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Zeolites with nanometer diffusion lengths and implications
in shape selective catalysis
Aditya Bhan and Michael Tsapatsis
A long-standing synthetic challenge is to reduce the size of
zeolitic domains to its absolute minimum, the unit or sub-unit
cell dimension. Hierarchical zeolites with singe-unit or few-unit
cell zeolite domains along with methods to assess adsorption,
diffusion and reaction in these materials are reviewed.
Addresses
University of Minnesota, Department of Chemical Engineering and
Materials Science, Minneapolis, MN 55455, United States
Corresponding authors: Bhan, Aditya (abhan@umn.edu) and Tsapatsis,
Michael (tsapatsis@umn.edu)
Current Opinion in Chemical Engineering 2013, 2:320–324
This review comes from a themed issue on Reaction engineering and
catalysis
Edited by Marc-Olivier Coppens and Theodore T Tsotsis
For a complete overview see the Issue and the Editorial
Available online 10th July 2013
2211-3398/$ – see front matter, # 2013 Elsevier Ltd. All rights
reserved.
http://dx.doi.org/10.1016/j.coche.2013.06.001
The art of making zeolite hosts containing not only
ordered microporous networks but various levels of pre-
cisely engineered mesoporosity has blossomed over the
past two decades and presents a renewed opportunity to
systematically assess critical length scales involved in the
transport and reactivity of hydrocarbon molecules in
shape selective materials [1–7]. This requires in turn that
we dissect the various consequences of spatial constraints
in determining transport, adsorption, and rates of bond
making/bond cleavage processes involved in catalysis.
Here, we present a brief account of recently introduced
synthesis methods of microporous/mesoporous zeolites
by first, zeolite growth confined within a mesoporous
hard template and secondly, spontaneous rhythmic
branching by rotational intergrowth at the nanoscale
(Scheme 1). We then highlight methods to determine
site accessibility, adsorption, and transport characteristics
in these materials to rigorously assess their catalytic
behavior (Scheme 2).
Zeolite growth in three-dimensionally ordered mesopor-
ous (3DOm) carbons was introduced in 2008 [8]. It is on
the basis of a fascinating and unexpected aspect of zeolite
growth in 3DOm carbons, that single crystal growth can
propagate through numerous pore constrictions, which
have sizes comparable to that of few zeolite unit cells.
Current Opinion in Chemical Engineering 2013, 2:320–324
This method utilizes two sacrificial materials: first, 10–
50 nm monodispersed silica nanoparticles [9,10], which
are used to template the 3DOm carbons, and second, the
3DOm carbons themselves [11], which, after serving as a
hard template for growing zeolites in their pore space, are
removed by calcination to generate a network of ordered
mesopores within zeolite single crystals. These zeolite
single crystals are called three-dimensionally ordered
mesoporous-imprinted (3DOm-i) zeolites [12] to reflect
the fact that the ordered mesoporosity is imprinted by the
sacrificial carbon template. 3DOm-i zeolite synthesis
along with the dual-porogenic surfactant-driven synthesis
route [13], remain the only techniques to create three-
dimensionally ordered mesoporous molecular sieves with
zeolitic frameworks. Recently, 3DOm-i versions of struc-
ture types MFI, FAU, BEA, LTA and LTL have been
reported by lengthy but straightforward synthesis pro-
cedures [14] and it is expected that, if desired, many other
framework types can be synthesized by this approach.
3DOm-i zeolites offer certain advantages, which are
convenient for fundamental understanding through
mathematical analysis of adsorption–diffusion–reaction
phenomena. Specifically, precisely sized, arranged and
connected mesopores and, most importantly, accurate
control of micropore diffusion length tunable with nm
precision in the 10–50 nm range are only offered by
3DOm-i zeolites, while other microporous/mesoporous
zeolites are characterized by disordered mesopore size
and connectivity and a distribution of micropore diffusion
lengths. It remains to be determined if the unique struc-
tural characteristics of three-dimensionally ordered meso-
porous molecular sieves create sufficiently superior
catalytic performance of commercial significance com-
pared to that of other less ordered meso-microporous
zeolites. Even if such superior performance is identified,
cost considerations for the production of commercial
catalysts will impose the need for developing simpler
high-yield synthesis procedures without the use of
expensive sacrificial hard or soft templates. Until then,
these materials will remain only of fundamental signifi-
cance and for uses in exploratory laboratory-scale exper-
iments. On the contrary, the one-step repetitive
branching crystal growth approach described next is also
of potential practical significance.
Along with (and often closely tied to) the challenge of
making three-dimensionally ordered mesoporous mol-
ecular sieves with zeolitic frameworks another long-
standing synthetic challenge is to reduce the size of
zeolitic domains to its absolute minimum, the unit or
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Scheme 1
silica nanoparticles
3DOm-i zeolite
200 nm
20 nm
Self-pillared zeolite MFI with
single-unit-cell layers
Top panel: Synthesis of three-dimensionally ordered mesoporous-imprinted zeolites by confined growth in mesoporous carbon, templated by silica
nanoparticles [8]. Bottom panel: TEM image and schematic of idealized structure of self-pillared single-unit-cell thick zeolite layers prepared by
repetitive branching [19].
sub-unit cell dimension. At this scale and depending on
the molecular size and shape, the distinction of external
and internal surface area may even cease to exist and new
adsorption and reaction properties may emerge. Although
the achievement of zeolitic molecules remains still a
highly debated subject, few-nm-thick zeolite layers pre-
pared by pillaring and/or exfoliation of layered zeolite
precursors and their uses as catalysts and membranes
have been clearly demonstrated [5,15–18]. However, all
these approaches require post-synthesis treatment of
the layered zeolite precursor for exfoliation and/or intro-
duction of non-zeolitic pillars between the zeolite layers.
A new approach to create self-supporting single-unit-cell
zeolites was introduced in 2012 [19,20]. It is on the basis
of the phenomenon of rotational intergrowth, which is
encountered very often in zeolite crystal growth as a result
of symmetry related changes in the crystal growth direc-
tion. A well-documented example is the almost unavoid-
able 90-degree rotational intergrowth (often also referred
to as twinning) of MFI crystals. It was discovered that in a
single-step synthesis using a common structure directing
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Zeolites with nanometer diffusion lengths Bhan and Tsapatsis 321
ordered packing
3DOm carbon
Carbon + zeolite
a
c
Current Opinion in Chemical Engineering
agent (tetrabulyl ammonium or phosphonium hydroxide)
repetitive twinning creates a branched structure that
resembles a house-of-cards arrangement of orthogonally
connected single-unit-cell zeolite MFI layers. The diffu-
sion length along the layer thickness is 2 nm (one unit cell
along the b-axis of MFI) while the mesopores created
between branching points are in the 2–7 nm range. This
remarkable structure is a result of non-equilibrium growth
created by a self-sustained rhythmic branching without
any external intervention or forcing. We have speculated
that the MFI plates are connected with MEL single-unit-
cell needles but definite proof by transmission electron
microscopy is yet to be obtained. Branched microstruc-
tures with thicker layers and more distant branching
points have been encountered before and recently, they
have been purposefully explored for the design of hier-
archical materials on the basis of FAU [21,22] and MFI
[23] frameworks. In these cases, self-pillared macropores
rather than mesopores are created between the (thicker)
layers. In all other respects, the self-pillared morphologies
and the underlying crystal growth phenomena are
Current Opinion in Chemical Engineering 2013, 2:320–324
322 Reaction engineering and catalysis

Scheme 2

Titration of zeolitic materials

Titrant uptake → quantitative assessment of the internal and external Brønsted acid sites

Titration by organic Titration by bulky

bases organic bases

N
N
+
H
-
O Si
Al
Internal Brønsted
External Brønsted +
acid site
acid site H
-
O Si
Al
+ +
NH NH
- -
O Si O Si

Al Al

+ +
NH H
- -
O Si O Si
Al Al
Titrates both the external Titrates only the external
and internal acid sites acid sites
Solid acid catalyzed reactions
Catalytic rates → accessibility and reactivity
Inhibition of reaction rates by diffusion → diffusivities applicable during reaction

OH
+
+
H
-
O Si
Al
On external surface
+
H
On internal micropores O
-
Si
Site-accessibility in meso- and Al
micro-porous environments and
quantitative assessment of OH OH O
internal and external acid sites +

Current Opinion in Chemical Engineering

Titration and chemical reaction as probes of accessibility and reactivity in zeolites possessing mesoporosity and microporosity.

remarkably similar. The repetitive branching method is
simple, scalable, and cost effective. In principle, it is
applicable for the numerous zeolite structures that can
exhibit rotational intergrowths and it can provide inde-
pendent control of diffusion length (by variation of layer
thickness) and mesopore size (by changing the frequency
of branching by intergrowth).
Structural characterization of the materials obtained by
the above and other methods of hierarchical zeolite
synthesis is usually performed by X-ray diffraction and
electron microscopy techniques. The catalytic properties
are then determined by comparing their performance
(reaction rate, selectivity, deactivation behavior, etc.) in
reactions involving bulky molecules, which are expected
to encounter diffusion limitations. Often, this approach,
by aiming to demonstrate improved function of the
hierarchical over the conventional compact zeolite cata-
lysts, does not provide detailed characterization of the
active sites or a quantitative description of the catalytic
performance on the basis of adsorption-diffusion and
reaction events. Next, we provide a discussion of certain
active site characterization methods that can be useful in
assessing quantitatively diffusion and reaction in hier-
archical zeolites (Scheme 2).
The encapsulation and accessibility of hydroxyl/metal
centers in zeolite scaffolds can be directly and precisely
probed by use of chemical titrants, if possible, during
catalysis. The titration of acid sites by organic bases in
ethanol dehydration reactions on MWW and MFI meso-
porous/microporous materials was monitored by both the

Current Opinion in Chemical Engineering 2013, 2:320–324 www.sciencedirect.com

 Zeolites with nanometer diffusion lengths Bhan and Tsapatsis 323
titrant uptake and the decrease in dehydration rates to
infer stoichiometric titration and accessibility of sites [24].
This approach has been used in dehydration, etherifica-
tion, and alkylation reactions to delineate site accessibil-
ity from mesoporous and microporous environments, the
site requirements for parallel reactions in zeolites, and the
role of ion exchange moieties and extralattice Al species
[19,24–29]. The same methodology with the use of
organo-sulfur titrants translates to inferring the seques-
tration of active metal centers in zeolites [30,31].
The hierarchical structure of zeolites possessing dual
mesoporosity and microporosity also results in these
materials possessing a much larger external surface area
and a commensurate fraction of external acid sites
compared to conventional zeolite materials. Titration
methods provide a quantitative assessment of the num-
ber of external acid sites and the catalytic rates they
engender. Using 2,6-di-tertbutyl pyridine as a titrant for
external acid sites on self-pillared, 3-dimensionally
ordered mesorporous-imprinted materials (3DOm-i),
and conventional MFI materials, we have reported that
the rate for alkylation reactions of mesitylene by benzyl
alcohol is invariant when normalized per external acid
site; the concentration of external acid sites in these
materials varies over a range of four orders of magni-
tude [19]. These direct probes of the number and
accessibility of active sites can be compared with the
estimates from ex situ methods, such as temperature
programmed reaction or nuclear magnetic resonance
based techniques, to ensure proper normalization of
catalytic rates by the number of active sites probed
during reaction.
The measurement of catalytic rates provides a direct
measure of both accessibility and reactivity in these
materials. The seminal work of Haag and co-workers
[32] using crystallites of different sizes and Si/Al ratio for
cracking of C6–C9 hydrocarbons on HZSM-5 provided a
clear assessment of mass flow induced concentration
gradients being inconsequential for reactions of linear
hydrocarbons. For materials possessing dual mesopor-
osity and microporosity however, the contributions for
external and internal sites need to be distinguished.
Using a combination of chemical titration methods
and on the basis of measured rates of ethanol dehy-
dration, monomolecular C3–C4 alkane activation, and
benzyl alcohol esterification and alkylation, our recent
reports have noted that the rate normalized per acces-
sible acid site is invariant for both external and internal
H+ sites in MFI materials possessing hierarchical por-
osity [19,24]. For the activation of small molecules, the
catalytic behavior of Brønsted acid sites in materials
with dual mesoporosity/microporosity is dominated by
the microporous environment because of preferential
adsorption of these molecules within the micropores
mediated by confinement.
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Mass transport-induced changes in rate, selectivity, and
stability are postulated as the critical effect of introducing
mesoporosity in zeolite-catalyzed systems. In the absence
of mathematical models or a comparison with model
reaction systems, however, the specific effects of intro-
ducing porosity on the nanometer length scale on trans-
port and reactivity remain elusive and subject to
contradictory interpretation. As discussed by Haag and
coworkers [32], in contrast to assessing diffusivity from
the non-steady state sorption characteristics measured at
temperatures that are not characteristic of catalytic reac-
tion conditions, a determination of the inhibition of
reaction rates by diffusion provides a quantitative
measure of diffusivities applicable during catalysis. Our
recent report [19] highlights the critical role of transport
for the etherification and alkylation reactions of benzyl
alcohol to provide both an assessment of transport and
rate per active and accessible catalytic center. The
observed rates for benzyl alcohol etherification normal-
ized per proton increase by a factor of 103 for HMFI
samples with crystallite sizes ranging from 2-nm sheets in
self-pillared pentasil materials to 17 mm in diameter. This
observed variation in rates can be described using a
classical reaction diffusion model to infer that mass-trans-
port limitations, described by a single value of the micro-
pore effective diffusion coefficient for both meso-micro
and only microporous MFI materials, result in the
observed variation in measured rates. In the case analyzed
in [19], mesopore resistances appear to be negligible but
in other cases they may have to be accounted for. The
applicability of reaction–diffusion models can be
extended to acid-catalyzed hydrocarbon chemistries com-
prising series–parallel networks by comparing the rates of
a probe reaction such as hexane cracking or benzyl alcohol
etherification to that of the complex acid chemistry in
materials possessing a range of crystal sizes and hence,
relevant diffusion lengths.
The prospect of combining shape-selective catalysis with
enhanced transport has primarily stimulated the synthesis
of zeolites possessing mesoporosity. While the majority of
scientific publications and patents in this field continue to
highlight and detail the synthesis of materials, an increas-
ing effort is directed toward comparing the rates, selec-
tivity, and lifetime of zeolites possessing mesoporosity
with that of their ‘parent’ compact microporous material.
We hope that the methods highlighted here concerning
the synthesis of ordered mesoporous/microporous zeolites
and self-pillared single unit-cell zeolites and the rigorous
assessment of rates of chemical and physical rate pro-
cesses will contribute to addressing outstanding questions
related to the role of dual mesoporosity and microporosity
in catalytic systems. They need to be combined with
descriptions of mass transport at the reactor and catalytic
pellet scale [33] and assessment of long-term structural
stability of these more complex and possibly more sensi-
tive zeolite catalysts.
Current Opinion in Chemical Engineering 2013, 2:320–324
324 Reaction engineering and catalysis
Acknowledgement
This work was supported as part of the Catalysis Center for Energy
Innovation, an Energy Frontier Research Center funded by the U.S.
Department of Energy, Office of Science, Basic Energy Sciences under
award # DE-SC0001004.
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