J Sol-Gel Sci Technol (2008) 48:11–17

DOI 10.1007/s10971-008-1742-z

ORIGINAL PAPER

Structure of hybrid organic–inorganic sols for the preparation

of hydrothermally stable membranes
Hessel L. Castricum Æ Ashima Sah Æ Jan A. J. Geenevasen Æ Robert Kreiter Æ
Dave H. A. Blank Æ Jaap F. Vente Æ Johan E. ten Elshof

Received: 3 February 2008 / Accepted: 27 March 2008 / Published online: 16 April 2008
Ó The Author(s) 2008

Abstract A procedure for the preparation of hybrid sols Keywords Silica
Organic–inorganic hybrid

for the synthesis of organic–inorganic microporous mate- Membrane
Microporous
Polymeric sol

rials and thin film membranes is reported. We describe Hydrothermal stability
silane reactivity and sol structure for acid-catalysed col-
loidal sols from mixtures of either tetraethylorthosilicate
(TEOS) and methyltriethoxysilane (MTES), or bis(trieth- 1 Introduction
oxysilyl)ethane (BTESE) and MTES. Early-stage
hydrolysis and condensation rates of the individual silane Microporous materials are of interest for a vast range of
precursors were followed with 29Si liquid NMR and applications, including adsorption, fine chemical synthesis,
structural characteristics of more developed sols were oil refining and molecular sieving (e.g. desiccation). Sol–
studied with Dynamic Light Scattering. Condensation was gel synthesis has proven to be a highly versatile technique
found to proceed at more or less similar rates for the dif- for the preparation of high-purity microporous materials
ferent precursors. Homogeneously mixed hybrid colloids with well-controlled physical and chemical properties [1–
can therefore be formed from precursor mixtures. The 5]. The applicability of sol–gel synthesis is especially
conditions of preparation under which clear sols with low apparent in functional materials, such as the ultra-thin
viscosity could be formed from BTESE/MTES were coatings that can be used as molecular sieving membranes.
determined. These sols were synthesised at moderate Molecular separations based on membrane technology
water/silane and acid/silane ratios and could be applied for are generally accepted as highly promising alternatives to
the coating of defect-free microporous membranes for existing technologies [4–11]. These separations are cur-
molecular separations under hydrothermal conditions. rently performed using (cryogenic) distillation or
adsorption-based techniques, but their exergy efficiency is
in general as low as 10%. At the same time, they are
responsible for an estimated 40% of the total energy con-
sumption in the (petro)chemical industry worldwide, i.e.
H. L. Castricum
A. Sah
D. H. A. Blank
J. E. ten Elshof (&)
more than 10 billion barrels of oil equivalent per year.
MESA+ Institute for Nanotechnology, University of Twente,
P.O. Box 217, 7500 AE Enschede, The Netherlands Unreliable long-term performance under industrial condi-
e-mail: j.e.tenelshof@utwente.nl tions is the main factor that has hampered actual
implementation of membrane technology in molecular
H. L. Castricum (&)
J. A. J. Geenevasen
separation processes [12]. Various research groups have
Van‘t Hoff Institute for Molecular Sciences, University
of Amsterdam, Nieuwe Achtergracht 166, 1018 WV studied membranes consisting of microporous amorphous
Amsterdam, The Netherlands silica which are prepared by sol–gel technology. These
e-mail: castric@science.uva.nl membranes show good performance in gas separation and
pervaporation applications and have a high thermal,
R. Kreiter
J. F. Vente
Energy Research Centre of the Netherlands, Postbus 1, mechanical and solvolytical stability [4, 5, 13]. However,
1755 ZG Petten, The Netherlands the hydrothermal stability of pure silica is too low to ensure

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12 J Sol-Gel Sci Technol (2008) 48:11–17

a reliable industrial application [14, 15], in the presence of studied the sol structure from which the most promising
water, even at moderate temperatures. The best results up organic–inorganic membranes are prepared, i.e. methylated
to now have been obtained with silica materials in with part silica [16, 23] and hybrid silica [12]. A combination of 29Si
of the non-binding silanol groups have been replaced by NMR and Dynamic Light Scattering was applied to char-
non-binding organic group. The so-called ‘methylated’ acterise both the early stage of synthesis and more
silica membranes are prepared from a mixture of developed sols, including the final sol that can be used for
tetraethylorthosilicate (TEOS) and methyltriethoxysilane membrane preparation. This allowed us to review existing
(MTES). Their stability is high enough to apply them up recipes for sol preparation, thereby focusing on the effect
to an operating temperature of 95 °C in the dehydration of of a prehydrolysis step prior to mixing. We investigated
n-butanol [16]. Recently, it was shown that the replacement whether the reactivities of the silane precursors indeed
of siloxane bonds by binding organic linkers can lead to a substantiate the assumptions made for the preparation of
membrane that can function stably up to 150 °C [12]. homogenously mixed methylated materials [17, 23]. Based
This new hybrid material is prepared from a combination on this, we attempted to predict whether there are oppor-
of an organically linked precursor, such as bis(triethoxy- tunities to further improve the structure and hydrothermal
silyl)ethane (BTESE), and methyltriethoxysilane (MTES). stability of these materials. We also used our findings for
The high hydrothermal and structural stability have opened the optimization of a hybrid material based on a mixture of
up the route towards practical industrial application of BTESE and MTES precursors. For the latter mixture, we
membrane technology in energy intensive separations. explored the influence of various preparation parameters on
Knowledge about the reactivity of the precursors is an the colloid size of the sol. Our results on both the reactivity
important element for the preparation of homogeneous sol of the individual components and the structure of the
recipes. Initial stages of acid-catalysed hydrolysis have homogeneous mixtures thereof can be used to further
been studied by various authors [17–20]. Higher reaction expand the potential of organic–inorganic materials for
rates have been observed with increasing water content and adsorption and molecular sieving applications.
acidity. Van Bommel et al. [17] found higher hydrolysis
and condensation rates for MTES than for TEOS. Still,
MTES was not reported to show a shorter gelation time, 2 Experimental
which is probably due to the fact that number of reactive
groups has been reduced from four in TEOS to three in Tetraethylorthosilicate (TEOS, 99.999% pure), methyltri-
MTES. Hook et al. [21] also observed an initially three ethoxysilane (MTES, 99% pure), 1,2-bis(triethoxysilyl)
times faster condensation for MTES, but found an equal ethane (BTESE, 96% pure) and dry ethanol were all obtained
extent of condensation in a later stage. The hydrolysis and from Aldrich. These chemicals were used as received. Only
initial stage of dimerisation were thoroughly studied for BTESE was distilled before use to increase purity. Sols were
acid-catalysed TEOS and MTES [20]. Again a faster prepared by the dilution of silanes in dry ethanol at 0 °C,
hydrolysis rate for MTES was observed. The rate of dimer followed by the addition of diluted nitric acid (65 wt.%,
formation was however higher for TEOS. The formation of Aldrich). The nitric acid was added drop-wise to the diluted
random copolymers originating from TEOS/MTES mix- precursor under vigorous stirring. The sol was then refluxed
tures was observed with 29Si NMR [19, 20] and 17O NMR in a water bath at 333 K under continuous stirring. For
[22]. The observations of Van Bommel [17] have led to the BTESE/MTES mixtures, half of the water was added after
introduction of a prehydrolysis stage for the synthesis of 1.5 h of refluxing. This was done after placing the sol in an
TEOS/MTES-based membrane materials. Other studies ice bath and thermal equilibration. Subsequently, the sol was
[19, 20, 22] thus suggest that such a procedure is not again placed in a water bath at 333 K.
strictly required. To the best of our knowledge, no com- In situ 29Si Nuclear Magnetic Resonance spectra were
parative study on the hydrolysis and condensation kinetics obtained from the sols from the individual precursors
has yet been published for BTESE. immediately after mixing with nitric acid and water. Syn-
Here, we report a study on the sol–gel hydrolysis and thesis was carried out under water-lean conditions at
condensation reactions, and colloid formation in sol syn- [Si] = 1.8 M, ra ([H+]:[silane]) = 0.1 and rw ([H2O]:
thesis using TEOS, MTES, and BTESE as precursors. [-OEt]) = 0.25 at a temperature of 273 K. NMR spectra
Based on the common recipes for silica-based membranes, were acquired on a Bruker 500 MHz NMR and referenced
HNO3 was used as a catalyst. In the above-mentioned to tetramethylsilane. The pulse duration was 10 ls
studies, HCl was applied. Hydrolysis and condensation of (*45°pulse), and the repetition rate 2.5 s. Tris(acetyl-
the different silane precursors were carried out under acetonato)chromium(III) (0.1 wt.%) was added to increase
identical reaction conditions, i.e. with the same [Si] con- the demagnetization rate of the silicon nucleus. Hydrolysis
centration, and [H+]:[Si] and [H2O]:[Si] ratios. We also was observed as a *1–2 ppm downfield shift of the signal,

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J Sol-Gel Sci Technol (2008) 48:11–17 13

and condensation (Si–O–Si bond formation) by a of the Si atom, with the result that BTESE hydrolyses at a
*10 ppm upfield shift [17, 19]. Post-synthesis analyses of lower rate than MTES.
well-developed BTESE/MTES sols and TEOS sols were The condensation rates of the three silanes differ ini-
similarly carried out at 273 K. tially, as can be recognised from the different slopes at
The hydrodynamic diameters of the colloids in the t = 0 s (Fig. 1). At this point, there is hardly any con-
freshly prepared sols were determined in a 25% dilution in nectivity (number of bonds between the moieties). The
ethanol by Dynamic Light Scattering at 298 K in a Mal- condensation rates became similar even before the average
vern Zetasizer Nano. From the Brownian motion of the degree of condensation was such that one of the reactive
particles in the solvent defined by the translational diffu- groups had formed a bond with another moiety. At this
sion coefficient D, the hydrodynamic diameter d was stage, observable from the similar slopes in Fig. 1 at about
obtained by the Stokes-Einstein equation: d = kT/3pgD, t = 10 ks, the degree of condensation (Si–O–Si bond for-
with k Boltzmann’s constant, T the temperature, and g the mation) in polymerising MTES is only about 30% higher
viscosity of the solvent. than in polymerising TEOS. A similar difference was
found between MTES and BTESE (per silicon atom).
Again, the higher condensation rate of MTES can be
3 Results and discussion explained by the electron donating influence of the –CHx
groups on the Si atom. This promotes the formation of the
3.1 Hydrolysis and condensation rates positively charged Si–OH+2 transition state, which results in
faster condensation. However, the faster hydrolysis rate of
The hydrolysis and condensation rates of TEOS, MTES MTES has a moderating effect, which is caused by the less
and BTESE were determined by in situ 29Si solution NMR. electron-donating influence of the hydroxy-groups as
The collection of NMR data is hindered by the low compared to alkoxy. For the somewhat lower condensation
abundancy of the 29Si nucleus and its very slow demag- rate of BTESE, as compared to MTES, a similar reasoning
netization. For this reason the reaction kinetics were holds as for hydrolysis. Although Si in BTESE and MTES
slowed down and determined at low temperature (273 K) are chemically almost identical, the faster condensation
under water-lean conditions. In addition, we added a small kinetics of MTES as compared to BTESE is probably
amount of Cr(III), which allowed us to increase the pulse related to steric effects due to its (twice) smaller size as
rate with a factor of 50 and obtain sufficient signal-to-noise well as to electronic effects. The total of these effects was
ratio. found to result in a similar condensation rate as for TEOS,
Substantial differences in the initial hydrolysis rates within experimental error.
were found (Table 1). This is in correspondence to earlier Dynamic Light Scattering (DLS) carried out on sols
work that reported faster hydrolysis of MTES than TEOS prepared under the same conditions revealed very small
by up to an order of magnitude [17, 21]. This was the particles, near the lower limit of detection of the technique
primary motivation for prehydrolysing TEOS prior to the (0.6 nm). A relationship between colloid size and degree of
addition of MTES in the preparation of sols for methylated condensation is shown in Fig. 2. The larger size for BTESE
silica membranes [23]. The electron-donating influence sols at a similar degree of condensation can be related to
of –CHx onto the Si atom is larger than that of –OR. This monomer size, which is about two times larger for BTESE.
enhances the proton-catalysed hydrolysis reaction, which It becomes clear from these results that the condensation
involves complexation with the proton and subsequent loss
of an alkoxygroup in the form of an alcohol. The hydrolysis
rate increases from TEOS to BTESE to MTES. The elec-
tron-donating influence of –CH2–CH2– is slightly smaller
than that of –CH3, and the more bulky structure of BTESE
may result in sterical hindrance and decreased accessibility

Table 1 Hydrolysis rates of three silane precursors, measured at

[Si] = 1.8 M, ra = 0.1 and rw = 0.25 at 273 K
Silane Rate 9 103 (OH/Si, s-1)

TEOS 0.11
MTES 1.2
BTESE 0.42 Fig. 1 Degree of condensation for three silanes (TEOS, MTES and
BTESE) measured at [Si] = 1.8 M, ra = 0.1 and rw = 0.25 at 273 K

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14 J Sol-Gel Sci Technol (2008) 48:11–17

1.4 than in the most developed TEOS sols investigated in the

BTESE
1.2
previous section. At the moment that MTES is added, a
mean colloid size (nm)

substantial number of bonds have thus already been

1
TEOS formed, even for the less developed sol that was prepared
0.8
via the 2-step route. The high degree of condensation is
MTES clearly related to the much higher synthesis temperature as
0.6 compared to the temperature of 273 K applied in Sect. 3.1.
0.4
If MTES had been added at the beginning of the process,
the condensation rates of TEOS and MTES would have
0.2 been comparable after similar preparation times. After
0
addition of MTES and further synthesis, Gel Permeation
0 0.2 0.4 0.6 0.8 1 1.2 Chromatography [16] had indicated a bimodal colloid size
# Si-O-Si per Si distribution for the one-step procedure, while a more
homogeneous size distribution was found for sols prepared
Fig. 2 Colloid sizes found with DLS after 1, 3, 6 and 24 h of
synthesis compared to the degree of condensation determined with following the two-step procedure. Hence, the 1-step pro-
29
Si NMR ([Si] = 1.8 M, ra = 0.1 and rw = 0.25 at 273 K) cedure results in a well-connected structure that does not
fully allow the mixture to develop into a homogeneous
rates of all three monomers are more or less similar at the copolymeric structure. Interestingly, despite the large dif-
lowest particle size near the limit of detection of DLS. ferences between the sols prior to MTES addition, very
little difference in performance and longevity were found
3.2 Methylated silica between membranes prepared following the two routes for
sol synthesis.
A prehydrolysis step has been included in synthesis pro- After coating and thermal treatment, the total degree
cedures for the preparation of methylated silica membranes of condensation of the TEOS/MTES materials is higher
[16, 23]. Selective membranes have been prepared from than 3 [16]. The degree of condensation is higher for the
sols following two different routes. The ‘one-step’ route TEOS monomers (Q) than for the MTES moieties (T) in
includes 165 min of TEOS hydrolysis at 333 K under the 1-step procedure (Table 2). A better connected TEOS
water-rich and highly acidic conditions, with molar ratios structure has thus been formed in the 1-step method, but at
TEOS:C2H5OH:HNO3:H2O = 1:3.8:0.085:6.5 [16, 23]. the expense of the MTES-connectivity. However, the dif-
The ‘two-step’ route involves 90 min of TEOS prehydro- ferences are small. It was shown in the previous section
lysis at 333 K under less water-rich conditions and at that a degree of condensation of 1 is sufficient to obtain
higher pH, with a molar ratio TEOS:C2H5OH:HNO3: similar condensation rates. The most important factor that
H2O = 1:3.8:0.0036:2.0 [16]. After the prehydrolysis determines the degree of mixing of two silane precursors is
stage, MTES is added in both synthesis schemes, and in the their relative rate of condensation during the interval in
2-step procedure also water/acid is added. We studied which most bonds are formed. This also explains why
the sol structure resulting from these two procedures after various authors found that a random copolymeric structure
the first stage, i.e. just before the addition of MTES. could be formed from TEOS/MTES mixtures [19, 20, 22],
As can be seen from the results in Table 2, the differ- despite the differences in initial reactivity. In the 2-step
ence between the two sols is substantial. The 1-step procedure, most bonds are formed after MTES addition, so
procedure resulted in sols with better connected moieties that a homogenous structure can still develop. In the 1-step
and larger colloid size than the 2-step procedure. Even procedure, fewer connections remain to be formed after
more important is that the number of bonds is much greater MTES addition, but some re-arrangements may take place

Table 2 Sol structure at the end of the TEOS prehydrolysis stage and connectivity of thermally consolidated gels from recipes for the
preparation of methylated materials [16, 23]
Sol recipe Sol (prior to MTES addition) Gel (after calcination)
Mean dcolloid (nm) Condensation degree (Si–O–Si per Si)
Q Q T

1 step 6.5 2.8 3.65 2.51

2 step 1.2 1.8 3.35 2.64
29 29
The connectivity of the sols was determined with liquid Si NMR and that of the gels with Si MAS-NMR [16]

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J Sol-Gel Sci Technol (2008) 48:11–17 15

due to thermally-induced breaking and re-creation of Our observations in Sect. 3.1 show that the condensa-
Si–O–Si bonds. This could explain why very few differ- tion rates of TEOS and MTES differ as much as those of
ences have been observed between membrane materials BTESE and MTES. As we found that a statistically random
prepared according to these two procedures. A high degree copolymer can be formed from TEOS/MTES upon full
of homogeneity has even been found for MTES/TEOS gels condensation, this should also hold for BTESE/MTES.
after the 1-step route [24]. This also means that auto-condensation of BTESE is sup-
Considering the high degree of condensation of TEOS pressed by addition of MTES. In view of our findings for
moieties before MTES addition, attained even with the TEOS/MTES, we considered that a prehydrolysis step prior
‘2-step’ route, it can be argued that a more homogeneous to addition of the second silane is not strictly required.
mixture and random organic-inorganic copolymeric struc- Similar as for TEOS/MTES, the condensation rates of
ture would be obtained without a prehydrolysis stage. High MTES and BTESE differ only in the earliest stage during
MTES concentrations were found to result in mesoporous which very few connections are made, and most of the
‘defects’ in membranes and no selective membranes have yet network is formed at roughly equal condensation rates. We
been prepared with an MTES concentration exceeding found that this procedure resulted in the synthesis of a
50 mol% [16, 23]. In fact, membranes with 50% MTES were hybrid material with an open microporous structure, no
somewhat less selective towards the transport of small mesopores, and good molecular separation ability [12]. The
molecules than purely inorganic membranes [23]. Meso- separation performance, defined as flux times selectivity,
pores of around 2 nm, which may act as defects depending on was even better than for methylated silica membranes.
the application in which the membrane is used, have also A good indication of the structural development of sols
been observed in unsupported gels prepared from MTES- from mixtures of BTESE and MTES was obtained with
rich mixtures. These mesopores were suggested to be related Dynamic Light Scattering (DLS). Figure 3 shows the col-
to phase separation into hydrophobic (methyl-rich) and loid size distribution as a function of reaction time for a
hydrophilic (methyl-lean) regions [24]. Our present findings mixture with rw = 0.5. Water-lean conditions were
suggest that the structure of methylated silica sols may be employed in the first stage of synthesis to limit fast (exo-
improved by mixing the silanes at an earlier moment or by thermic) hydrolysis. A second water addition step was
even completely omitting the prehydrolysis stage. However, required to allow full development of the colloids. A sharp
as an upper limit of 50% MTES has also been observed on increase in growth rate was observed after addition of
defect-free membrane materials that had been made by a water at t = 90 min. The growth rate was found to be
procedure that did not include TEOS prehydrolysis [25], related to the total amount of water added to the sample.
further improvements will likely require careful tuning of the
recipe and thorough sol characterisation.

3.3 Hybrid silica

The high hydrothermal stability of microporous membrane

materials prepared from BTESE/MTES mixtures is related
to the high fracture resistance of BTESE-based materials
Intensity

[12]. This is also advantageous for the preparation of crack-

and defect-free thin layers. Our motivation for working with
a mixture of BTESE and MTES instead of with pure
BTESE was twofold. The first reason was that the incor-
poration of methyl groups would help to ‘shield’ the
siloxane bonds from water, similar as in TEOS/MTES- 0
based materials [16], making them even less sensitive 1
2
towards hydrolysis. The second reason was related to the
3 500
Co

extensive formation of cyclic carbosiloxane structures from

llo

4 400
id

bridged silanes that has been reported [26]. These structures 5 300
siz

reduce the level of functionality and do not contribute to 3D )

e

6 200
mi n
(n

network formation. Our hypothesis was that the addition of e(

m

7 100
Tim
)

MTES would lower the statistical chance of formation of

0
inert cyclic structures and lead to a more open porous
structure. In a similar way, larger pore volumes have been Fig. 3 Colloid size distribution plotted against reflux time for a sol
observed upon the addition of MTES to TEOS [24]. from a BTESE/MTES mixture with rw = 0.5

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16 J Sol-Gel Sci Technol (2008) 48:11–17

Quantitative 29Si NMR analyses of the overall conden- 18

sation rate could not be carried out on sols from mixtures of 16

BTESE and MTES, because of extensive overlap of peaks.

mean colloid size (nm)

14
However, we could observe the effect of the second water rw = 2
12
addition step for a mixture with a (final) rw of 0.5. While
10
uncondensed Si species (T0) were still present after 90 min
of refluxing, we observed the complete disappearance of 8

these species within minutes after the second addition of 6

water (Fig. 4). At the same time, the downfield components 4
of dimers (T1) and trimers (T2) became more prominent,
2 r w = 0.5
indicating hydrolysis of these units. Thus, the reactivity
0
towards further condensation increased strongly upon 0.0001 0.001 0.01 0.1 1
addition of more water by the presence of more –OH +
[H ] : [Si]
groups. A concomitant discontinuity in colloid size
development was observed with DLS between 90 and Fig. 5 Mean colloid sizes determined by averaging over the popu-
95 min (Fig. 3). Thus, by limiting the availability of water lation according to scattering intensity. Sols were prepared from
BTESE and MTES with total [Si] = 1.8 M, after 3 h reflux at 333 K
in an early stage, the (co)polymeric structure develops and addition of half of the total amount of water at rw = 1 (unless
more gradually. At a later stage, the size of the sol particles otherwise indicated) after 90 minutes
can be further tuned by adjusting the total amount of added
water. After addition, water rapidly hydrolysed remaining Brittle gels formed under the latter two conditions in case
ethoxy groups, which resulted in an increased reactivity all water was supplied at once. Thin continuous defect-free
towards condensation and faster growth of the colloids. films could be synthesised (Fig. 6) from low viscosity sols
Larger colloids were observed not only after longer with colloid sizes around the pore size of the support
reaction times and higher values of rw, but it was also (5 nm), and applied as molecular sieving membranes [12].
possible to tailor the colloid size by increasing ra. Recipes Figure 6 shows that a limited spread exists in the appli-
covering a range of acid and water concentrations were cable concentration ranges, which are basically centered
studied to define the range in which suitable sols can be around ra = 0.1 and rw = 1. We expect that a large class of
prepared. Clear sols were obtained from all investigated other microporous materials and thin films can be designed
BTESE/MTES mixtures, whereas acid-catalysed hydroly- with similar methods as described here.
sis and condensation of pure MTES eventually resulted in
the formation of precipitates. Hence, the clear sols were
another indication for the formation of a truly copolymeric 4 Conclusions
structure. The mean sol colloid sizes of all studied recipes
are shown in Fig. 5. Low viscosity sols were formed at The initial hydrolysis and condensation rates of tetra-
ra B 0.1 and rw B 1. More viscous sols were found for ethylorthosilicate, methyltriethoxysilane and bis(triethoxy-
sols with ra = 0.32 and rw = 1, and ra = 0.1 and rw = 2. silyl)ethane under acidic conditions were determined with

Fig. 4 29Si NMR patterns of a

BTESE/MTES sol with
rw = 0.5 after a reflux time of
90 and 95 minutes (after water
addition). Arrows highlight the
vanished T0 peaks and the
increased downfield
contributions of T1 and T2
regions that indicate more
extensive hydrolysis. As the T0,
T1 and T2 spectral regions of the
two individual silanes show
some overlap, a rough
indication of the regions is
given below the figure

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J Sol-Gel Sci Technol (2008) 48:11–17 17

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