Zeolite-b grown epitaxially on SSZ-31 nanofibers

Sankar Nair,a Luis A. Villaescusa,b Miguel A. Camblor*b and Michael Tsapatsis*a

a Department of Chemical Engineering, University of Massachusetts, Amherst MA 01003, USA.
E-mail: tsapatsi@ecs.umass.edu
b Instituto de Tecnologı́a Quı́mica (CSIC-UPV), Universidad Politécnica de Valencia, Avda. Los Naranjos s/n, 46071

Valencia, Spain. E-mail: macamblo@itq.upv.es

Received (in Columbia, MO, USA) 31st December 1998, Accepted 31st March 1999

The synthesis and characterization of an epitaxial growth of decreased to 7.5, ITQ-39 was the crystallization product). All
zeolite b on SSZ-31 nanofibers is described, and a structural these suggested that the synthesized solid could actually be an
model of the interface between the two zeolites is pro- intergrowth of zeolites b and SSZ-31.
posed. To characterize the synthesized crystals, transmission elec-
tron microscopy was performed with a JEOL 3010 microscope
Zeolite crystals in the form of nanofibers have several potential operating at 300 kV. A low-resolution TEM image shows that a
catalytic applications, owing to the short diffusion lengths significant number of crystals are nanofibers of length 1–2 mm,
across these fibers and their low resistance to fluid flow (low with radial outgrowths ca. 20 nm in radius [Fig. 1(a)]. A few
pressure drop), as well as other advanced materials applications fibers of length up to 5 mm have also been observed. A high-
owing to the possibility of incorporating them in membrane, resolution TEM image [Fig. 1(b)] from the center of such a
sensor or electronic devices. A few zeolites with one- crystallite reveals that a nanofiber of zeolite SSZ-31 forms a
dimensional (1-D) pore systems are known to crystallize in a ‘backbone’ (running along the centerline of the nanofiber) for
needle-like morphology1–3 with the channels running along the epitaxial growth of zeolite-b. This is further corroborated by the
long axis of the particles. This raises the possibility of presence of SSZ-31 nanofibers free of zeolite-b outgrowths.
epitaxially growing other zeolitic structures on nanofibers of Complete channels of b (polymorph B) lie immediately above
such 1-D pore zeolites. We report here, the first such epitaxial the b/SSZ-31 interface. Two SSZ-31 channels are observed,
process, involving the growth of zeolite-b on nanofibers of the apparently running parallel to the second channel direction of
1-D zeolite SSZ-31, and we propose a structural model for the zeolite-b. These observations suggest that the b/SSZ-31
interface between the two zeolites. interface contains composite 12-membered channels con-
Zeolite-b is an industrially important large-pore material, structed from b and SSZ-31 ‘half-channels’. The SSZ-31
widely used in catalytic and adsorption processes.4,5 Previous ‘backbone’ is observed to be always three unit cells thick.
syntheses of zeolite-b resulted in equiaxed particles that contain
both the b polymorphs A and B. In this study, zeolite-b was
synthesized as pure silica polymorph using 1,3,3,6,6-pentame-
thyl-6-azoniumbicyclo[3.2.1]octane cation as the organic struc-
ture-directing agent (SDA). This cation was synthesized by
quaternization of the parent amine with an excess of MeI in
CCl3H, and was used in hydroxide form after anion exchange of
the iodide.
For the zeolite synthesis, tetraethylorthosilicate (21.89 g) was
hydrolysed in 35.02 g of an aqueous solution of the SDA in
hydroxide form (1.49 mmol g21). The mixture was stirred,
allowing evaporation of the ethanol produced in the hydrolysis.
Further stirring for 3 h at room temperature allowed the
evaporation of a total mass of 22.69 g (ethanol plus water).
Then, HF (2.18 g, 48% aqueous solution) was added and the
mixture was shaken till homogeneous. Hydrothermal crystal-
lization of this mixture (final composition SiO2 : 0.5
C12H24NOH : 0.5 HF : 9.9 H2O) in rotating (60 rpm) Teflon-
lined stainless steel autoclaves at 150 °C for 20 days produced
a crystalline solid with an XRD pattern similar to that of zeolite-
b.6,7
However, there were several facts suggesting that this
material was not identical to zeolite-b and that it could also be
related to zeolite SSZ-31. First, the XRD pattern shows some
differences with the pattern of zeolite-b and some similarities
with that of SSZ-313,8. For instance, the shape of the first broad
peak at low angle is more like that of the second peak in SSZ-31
rather than the first peak in zeolite-b. Also, the separation of the
two main peaks in the range 2q 20–22.5° of 1.20° is closer to
that in SSZ-31 (1.28°) than in b (1.08°). Furthermore, the
adsorption capacity of this material (0.13 cm3 g21) calculated
from the N2 adsorption isotherm using the t-plot method, is Fig. 1 (a) TEM image of synthesized crystals showing SSZ-31 nanofibers
intermediate between those of zeolites b (0.19 cm3 g21) and with epitaxial outgrowths of zeolite-b; (b) high-resolution TEM image of
SSZ-31 (0.08 cm3 g21). Interestingly, when the final water- the epitaxial growth of zeolite-b on zeolite SSZ-31; model of the
: silica ratio in the above synthesis mixture composition was intergrowth (inset, upper); and TEM simulation of this model (inset,
increased to 15, SSZ-31 was obtained (when the ratio was lower).

Chem. Commun., 1999, 921–922 921

 form periodic (2–4–2–4–) chains (abbreviated to 24) running
along the channel direction. However, these chains are laterally
shifted with respect to each other, so that a two-membered
fragment on one chain has as its neighbor, a four-membered
fragment of the adjacent chain. The two sequences running
alongside an SSZ-31 half-channel can be represented as (24) 8
(42) for polymorphs A–D. The symbol 8 indicates the half-
channel as viewed down [010], with one sequence running
along its left and right. Polymorphs E–H have adjacent (24) 8
(26), and (26) 8 (24) half-channels.
The epitaxy is achieved by bonding the half-channels of b
and SSZ-31 (via oxygen atoms) to form 12-membered inter-
facial composite channels. The combination of the sequences of
zeolite-b with the sequences of SSZ-31 polymorphs A–D
results in closed rings following the periodic sequences
(475657) - (657475); where the symbol - indicates the
composite channel. Interfaces of b with SSZ-31 polymorphs E–
H have two types of composite channels when viewed down the
channel direction: (475657) - (495858), and (495858) -
(475657). These channels are adjacent to each other at the
interface. The interfaces therefore contain seven-membered
rings, and even nine-membered rings in the case of epitaxial
growths involving SSZ-31 polymorphs E–H. The two poly-
morphs of b together with the eight polymorphs of SSZ-31 lead
to 16 possible epitaxial growths, with only two possible
interfacial structures, (475657) and (495858), as shown above.
Considering the unit cell dimensions of the two zeolites, the 2-D
rectangular epitaxial unit cell at the interface would have
dimensions of 25.2 Å in the SSZ-31 channel direction and 12.33
Å in the perpendicular b channel direction. Composite channels
comprising unequal numbers of tetrahedra from each zeolite
(e.g., eight from b and four from SSZ-31) do not appear to be
feasible due to non-matching bond positions on either side of
the interface.
Fig. 2 (a) Projection of b structure along < 110 > showing the two- and The epitaxy of b polymorph B on SSZ-31 polymorph B is
three-membered ring fragments in a (233) sequence; (b) projection along simulated as described above, using the Cerius2 Interface
< 2110 > showing the half-channels. Each of the eight lowermost silicon
Builder. The resulting structure [Fig. 1(b), upper inset] is found
atoms is a member of a (233) sequence running alongside a half-channel in
the < 2110 > direction; (c) projection of SSZ-31 polymorph B along [010] to match the TEM image. In the TEM image, the two zeolite-b
showing the half-channels. Each of the uppermost silicon atoms is a domains on either side of the SSZ-31 domain appear to be
member of a (24) sequence running alongside the half-channel. These laterally shifted with respect to each other. The structural model
sequences are laterally shifted with respect to each other. The generation of proposed above accounts for this observation, since it allows the
the (657475) and (475657) sequences at the interface of zeolite-b with SSZ- b structure to be shifted along the channel direction of SSZ-31.
31 polymorphs A–D is indicated. This shift is captured in the interface simulation, and appears in
the upper inset of Fig. 1(b). A TEM simulation of the interface
To construct possible interfaces, it is first assumed that the is also shown (lower inset), and it is seen to match the actual
12-membered composite channels are comprised of six silicate image. However, the information available from the TEM
tetrahedra derived from a b channel, and the remaining six image appears insufficient to identify the SSZ-31 polymorph
tetrahedra from an SSZ-31 channel. We terminate the b that is actually involved in the epitaxy. It is also possible that the
structure at a plane parallel to the < 2110 > channel direction, synthesized sample contains intergrowths of zeolite-b and SSZ-
leaving six-membered half-channels in this direction and 31 in addition to the epitaxial regions that we observe.
complete channels in the < 110 > direction. Fig. 2(a) shows a S. N. and M. T. acknowledge funding from the NETI, the
view of the b polymorph B along the < 110 > direction, and David and Lucile Packard Foundation, and the Camille and
Fig. 2(b) shows a view along the < 2110 > direction showing Henry Dreyfus Foundation. L. A. V. and M. A. C. are grateful
the half-channels. Since the b channels are enclosed by four-, to the Spanish CICYT (project MAT97-0723) for financial
five- and six-membered rings, the termination results in ring support.
‘fragments’ of two or three tetrahedra, which are visible at the
bottom of Fig. 2(a). These fragments follow a periodic Notes and references
2–3–3–2–3–3 . . . sequence (abbreviated to 233), as shown in
1 C. C. Freyhardt, M. Tsapatsis, R. F. Lobo, K. J. Balkus and M. E. Davis,
the figure. At the interface plane, a b half-channel is therefore
Nature, 1996, 381, 295.
bounded by two identical 233 sequences (one on either side of 2 A. Araya and B. M. Lowe, Zeolites, 1984, 4, 280.
the half-channel) propagating down the < 2110 > channel 3 R. F. Lobo, M. Tsapatsis, C. C. Freyhardt, I. Chan, C.-Y. Chen, S. I.
direction, as indicated in Fig. 2(b). Similar termination of b Zones and M. E. Davis, J. Am. Chem. Soc., 1997, 119, 3732.
polymorph A results in the same structure at the interface. Since 4 D. V. Jorgensen and C. R. Kennedy, US Pat., 4714537, 1988.
b polymorph B is observed at the interface in Fig. 1(b), only this 5 D. M. Barthomeuf, US Pat., 4584424, 1986.
polymorph is considered in the following discussion. 6 J. M. Newsam, M. M. J. Treacy, W. T. Koetsier and C. B. de Gruyter,
There are eight polymorphs (A–H) of SSZ-31 with different Proc. R. Soc. London Ser. A, 1988, 420, 375.
connectivities down the [010] channel direction.8 The SSZ-31 7 M. A. Camblor, A. Corma, A. Mifsud and S. Valencia, Chem. Commun.,
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8 S. I. Zones, T. V. Harris, A. Rainis and D. S. Santilli, US Pat., 5106801,
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plane contains ring fragments of two or four tetrahedra, that Communication 9/00538B

922 Chem. Commun., 1999, 921–922