reduced the number of available adsorp-
tion sites accessible for analyte molecules leading to a decrease
of the apparent retention factor. Such reduction of the number of
available sites for analyte molecules is less important when the
temperature increases or when the carrier gas pressure decreases
In order to study the inuence of vinyl groups on the retention
and selectivity of 80-VTMS columns, compared to silica columns,
the logarithm of the retention factor of several liquid and gaseous
compounds was plotted versus the number of carbon atoms for SiO2
and 80-VTMS columns (Fig. 4). These analysis have been performed
under helium to avoid the effect of the carrier gas pressure on reten-
tion and at 120 C allowing methane to be monitored as the holdup
time marker [3]. Kovats retention indexes have been reported in
Table 3 to compare in an easier way the change in retention and
selectivity between the two stationary phases.
Retention of linear alkanes increased from silica to 80-VTMS
columns, and such phenomenon could be related to the vinyl
groups which enhance the surface hydrophobicity or to a larger
surface area of the stationary phase. So both silica and 80-VTMS
columns have been synthesised as macro monoliths (6 mm diam-
eter, 2 cm height) and their specic surface areas were measured.
The specic surface area of silica columns (550 m2 g1 ) was higher
than for 80-VTMS columns (159 m2 g1 ). Assuming the same spe-
cic surface area ratio in capillary columns, the higher alkane
retention on 80-VTMS columns, despite lower surface of adsorp-
tion, appeared to be related to the more hydrophobic vinyl groups.

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3.0
log(k) SiO2

2.5 Alkanes Alkenes Acetylene Alcohols Aromac rings Dichloromethane

C11H24
2.0
C2H5OH C10H22
C9H20
1.5 CH3OH Cyclo-C7H8
C8H18
1.0 C7H16
CH2Cl2
C6H14
0.5
C5H12
C4 H 8
0.0 Cyclo-C3H6
0 1 2
C3 H 6 3 4 C4H10 5 6 7 8 9 10 11 12
C2 H 2
-0.5 C3 H 8
C2 H 4
C2 H 6
-1.0
Carbon number
3.0
log(k)
80-VTMS C11H24
2.5
C10H22

2.0 C9H20
Cyclo-C7H8 C8H18
1.5 C3H7OH
C7H16
C2H5OH
1.0
C6H14
CH3OH
C5H12
CH2Cl2
0.5
C4H8
Cyclo-C3H6 C4H10
0.0
0 1 2 3 CH 4 5 6 7 8 9 10 11 12
3 8
C3H6
-0.5
C2H 2 C2 H 6
C2H 4
-1.0
Carbon number

Fig. 4. Log(k) versus the number of carbon atoms under helium on SiO2 (M3-1) and 80-VTMS (L3-1) columns at 120 C.

Concomitantly, alkene retention increased but with a lower
extend compared to alkanes so their Kovats indexes decreased,
even leading to a co-elution between ethylene and ethane, propene
and propane, and 1-butene and butane at 120 C. Acetylene
Kovats index decreased more signicantly (IK 100) compared
to alkenes (IK 20-50). Acetylene which was clearly separated
to other C2 compounds on silica, now appeared closer to ethane
and ethene. This phenomenon was similar to all groups of alkanes
and alkenes with the same number of carbon atoms which formed
clusters on 80-VTMS columns, as display on chromatograms per-
formed at 25 C (Fig. 5) with a shift in peak positions also observed
for butane and butene.
Kovats indexes of alcohols decreased dramatically on 80-VTMS
columns. And more interestingly, alcohols which showed a strong
peak asymmetry on silica columns due to the presence of silanol
groups on the surface, appeared with more symmetric shape on
80-VTMS columns probably due to a reduced number of residual
silanol groups on the surface. For another polar compound such
as dichloromethane, retention also decreased as Kovats indexes
varied from 638 to 555.
4. Conclusion
Characterization of several silica and 80-VTMS monolithic
capillary columns has conrmed the good repeatability and repro-
ducibility for intra-batch columns which reach efciency at the
optimum velocity in the order to 60 000 plates per meter for silica.
Differences of efciency between the two types of columns were
dependent of temperature and nature of carrier gas. The inuence
of the nature of the carrier gas on efciency revealed a gain by a fac-
tor 4 on silica columns and a factor 2 and 80-VTMS columns when
CO2 was used instead of He. The adsorption of CO2 on the station-
ary phase plays also an important role on the retention whatever
the column type used, leading to a strong reduction of retention

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FID response /pA C2 SiO2

4.0
Mthane Ethane
3.5 C3
Ethylne
3.0
Propane
2.5 C4
Actylne
2.0 Cyclopropane

1.5 n-butane

1.0 1-butne
0.5
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Time /min
14
Mthane
12 Ethane / C2
Ethylne 80-VTMS
10

8 Actylne
C3
6

4
Propane Cyclopropane C4

2 n-butane 1-butne

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Time /min

Fig. 5. Chromatogram of mixture A at 20 bar and 25 C using CO2 as carrier gas on silica and 80-VTMS columns.

when carrier gas pressure increased. Temperature effects, from 50
to 120 C, are negligible on silica columns and allow a substantial
gain (factor 2) on 80-VTMS columns. The difference of selectivity
between the two stationary phases has shown the formation of
clusters according to their number of carbon atoms on 80-VTMS
columns. These columns are complementary and allow fast analysis
of a wide range of volatile and rather apolar compounds.
Acknowledgments
The authors are grateful to SRA Instruments for providing the
conventional GC and installing the injection valve. They also thank
Tiffany Vittori and Mikal Aksoy for conducting preliminary tests
during their internships.
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Please cite this article in press as: A. Maniquet, et al., Behavior of macroporous vinyl silica and silica monolithic columns in high pressure
gas chromatography, J. Chromatogr. A (2017), http://dx.doi.org/10.1016/j.chroma.2017.05.002