Journal of Membrane Science 345 (2009) 267–275

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Journal of Membrane Science

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Permeation properties and hydrothermal stability of silica–titania membranes

supported on porous alumina substrates
Yunfeng Gu 1 , S. Ted Oyama ∗
Environmental Catalysis and Nanomaterials Lab, Department of Chemical Engineering, Virginia Polytechnic Institute & State University, Blacksburg, VA 24061, United States

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

Article history: A hydrothermally stable and H2 -selective composite membrane was successfully prepared on a
Received 25 June 2009 mesoporous alumina support by thermal decomposition of titanium isopropoxide (TIP) and tetraethy-
Received in revised form 28 August 2009 lorthosilicate (TEOS) at high temperature. The membrane with a H2 -selective silica–titania top layer of
Accepted 3 September 2009
10–20 nm in thickness had a H2 permeance 3 × 10−7 mol m−2 s−1 Pa−1 and a H2 selectivity over CH4 and
Available online 10 September 2009
CO2 in the range of 40–60. After 130 h exposure in 75 mol% H2 O at 923 K, the H2 permeance was reduced by
only 30%, compared to a pure silica membrane which suffered a loss of 90%. The use of the opposing reac-
Keywords:
tants technique improved the quality of the composite membrane. Although considerable more efforts
Hydrogen separation
Composite membrane
are needed to increase surface area, the stability properties suggest applicability of the composition at
Titania high temperature in the presence of high concentrations of steam.
Silica © 2009 Elsevier B.V. All rights reserved.
CVD
Hydrothermal stability

1. Introduction cations in membrane reactors for reactions that utilize or generate

Silica membranes have attracted considerable attention in the
past for their selective hydrogen permeation properties [1–7].
However, the instability of silica materials limits their applica-
tions such as in high temperature membrane reactors, especially
in the presence of steam. Prolonged exposure of these materials to
water vapor at elevated temperatures causes rapid densification,
and changes to the pore structure lead to reduced permeability of
the membranes. For example, Sea et al. reported that the H2 per-
meance of a silica membrane prepared on a mesoporous ␥-alumina
support by chemical vapor deposition (CVD) underwent a reduc-
tion of 90% from 3.5 × 10−7 to 4.0 × 10−8 mol m−2 s−1 Pa−1 by an
exposure to 50 mol% water vapor at 673 K for 100 h [8]. Tsuru et
al. found that the permeances of H2 and He for a sol–gel derived
silica membrane decreased by 65% and 40% after treatment for 9 h
at 773 K and 50 kPa of steam partial pressure (50 mol%) [9]. Con-
siderate efforts have been made to improve the stability of silica
membranes including incorporation of methyl groups in the silica
microstructure [10], calcination of silica membranes in steam [11],
and combination of SiO2 with other oxides such as Al2 O3 , MgO,
ZrO2 , Co3 O4 , NiO, and Nb2 O5 [12–18]. This has led to some appli-
∗ Corresponding author. Tel.: +1 540 231 5309; fax: +1 540 231 5022.
E-mail addresses: guy@corning.com (Y. Gu), oyama@vt.edu (S.T. Oyama).
1
Present address: Corning Incorporated, Science and Technology Division, SP-FR-
03, Corning, NY 14831, United States.
steam [19–22].
The addition of TiO2 to SiO2 films produces composite oxides
of better mechanical and optical stability as well as a wider
range of achievable refractive index due to the large difference in
refractive index between SiO2 (∼1.45) and TiO2 (∼2.55) [23,24].
In the TiO2 –SiO2 glass system, the replacement of SiO2 by TiO2
decreases the activation energy for helium diffusion and perme-
ation, explained to occur from reduction in the average strain
energy necessary to distort the R–O–R bond in the glass structure
[25]. Some research has been carried out on TiO2 modified SiO2
composites to obtain membranes with better permeation perfor-
mance. For example, de Lange et al. [26] used a binary SiO2 /TiO2
(10 mol% TiO2 ) sol to prepare microporous TiO2 –SiO2 membranes
on a mesoporous alumina support. The resulting composite mem-
brane showed a high H2 selectivity over CH4 of 160 with a H2
permeance of 1 × 10−7 mol m−2 s−1 Pa−1 at 473 K, while similar
sol–gel derived silica membranes without Ti had a H2 /CH4 selec-
tivity of 18 and a H2 permeance of 5.2 × 10−7 mol m−2 s−1 Pa−1
at the same temperature. Nam et al. deposited a H2 -selective
layer of TiO2 –SiO2 on the inner surface of porous Vycor glass
tubes with a mean pore diameter of 4 nm by decomposition of
tetraisopropyltitanate (TIPT) and tetraethylorthosilicate (TEOS) in
the presence of O2 at atmospheric pressure [27]. Using a molar
ratio of TIPT/TEOS of 1.2, the obtained composite membranes
showed high selectivities of around 900 but with low permeances
of 1.8 × 10−8 mol m−2 s−1 Pa−1 at 873 K. The low permeance was
the result of the intrinsic low permeability of Vycor glass.

0376-7388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2009.09.009
268 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275
In this study, TiO2 modified SiO2 composite membranes were
prepared on mesoporous ␥-alumina supports by employing a
multielement CVD technique with titanium isopropoxide (TIP)
and TEOS as precursors at high temperature without O2 with
permeance in the range of 10−7 mol m−2 s−1 Pa−1 . Although it is
generally accepted that minimum permeances of the order of
10−7 mol m−2 s−1 Pa−1 are needed for commercialization, there is
still need to develop membranes with improved surface area, sta-
bility, and low cost. Comparison is made to previously reported
pure silica and silica–alumina membranes. In addition this study
reports the use of an opposing reactants technique using water
vapor to improve the permeation properties of the compos-
ite membranes. The hydrothermal stabilities of the resulting
SiO2 –TiO2 composite membranes were studied at high tempera-
ture in the range of 673–923 K with water vapor concentrations of
60–75 mol%. To our knowledge there is no previous work on the
hydrothermal stability of SiO2 –TiO2 membranes.
2. Experimental
2.1. Materials and characterization
The TiO2 modified SiO2 composite membranes in this work were
deposited on commercial mesoporous alumina supports with a
nominal pore size of 5 nm by a chemical vapor deposition (CVD)
technique. Prior to deposition, a modified layer of ␥-alumina was
coated on the alumina supports. The modification is necessary to
make the surface of the supports uniform and defect-free, which is
critical for the placement of a thin and selective top-layer.
The modified ␥-alumina layer was prepared by using a dilute
boehmite (AlOOH) sol at a sol concentration of 0.15 M. The
boehmite sol with a median particle size of 40 nm was prepared
by controlled hydrolysis of an aluminum alkoxide and the sub-
sequent acid peptization of the boehmite precipitate obtained. A
quantity of 0.2 mol of aluminum isopropoxide (Aldrich, 98+%) was
added to 300 ml of distilled water at room temperature. The mix-
ture was quickly heated to 353 K within 0.5 h with high speed
stirring and was maintained at this temperature for 1 h for the
hydrolysis of the isopropoxide. The resulting boehmite precipi-
tate was then heated to 365 K and was peptized using 1.81 g acetic
acid (GR, 99.7%) to give a molar ratio of H+ /alkoxide of 0.15. The
solution was refluxed at 365 K for 20 h to get a clear sol. The con-
centration of boehmite sols was calculated from the volume of
the sol and the known quantity (moles) of isopropoxide used. A
Dynamic Light Scattering Analyzer (Horiba Model LB-500) was used
to measure the particle size of the boehmite sols. The analyzer was
calibrated using a standard polystyrene latex microsphere solu-
tion with mean diameter of 102 ± 3 nm (Duke Scientific Co.), and
a value of 1.65 was used as the refractive index of boehmite for
the internal calculation of particle size using a Fourier transform
procedure.
The cross-sectional microstructures of the intermediate layer
of ␥-alumina and the top-layer of composite silica–titania were
observed using a field emission scanning electron microscope
(FESEM, Leo 1550) operated at 5 keV with a magnification of
300,000×. The samples were coated with sputtered gold before
observation with the electron microscope. The thickness of the top
silica–titania layer was obtained from cross-sectional photos with
high resolution.
Gas permeation measurements were conducted in the range of
673–923 K on H2 , CH4 , CO and CO2 by admitting the pure gases
at a pressure of around 200 kPa into the inner tube side, one end
of which was closed, and measuring the quantity of gas flowing
from the outer tube. The selectivities of H2 over CH4 and CO2 were
calculated as the ratio of the single-gas permeances of H2 to CH4 and
CO2 , respectively. Detailed studies of the mechanism indicate that
the membranes operate by a hopping mechanism between sites
[5,6], and that the hopping rate is inversely related to the mass, so
in a mixture H2 is expected to permeate faster than CH4 or CO2 .
Hydrothermal stability tests were carried out at 673–923 K up to
130 h under an Ar flow containing 60 or 75 mol% water vapor. First,
an Ar flow at 15 ␮mol s−1 (flow rates in ␮mol s−1 can be converted
to cm3 (NTP) min−1 by multiplication by 1.5) was passed through a
heated bubbler containing distilled water and was then introduced
on the inner membrane tube side to directly contact the fresh com-
posite membranes, while another Ar flow also at 15 ␮mol s−1 was
maintained on the outer shell side. The H2 , CH4 and CO2 permeation
rates were measured periodically during the hydrothermal stabil-
ity test to monitor the changes in the permeance and selectivity.
To make the permeance measurements the water vapor was shut
off for about 30 min to dry the membranes under a dry Ar flow.
The wet Ar flow was resumed immediately after the permeance
measurements.
2.2. Preparation of membranes
The preparation of the membranes involved several steps.
A commercial alumina membrane tube (PALL Corpora-
tion, Membralox® TI-70-25G Membrane Tube, I.D. = 7 mm,
O.D. = 10 mm) with a nominal pore size of 5 nm was used as the
support. First, the alumina tube was cut to a length of 3–4 cm with
a diamond saw and was connected to non-porous alumina tubes
at both ends with ceramic joints. The ceramic joints were made
with a glaze (Duncan IN 1001) fired at 1153 K for 0.5 h. Second, a
dilute dipping solution was prepared by mixing the boehmite sol
with a polyvinyl alcohol (PVA, M.W. = 72,000) solution and diluting
with distilled water to obtain a 0.15 M concentration of the sol and
a 0.35 wt.% concentration of the PVA. Third, the alumina support
was dipped into the dipping solution and was withdrawn after 10 s
at a rate of 0.01 m s−1 using a motor-driven dip-coating machine.
Fourth, the dip-coated alumina was dried in ambient air for 24 h,
and then was heated to 923 K in air at a rate of 1 K min−1 and
calcined at 923 K for 2 h.
The selective top-layer was deposited on the previously
described modified ␥-alumina supports by chemical vapor depo-
sition of titanium isopropoxide (TIP) and tetraethylorthosilicate
(TEOS) at high temperature using an inert gas carrier. This pro-
cess places a SiO2 –TiO2 layer on the surface of the tubular support
by thermal decomposition. The setup is shown in Fig. 1. The mod-
ified alumina support was installed concentrically inside a piece
of glass tubing of 14 mm inner diameter using machined Swagelok
fittings with Teflon ferrules. After placing the assembly in an elec-
trical furnace and heating it to 873 K at a heating rate of 1 K min−1 ,
an argon gas stream was introduced on the outer shell side (the bal-
ance stream) and a dilute argon gas flow was passed on the inner
tube side. After 0.5 h a TEOS carrier gas flow was passed through one
bubbler filled with TEOS at 296 K while a separate TIP carrier gas
flow was passed through another bubbler filled with TIP at a tem-
perature of 296–316 K. The two carrier gases were then premixed
with another Ar flow stream (the diluting stream) prior to intro-
duction to the inner tube side of the support. The molar ratio of TIP
to TEOS was adjusted by carefully controlling the flow rates of the
carrier gases and the temperature of the TIP bubbler. Table 1 lists
the multielement CVD process parameters for the preparation of
SiO2 –TiO2 membranes using different molar ratio of TIP/TEOS in the
range of 0.03–0.20. The deposition temperature was in the range
of 773–923 K and the deposition time varied from 3 to 16 h. The
resulting SiO2 –TiO2 membranes were denoted as follows. The des-
ignation 065SiTi-873 indicates a membrane prepared with a molar
ratio of TIP to TEOS of 0.065 at 873 K. After the CVD process was
finished, the two carrier gas flows were stopped, and the assem-
 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275 269

Fig. 1. Schematic of apparatus used for the preparation of membranes. The water saturator was used in the opposing reactants method.

bly was purged for 0.5 h with both of the balance gas flow and the (0.27 mol%) and high (1.2 mol%) water vapor concentrations were
dilute gas flow. denoted as 065SiTi-L-773 and 065SiTi-H-773, respectively.
Another preparation method that was briefly investigated is a
variation of the opposing reactants technique (ORT) [2]. In this 3. Results and discussion
method streams of TIP/TEOS and water vapor were passed on oppo-
site side of the membrane and the Si and Ti precursors were made 3.1. Morphology of the silica–titania membranes
to react in the interior. The setup is the same as before except that a
bubbler to deliver water vapor is employed (Fig. 1). The diluting gas Fig. 2 displays micrographs of the cross-sections and outer
stream was mixed with the TIP and TEOS carrier gas flows and was surfaces of two SiO2 –TiO2 membranes prepared at two different
introduced on the inner side of the support (tube side). A water temperatures. Fig. 2(a) shows the micrograph of the fracture surface
vapor carrier gas flow was passed through a bubbler filled with of the silica–titania membrane 065SiTi-923, which was prepared
water (273 or 296 K), premixed with the balance gas flow and then using a molar ratio of TIP/TEOS of 0.065 at 923 K for 3 h. The image
introduced on the outer side of the support (shell side). The water shows the porous alumina support formed from alumina parti-
vapor content in the shell side was adjusted by controlling the cles and a dense surface layer of thickness about 20 nm, which is
water bath temperature and flow rate. The deposition temperature the silica–titania overlayer. Visible on the top surface in Fig. 2(a)
was varied from 773 to 873 K. Table 2 lists the process parame- are a few “boulders” of size around 30–40 nm protruding from the
ters for the preparation of TiO2 –SiO2 membranes by this opposing membrane surface. These features can also be observed from the
reactants technique using different H2 O concentrations (0.27 and micrograph on the top surface of the membrane, shown in Fig. 2(b),
1.2 mol%). The TEOS concentration was fixed at 0.047 mol% and and are probably titania particles. It was reported that decom-
the molar ratio of TIP/TEOS at 0.065. The SiO2 –TiO2 membranes
prepared at 773 K by the opposing reactants technique using low Table 2
Opposing reactants technique assisted CVD process parameters for the preparation
of silica–titania membranes (CVD temperature: 673, 773 or 873 K).
Table 1
CVD process parameters for the preparation of silica–titania membranes (CVD tem- Membrane 065SiTi-L 065SiTi-H
perature: 773, 873 or 923 K). TEOS bath temp. (K) 296 296
TIP bath temp. (K) 296 296
Membrane 03SiTi 065SiTi 10SiTi 15SiTi 20SiTi
Water vapor bath temp. (K) 273 296
TEOS bath temp. (K) 296 296 296 296 296 TEOS carrier gas (␮mol s−1 ) 3.7 3.7
TIP bath temp. (K) 296 296 296 310 316 TIP carrier gas (␮mol s−1 ) 7.2 7.2
TEOS carrier gas (␮mol s−1 ) 3.7 3.7 3.7 3.7 3.7 Diluting gas (␮mol s−1 ) 6.4 6.4
TIP carrier gas (␮mol s−1 ) 3.4 7.2 11 5.6 4.8 Water vapor carrier gas 9.6 9.6
Diluting gas (␮mol s−1 ) 10 6.4 2.4 8.0 8.7 Balance gas (␮mol s−1 ) 7.7 7.7
Balance gas (␮mol s−1 ) 17 17 17 17 17 TEOS conc. (mol%) 0.047 0.047
TEOS conc. (mol%) 0.047 0.047 0.047 0.047 0.047 TIP conc. (mol%) 0.0031 0.0031
TIP conc. (mol%) 0.0014 0.0031 0.0047 0.0071 0.094 TIP/TEOS (molar ratio) 0.065 0.065
TIP/TEOS (molar ratio) 0.03 0.065 0.10 0.15 0.20 Water vapor conc. (mol%) 0.27 1.22
270 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275
Fig. 2. Scanning electron micrographs of membranes. (a) Cross-section of membrane prepared with TIP/TEOS of 0.065 at 923 K, (b) top surface of same membrane, (c)
cross-section of membrane prepared with TIP/TEOS of 0.065 at 773 K and (d) top surface of same membrane.
position of TIP at temperatures above 673 K produced not only
porous crystalline titania membranes but also titania particles via
homogeneous nucleation reactions [28]. As deposition tempera-
ture increased, the homogeneous particle formation rate increases,
thus leading to the formation of bigger titania particles. The regions
around the titania particles probably have voids of a mesoporous
size, which are the defects that responsible for the limited selectiv-
ity of the material.
Fig. 2(c) shows the morphology of the fracture surface of
the membrane 065SiTi-773, which was prepared using a molar
ratio of TIP/TEOS of 0.065 at 773 K. Compared with the higher
temperature deposited membrane 065SiTi-923, the lower temper-
ature derived membrane 065SiTi-773 had a smaller thickness of
around 10–15 nm, although it was prepared using a much longer
deposition time (16 h vs. 3 h). Because of the lower deposition tem-
perature, the precursors (TEOS and TIP) are less reactive, and thus
a thinner membrane is obtained. However, the lower deposition
temperature leads to formation of less titania particles. This behav-
ior is demonstrated in the micrograph of the top surface of the
membrane 065SiTi-773 as shown in Fig. 2(d).
The silica–titania membrane reported here is a member of
a class of membranes prepared by high-temperature chemical
vapor deposition in inert gas which includes silica [6,7] and
silica–alumina membranes [14]. These membranes share the
same morphological features, namely they consist of thin lay-
ers (20–30 nm) of the permselective layer deposited on a porous
support with an intermediate ␥-alumina layer. A comparison of
the three types of membranes (Fig. 3) shows that they are sim-
ilar. The silica has an amorphous structure composed of mainly
6-membered siloxane rings, which is more open than vitreous
glass [29]. The alumina and titania components are known to form
glasses with silica, and so are readily incorporated into the silica
structure. The amorphous nature of the material likely imparts the
membranes with stability, as any defects are readily repaired by
migration of bonds. Crystalline materials would tend to densify, and
the naturally occurring grain boundaries in them would constitute
defects.
3.2. Gas permeation properties of the composite membranes
Fig. 4 shows the changes in gas permeances and hydrogen
selectivities with the deposition time through the silica–titania
composite membrane 065SiTi-773, which was prepared with a
molar ratio of TIP/TEOS of 0.065 at 773 K. Before CVD, the freshly
modified ␥-alumina support had high gas permeance for H2 , CH4
and CO2 in the order of 10−5 mol m−2 s−1 Pa−1 but had a rather
low selectivity of H2 , 2.4 and 4.0 for H2 /CH4 and H2 /CO2 , which
were close to the ratio expected for Knudsen diffusion (2.8 and
4.7). This result is consistent with the pore size (3.7 nm) of the
modified layer of ␥-alumina. After 6 h of deposition, the gas per-
meance dropped to 7 × 10−7 mol m−2 s−1 Pa−1 for H2 and to the
order of 10−8 mol m−2 s−1 Pa−1 for CH4 and CO2 , resulting in a
small selectivity increase to 8. As the CVD deposition continued,
the permeance of H2 decreased more slowly than that of the
other gases (CH4 and CO2 ), leading to a constant increase in the
H2 selectivity. After 16 h of deposition, the H2 permeance was
3.3 × 10−7 mol m−2 s−1 Pa−1 at 773 K, and the selectivity of H2 over
CH4 and CO2 went up to 14 and 16, respectively. Although these
values are higher than the Knudsen value, they indicated that some
defects were present after deposition which permitted the passage
of CH4 and CO2 molecules.
During the multielement CVD deposition, the permeation prop-
erties through the membranes were much influenced by the CVD
process parameters such as deposition temperature, deposition
time and precursor concentration ratio. Fig. 5(a and b) shows the
permeation properties of silica–titania composite membranes pre-
pared at different temperatures 773–923 K with the use of the same
molar ratio of TIP/TEOS = 0.065. The results in Fig. 5(a) show that
the H2 permeance of the membrane prepared at higher deposition
temperature dropped faster than that prepared at lower temper-
ature. After 3 h of deposition at 923 K, the H2 permeance of the
resulting membrane 065SiTi-923 was 2.0 × 10−7 mol m−2 s−1 Pa−1 ,
while the H2 permeance for the membrane 065SiTi-773 was
3.3 × 10−7 mol m−2 s−1 Pa−1 . The results are reasonable because at
higher temperature the Si and Ti precursors decompose faster, and
 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275 271

Fig. 3. Comparison of membranes prepared by the high-temperature CVD method. (a) Alumina support, (b) silica membrane, (c) silica–alumina membrane and (d)
silica–titania membrane.

thus the pores of the support are closed faster, leading to a quicker
drop in permeance, and quicker increase in selectivity, as shown
in Fig. 5(b). After the same 3 h of CVD, the H2 /CH4 selectivity of
the membrane 065SiTi-923 made at higher temperature was 16, in
comparison to a selectivity of 3.4 for the membrane 065SiTi-773
made at lower temperature.
Fig. 6 shows the effect of the molar ratio of TIP/TEOS used on the
permeation properties of the silica–titania membranes deposited
at the same temperature of 873 K. The selectivity of H2 over CH4 for
the pure TEOS membrane is very high (5840) but drops consider-
ably with addition of Ti to a TIP/TEOS ratio of 0.03. The permeance
does not change significantly, indicating that the small addition of
Ti opens up a small number of big defects. When the molar ratio of
TIP/TEOS increased from 0.03 to 0.10, the selectivity of H2 over CH4
through the resulting membranes improved by more than eight
times from 4 to 37, while the H2 permeance just decreased by half
from 5.3 to 2.3 × 10−7 mol m−2 s−1 Pa−1 . However, when a higher
Fig. 4. Changes of permeances and selectivities with the deposition time of a com-
ratio of TIP/TEOS was used, especially a TIP/TEOS higher than 0.15,
posite membrane prepared at 773 K with the use of TIP/TEOS of 0.065.
the selectivity dropped substantially to 1.9, while the permeance
rose to the 10−6 range. This was likely due to defects in the mem-
brane caused by the formation of titania particles [28]. These titania
particles get admixed with the silica membrane rather than form-

Fig. 5. Changes of permeances and selectivities with the deposition time of composite membranes prepared by using the same molar ratio of TIP/TEOS of 0.065 at 773, 873
and 923 K, respectively. (a) H2 permeance and (b) H2 /CH4 selectivity.
272 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275

Fig. 6. Influence of molar ratio of TIP/TEOS used on permeation properties of com-

Fig. 7. Changes of H2 permeance and H2 /CH4 selectivity with the deposition time of
posite membranes prepared at 873 K.
composite membranes prepared at 873 K by using a standard CVD and an opposing
reactants technique assisted CVD.

ing a uniform Si–Ti glass. Thus, the membrane prepared using a

molar ratio of TIP/TEOS = 0.10 had the best performance with a H2 Fig. 8 shows the effect of water vapor concentration. The figure
permeance of 2.3 × 10−7 mol m−2 s−1 Pa−1 and H2 selectivities over displays changes in the permeation properties through the compos-
CH4 and CO2 of 37 and 57, respectively at 873 K. Since the selectivity ite membranes prepared at the low temperature of 773 K without
is defined as the ratio of single-gas permeances, this corresponds and with introduction of low (0.27 mol%) and high (1.22 mol%)
to a H2 purity above (37/38) or 97%. water vapor concentrations. The presence of water vapor at 773 K
Compared with the pure silica membranes [30,31], the compos- not only shortened the deposition time by at least half, but also
ite silica–titania membranes in this work show higher permeance, improved the selectivity while maintaining the permeance. After
but smaller selectivity. This is probably due to the higher intrinsic 7 h of CVD, the membrane 065SiTi-L-773 prepared with the low
reactivity of the Ti precursor over the Si precursor, which results water vapor concentration showed a H2 /CH4 selectivity of 17 with
in the formation of defects in the form of titania inclusions. In a H2 permeance of 2.8 × 10−7 mol m−2 s−1 Pa−1 at 773 K, while it
the absence of reactants such as O2 , O3 or H2 O, the Ti precursor took 16 h for the membrane 065SiTi-773 without introduction of
TIP can be decomposed in the temperature range of 503–573 K water vapor to obtain a H2 /CH4 selectivity of 14 with a H2 per-
to form a dense and H2 -selective TiO2 membrane [28], while the meance of 3.3 × 10−7 mol m−2 s−1 Pa−1 at 773 K. The higher water
decomposition of the Si precursor TEOS occurs at 873–923 K for vapor concentration reduced the selectivity, although it had almost
the formation of dense and H2 -selective SiO2 membranes. In the no effect on the permeance for H2 . This may have been due to exces-
presence of reactants such as O2 or O3 , however, TEOS could be sive passage of the water to the side of the membrane with the TEOS
decomposed completely at temperatures as low as 473 K [1,32]. and TIP components resulting in the homogeneous decomposition
In this work, SiO2 is the principal component, and thus, the intro- of those reactants.
duction of water vapor in the synthesis is expected to improve the The opposing reactants technique allows preparation of mem-
quality of the silica–titania membranes, as shown next. branes at low temperatures. Fig. 9 shows the properties of a
membrane prepared at 673 K. The figure displays the perme-
ance and selectivity through a silica–titania composite membrane
3.3. Opposing reactants technique
065SiTi-L-673 prepared by ORT-assisted CVD as a function of
deposition time. This membrane was prepared using a molar
In order to overcome the problems with the standard-CVD
preparation method we developed an alternative method that
employs water vapor to assist and control the decomposition of the
precursors. In this opposing reactants technique (ORT), the water
vapor is made to permeate from the opposite side of the membrane,
so that the Si and Ti precursors (TEOS and TIP) do not decompose
in the gas-phase.
Fig. 7 compares changes with deposition time of the permeation
properties through a standard-CVD derived silica–titania mem-
brane 065SiTi-873 and an ORT-assisted CVD (ORT-CVD) derived
membrane 065SiTi-L-873 using a low concentration of water
vapor (0.27 mol%). These two composite membranes were pre-
pared at the same temperature (873 K) and the same molar ratio
of TIP/TEOS (0.065). Clearly, the opposing reactants technique
improves the selectivity properties. After 3 h of deposition, the
H2 selectivities over CH4 and CO2 were 20 and 29, respectively
for the ORT-CVD derived membrane, while they were 8.2 and
12 for the standard-CVD derived membrane. The H2 permeance
through the ORT-CVD membrane, however, was slightly lower,
1.3 × 10−7 mol m−2 s−1 Pa−1 vs 3.3 × 10−7 mol m−2 s−1 Pa−1 . Over- Fig. 8. Changes of H2 permeance and H2 /CH4 selectivity with the deposition time
of three composite membranes prepared at 773 K by using a standard CVD and an
all, the introduction of water vapor improves the membrane opposing reactants technique assisted CVD with the use of different water concen-
properties. tration.
 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275
Fig. 9. Changes of permeances and selectivities with the deposition time of a com-
posite membrane prepared at 673 K by using an opposing reactants technique
assisted CVD.
ratio of TIP/TEOS of 0.065, and TEOS and water vapor concentra-
tions of 0.047 and 0.27 mol%, respectively. With the use of water
vapor the permeance for H2 was reduced more slowly than that
for CH4 and CO2 , thus leading to a continuous increase in H2
selectivity. After 18 h of deposition, the H2 /CO2 selectivity was
improved from 2.2 to 8.9 and the H2 permeance was as high as
2.0 × 10−7 mol m−2 s−1 Pa−1 at 673 K. Compared with the results
of the deposition at 773 and 873 K in Figs. 8 and 9, much longer
time is required to obtain a selective composite membrane, but the
performance is not enhanced.
Overall, the use of water vapor reduces the temperature and
time required to prepare the membranes, and improves the per-
formance of the membranes. The water likely assists in the
decomposition of the TIP and TEOS through hydrolytic cleavage
of the alkoxide bonds. The end-product is substantially the same,
an amorphous silica–titania material, but the lower temperature
of synthesis reduces the formation of the titania particles that are
responsible for defects.
3.4. Hydrothermal stability
Fig. 10 shows the effect of water vapor on the H2 permeance of
composite silica–titania membranes prepared at 773 K using stan-
Fig. 10. Changes of H2 permeance during the exposure to 60 mol% H2 O at 673 K
for three composite membranes prepared at 773 K by using a standard CVD and an
opposing reactants technique assisted CVD with the use of different water concen-
tration.
273
dard CVD and ORT-CVD. The membranes were exposed to 60 mol%
water vapor at 673 K for 130 h. These three membranes showed
similar behavior in their resistance to water vapor, probably due
to the use of the same preparation conditions including deposition
temperature and molar ratio of TIP/TEOS. They suffered the most
significant loss of permeance in the initial states, i.e., the first 20 h.
After 40 h of exposure to water vapor, the H2 permeance of the
composite membranes stabilized. The total reduction of H2 perme-
ance for an exposure of 130 h is in the range of 50–60%. For the
sample with 0.27 mol% H2 O the changes in selectivity before steam
exposure (H2 /CH4 = 14.7, H2 /CO2 = 13.6) and after steam exposure
(H2 /CH4 = 6.0, H2 /CO2 = 10.2) did not change much. For the sam-
ple with 1.22 mol% H2 O the changes in selectivity before steam
exposure (H2 /CH4 = 10.4, H2 /CO2 = 9.5) and after steam exposure
(H2 /CH4 = 5.3, H2 /CO2 = 14.1) also were not altered appreciably. For
comparison, the H2 permeance of a pure CVD-derived silica mem-
brane suffered 90% reduction after exposure to 50 mol% water vapor
at 673 K for 100 h [8]. For the sample without H2 O the selectiv-
ity before steam exposure (H2 /CH4 = 11.2, H2 /CO2 = 13.3) and after
steam exposure (H2 /CH4 = 5.1, H2 /CO2 = 8.9) were comparable.
Fig. 11 shows the effect of the deposition temperature on
the hydrothermal stability of composite membranes prepared
using the same TIP/TEOS molar ratio, TEOS and water vapor
concentrations. The permeance and selectivity of the membrane
065SiTi-L-773 is given in Table 3. There is only a minor effect on the
selectivity. Interestingly, the membrane 065SiTi-L-873 prepared at
873 K showed very strong hydrothermal stability. After exposure
to a stream containing 60 mol% water vapor at 673 K for over 120 h,
the H2 permeance through 065TS-L-873 almost did not change.
Its lower permeance is due to the use of the lower permeation
temperature (673 K) in comparison to its deposition temperature
(873 K). The membranes can be viewed as a solid matrix of a
silica–titania amorphous material with embedded titania particles
with associated defects in the form of mesoporous voids. The higher
permeance materials, which have larger amounts of these meso-
porous voids, suffer greater loss in permeance, so it appears that
densification occurs in the vicinity of the large particles.
In order to further investigate the hydrothermal stability of
these composite membranes at very harsh condition, the mem-
brane 065SiTi-923 prepared at 923 K was exposed at 923 K to a
stream containing 75 mol% water vapor. Significantly as shown in
Fig. 12, the H2 permeance through this membrane was reduced
to around 24% in the first 10 h, and then was stabilized in the
range of 24–30% for the remaining 122 h of the test and still kept a
Fig. 11. Changes of H2 permeance during the exposure to 60 mol% H2 O at 673 K for
three composite membranes prepared at 673–873 K by using an opposing reactants
technique assisted CVD.
274 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275
Table 3
Permeance and selectivity of membrane 065SiTi-L-773 (Fig. 11) before and after exposure to 60 mol% water.
Property Permeance (mol m−2 s−1 Pa−1 )
H2 CH4
Before exposure 2.42 × 10−7 1.65 × 10−8
After 21 h of exposure 1.77 × 10−7 1.71 × 10−8
After 126 h of exposure 9.89 × 10−8 1.65 × 10−8
Fig. 12. Changes of H2 permeance during the exposure to 75 mol% H2 O at 923 K for
a composite membrane prepared at 923 K by a standard CVD with the use of molar
ratio of TIP/TEOS of 0.065.
permeance in the order of 10−7 mol m−2 s−1 Pa−1 . For this sample
the selectivity before steam exposure (H2 /CH4 = 16, H2 /CO2 = 23.6)
and after steam exposure (H2 /CH4 = 6.4, H2 /CO2 = 11.7) declined
slightly.
In comparison a pure silica membrane at milder conditions of
873 K at 15 mol% water underwent a drop of permeance of 90% to
6 × 10−8 mol m−2 s−1 Pa−1 . In this case the selectivity before steam
exposure (H2 /CH4 = 5840, H2 /CO2 = 1540) and after steam exposure
(H2 /CH4 = not available, H2 /CO2 = 520) declined moderately.
A silica–alumina membrane showed better permeance of
1.5 × 10−7 mol m−2 s−1 mPa−1 , but a greater drop in permeance of
37%. Nevertheless, the membrane was stable. For this sample the
selectivity before steam exposure (H2 /CH4 = 170, H2 /CO2 = 180) and
after steam exposure (H2 /CH4 = 40, H2 /CO2 = 70) also declined mod-
erately.
The addition of the titania and alumina to the silica resulted in
membranes of good permeability and stability. The essential reason
for the improvement is likely the enhanced resistance of Ti–O–Si
and Al–O–Si bonds to hydrolytic bond cleavage.
4. Conclusions
Composite silica–titania membranes for hydrogen permeance
with excellent hydrothermal stability were prepared at 773–923 K
by the multi-component CVD technique on a commercial alumina
support with a nominal pore size of 5 nm. Titanium isopropoxide
(TIP) and tetraethylorthosilicate (TEOS) were used as the Ti and
Si precursors. The effects of deposition temperature, molar ratio
of the Ti and Si precursors and deposition time on the morphol-
ogy and permeation properties of the silica–titania membranes
obtained were investigated. Higher deposition temperatures led
to faster deposition and thicker membranes with lower perme-
ability. SEM cross-sectional microphotographs of the composite
membranes indicated that a silica–titania layer with a thickness of
20 nm was formed on the porous alumina support after 3-h depo-
sition at 923 K, while a layer of thickness 10–15 nm was deposited
Selectivity
CO2 H2 /CH4 H2 /CO2
1.78 × 10−8 14.7 13.6
1.29 × 10−8 10.4 13.7
9.73 × 10−9 6.0 10.2
after 16 h deposition at 773 K. The membrane prepared at 873 K
using a molar ratio of TIP/TEOS = 0.10 had the best performance
with a H2 permeance of 2.3 × 10−7 mol m−2 s−1 Pa−1 and H2 selec-
tivities over CH4 and CO2 of 37 and 57, respectively at 873 K. The
composite membrane displayed significantly improved hydrother-
mal stability. After exposure to steam with 75 mol% H2 O at 923 K
for more than 130 h, the H2 permeance through the membrane was
reduced by only 30%, and was still close to 10−7 mol m−2 s−1 Pa−1 .
As an alternative method, the “opposing reactants technique”
(ORT) was developed to improve the selectivity of the composite
membrane by the introduction of water vapor as a reactant, which
makes it possible to lower the temperature of deposition. After
deposition at 773 K for 6 h, the ORT-assisted CVD derived mem-
brane showed enhanced selectivity, two times higher than that
prepared by the standard-CVD method.
Acknowledgements
The authors acknowledge the Director, National Science Foun-
dation, Division of Chemical, Bioengineering, Environmental, and
Transport Systems (CBET) for award of Grant No. CBET-0854316
in support of this work. The authors also thank the ConocoPhillips
Company for their sponsorship of the research program.
References
[1] T. Okubo, H. Inoue, Introduction of specific gas selectivity to porous glass mem-
branes by treatment with tetraethoxysilane, J. Membr. Sci. 42 (1989) 109.
[2] G.R. Gavalas, C.E. Megiris, S.W. Nam, Deposition of H2 -permselective SiO2 films,
Chem. Eng. Sci. 44 (1989) 1829.
[3] S. Yan, H. Maeda, K. Kusakabe, S. Morooka, Y. Akiyama, Hydrogen-permselective
SiO2 membrane formed in pores of alumina support tube by chemical vapor
deposition with tetraethylorthosilicate, Ind. Eng. Chem. Res. 33 (1994) 2096.
[4] D. Lee, S.T. Oyama, Gas permeation characteristics of a hydrogen selective sup-
ported silica membrane, J. Membr. Sci. 210 (2002) 291–306.
[5] S.T. Oyama, D. Lee, P. Hacarlioglu, R.F. Saraf, Theory of hydrogen permeability
in nonporous silica membranes, J. Membr. Sci. 244 (2004) 45–53.
[6] Y. Gu, S.T. Oyama, High molecular permeance in a pore-less ceramic membrane,
Adv. Mater. 19 (2007) 1636–1640.
[7] Y. Gu, S.T. Oyama, Novel silica/alumina multilayer membranes with graded
structures, J. Membr. Sci. 306 (2007) 216–227.
[8] B.-K. Sea, E. Soewito, M. Watanabe, K. Kusakabe, S. Morooka, S.S. Kim, Hydro-
gen recovery from a H2 –H2 O–HBr mixture utilizing silica-based membranes
at elevated temperatures. 1. Preparation of H2 O- and H2 -selective membranes,
Ind. Eng. Chem. Res. 37 (1998) 2502.
[9] T. Tsuru, K. Yamaguchi, T. Yoshioka, M. Asaeda, Methane steam reforming by
microporous catalytic membrane reactors, AIChE J. 50 (2004) 2794.
[10] R.M. de Vos, W.F. Maier, H. Verweij, Hydrophobic silica membranes for gas
separation, J. Membr. Sci. 158 (1999) 277.
[11] M. Asaeda, M. Kashimoto, Sol–gel derived silica membranes for separation of
hydrogen at high temperature—separation performance and stability against
steam, in: Proc. Fifth Inter. Conf. on Inorg. Membr., Nagoya, Japan, 1998, pp.
172–173.
[12] G.P. Fotou, Y.S. Lin, S.E. Pratsinis, Hydrothermal stability of pure and modified
microporous silica membranes, J. Mater. Sci. 30 (1995) 2803.
[13] K. Yoshida, Y. Hirano, H. Fujii, T. Tsuru, M. Asaeda, Hydrothermal stability
and performance of silica–zirconia membranes for hydrogen separation in
hydrothermal conditions, J. Chem. Eng. Japan 34 (2001) 523.
[14] Y. Gu, P. Hacarlioglu, S.T. Oyama, Hydrothermally stable silica–alumina com-
posite membranes for hydrogen separation, J. Membr. Sci. 310 (2008) 28.
[15] R. Igi, T. Yoshioka, Y.H. Ikuhara, Y. Iwamoto, T. Tsuru, Characterization of Co-
doped silica for improved hydrothermal stability and application to hydrogen
separation membrane at high temperature, J. Am. Ceram. Soc. 91 (2008) 2975.
[16] S. Battersby, S. Smart, B. Ladewig, S. Liu, M.C. Duke, V. Rudolph, J.C. Diniz da
Costa, Hydrothermal stability of cobalt silica membranes in a water gas shift
membrane reactor, Sep. Purif. Technol. 66 (2009) 299.
 Y. Gu, S.T. Oyama / Journal of Membrane Science 345 (2009) 267–275
[17] M. Kanezashi, M. Asaeda, Hydrogen permeation characteristics and stability of
Ni-doped silica membranes in steam at high temperature, J. Membr. Sci. 271
(2005) 86.
[18] V. Boffa, D.H.A. Blank, J.E. ten Elshof, Hydrothermal stability of microporous
silica and niobia–silica membranes, J. Membr. Sci. 319 (2008) 256.
[19] D. Lee, P. Hacarlioglu, S.T. Oyama, Effect of pressure in membrane reactors:
tradeoff in permeability and equilibrium conversion in the catalytic reforming
of CH4 with CO2 at high pressure, Top. Catal. 29 (2004) 45–57.
[20] S.T. Oyama, X. Zhang, J. Lu, Y. Gu, T. Fujitani, Epoxidation of propylene with H2
and O2 in the explosive regime in a packed-bed catalytic membrane reactor, J.
Catal. 257 (2008) 1–4.
[21] S.T. Oyama, P. Hacarlioglu, The boundary between simple and complex descrip-
tions of membrane reactors: the transition between 1-D and 2-D analysis, J.
Membr. Sci. 337 (2009) 188–199.
[22] S.T. Oyama, H. Lim, An Operability Level Coefficient (OLC) as a useful tool for
correlating the performance of membrane reactors, Chem. Eng. Sci. 151 (2009)
351–358.
[23] A. Feldman, E.N. Farabaugh, W.K. Haller, D.M. Sanders, R.A. Stempniak, Mod-
ifying structure and properties of optical films by coevaporation, J. Vac. Sci.
Technol. A: Vac. Surf. Films 4 (1986) 2969.
[24] J.S. Chen, S. Chao, J.S. Kao, H. Liu, C.H. Chen, Mixed films of TiO2 –SiO2 deposited
by double electron-beam coevaporation, Appl. Opt. 35 (1996) 90.
[25] J.E. Shelby, Helium migration in TiO2 –SiO2 glass, J. Am. Ceram. Soc. 55 (1972)
195.
275
[26] R.S.A. de Lange, J.H.A. Hekkink, K. Keizer, A.J. Burggraaf, Formation and charac-
terization of supported microporous ceramic membranes prepared by sol–gel
modification techniques, J. Membr. Sci. 99 (1995) 57.
[27] S.W. Nam, H.Y. Ha, S.P. Yoon, J. Han, T.H. Lim, I.-H. Oh, S.-A. Hong, Hydrogen-
permselective TiO2 /SiO2 membranes formed by chemical vapor deposition,
Korean Membr. J. 3 (2001) 69.
[28] H.Y. Ha, S.W. Nam, T.H. Lim, I.-H. Oh, S.-A. Hong, Properties of the TiO2 mem-
branes prepared by CVD of titanium tetraisopropoxide, J. Membr. Sci. 111
(1996) 81.
[29] P. Hacarlioglu, D. Lee, J.G. Gibbs, S.T. Oyama, Activation energies for permeation
of hydrogen and helium through silica membranes: an ab initio calculation
study, J. Membr. Sci. 313 (2008) 278–283.
[30] A.K. Prabhu, S.T. Oyama, Highly hydrogen selective ceramic membranes: appli-
cation to the transformation of greenhouse gases, J. Membr. Sci. 176 (2000)
233.
[31] D. Lee, L. Zhang, S.T. Oyama, S. Niu, R.F. Saraf, Synthesis, characterization and gas
permeation properties of a hydrogen permeable silica membrane supported on
porous alumina, J. Membr. Sci. 231 (2004) 117.
[32] S.-I. Nakao, T. Suzuki, T. Sugawara, T. Tsuru, S. Kimura, Preparation of micro-
porous membranes by TEOS/O3 CVD in the opposing reactants geometry,
Micropor. Mesopor. Mater. 37 (2000) 145.