A new layered MWW zeolite synthesized with the bifunctional surfactant template and the updated classification of layered zeolite forms obtained by direct synthesis

Article abstract of DOI:10.1039/C8TA09826C

The medium pore-size zeolite MWW is very valuable as an industrial catalyst for aromatic alkylation and the first zeolite identified in the layered form. It shows extraordinary diversity by producing a great variety of different layered structures and forms: so far about 15 obtained by direct preparation and post-synthesis modifications, with 18 altogether recognised for all layered zeolites. We report a new layered MWW material, denoted UJM-1P (Uniwersytet Jagiellonski Material #1), which was obtained by prolonging synthesis of the mono-layered MWW material reported earlier, MIT-1. This transformation is new but not totally surprising. MIT-1 was obtained by using a special bifunctional structure directing agent (SDA) containing adamantyl head group and a long hydrocarbon chain. This strategy was applied first to produce by design layered forms of one of the most important zeolites-MFI. The MWW framework was previously obtained by direct synthesis in 5 different forms that could be rationalized by particular layer arrangements. MFI added 3 more types with two prepared, before MIT-1, with the aforementioned bifunctional SDA. MIT-1 and UJM-1P (as synthesized) and UJM-1 (calcined) are analogues of these layered MFI materials and are considered as the 6^th and 7^th MWW forms obtained by a direct one-pot preparation. UJM-1P has a multilayered slightly expanded structure similar to MCM-22P by with extensive layer disorder. It is easier to swell with surfactants than MCM-22P, which indicates weak interlayer connection that may be due to the special SDA molecules lining the surface of its layers. This is promising for delamination and formation of colloidal dispersions of MWW mono-layers. UJM-1 was confirmed to be a very active solid acid catalyst showing high concentration of Br?nsted acid sites of about 900 μmol g^?1. It was tested in the mesitylene alkylation reaction showing high activity comparable to MCM-56, while MIT-1 was about 50% less active.

Full text of DOI:10.1039/C8TA09826C

View Article Online
View Journal
Journal of
M at erials Chemistry A
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Grzybek, W. J.
Roth, B. Gil, A. Korzeniowska, M. Mazur, J. ejka and R. Morris, J. Mater. Chem. A, 2019, DOI:
1
0.1039/C8TA09826C.
Volume
4
Number
1
7
January 2016 Pages 1–330
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Journal of
Materials Chemistry A
Accepted Manuscripts are published online shortly after
Materials for energy and sustainability
www.rsc.org/MaterialsA
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
rsc.li/materials-a

Page 1 of 9
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
View Article Online
DOI: 10.1039/C8TA09826C
Journal of Materials Chemistry A
ARTICLE
A new layered MWW zeolite synthesized with the bifunctional
surfactant template and the updated classification of layered
zeolite forms obtained by direct synthesis
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
b,c
DOI: 10.1039/x0xx00000x
Justyna Grzybek, Wieslaw J. Roth,* Barbara Gil, Aleksandra Korzeniowska, Michal Mazur, Jiři
b
b,c
Čejka, and Russell E. Morris
www.rsc.org/
The medium pore-size zeolite MWW is very valuable as an industrial catalyst for aromatic alkylation and the first zeolite
identified in the layered form. It shows extraordinary diversity by producing a great variety of different layered structures
and forms: so far about 15 obtained by direct preparation and post-synthesis modifications, with 18 altogether recognised
for all layered zeolites. We report a new layered MWW material, denoted UJM-1P (Uniwersytet Jagiellonski Material #1),
which was obtained by prolonging synthesis of the mono-layered MWW material reported earlier, MIT-1. This
transformation is new but not totally surprising. MIT-1 was obtained by using a special bifunctional structure directing
agent (SDA) containing adamantyl head group and a long hydrocarbon chain. This strategy was applied first to produce by
design layered forms of one of the most important zeolites - MFI. The MWW framework was previously obtained by direct
synthesis in 5 different forms that could be rationalized by particular layer arrangements. MFI added 3 more types with
two prepared, before MIT-1, with the aforementioned bifunctional SDA. MIT-1 and UJM-1P/1 are analogues of these
layered MFI materials and are considered as the 6th and 7th MWW forms obtained by a direct one-pot preparation. UJM-
1
P/1 has a multilayered slightly expanded structure similar to MCM-22P by with extensive layer disorder. It is easier to
swell with surfactants than MCM-22P, which indicates weak interlayer connection that may be due to the special SDA
molecules lining the surface of its layers. This is promising for delamination and formation of colloidal dispersions of MWW
mono-layers. UJM-1 was confirmed to be a very active solid acid catalyst showing high concentration of Brønsted acid sites
of about 900 μmol/g. It was tested in the mesitylene alkylation reaction showing high activity comparable to MCM-56,
while MIT-1 was about 50% less active.
have been obtained by 3 basic approaches:12 conventional
(zeolite) hydrothermal synthesis usually with organic additives
as structure directing agents (SDA), degradation of zeolites
Introduction
Zeolites are a special class of inorganic materials, initially
aluminosilicates, with microporous framework structures
that show exceptional activity as heterogeneous catalysts for
1
3
1
4, 15
with built in weaknesses called ADOR strategy,
using special bifunctional SDAs with surfactant tails.
and by
1
,2
1
6,17
The
nd
last method was invented to synthesize by design the 2 most
important and valuable zeolite ZSM-5/MFI as a layered
3
,4
conversion of organic compounds. The development of
zeolites started expansion in a new direction in the 1990s with
the surprising discovery that they can form layered
1
6
structure.
5
-7
structures, similar to 2-dimensional solids and thus called 2D
zeolites.8 Originally zeolite frameworks were viewed as
Bifunctional surfactant templates Unilamellar
Multilamellar
9
+
exclusively fully connected 3D structures. Zeolite layers are
molecularly thin, up to about 3 nm and so far a have been
produced by about 20 out of 240 known frameworks.
+
N
MFI
CH (CH )
N
MFI
3
2
n
1
0,11
They
+
+
N
CH (CH )
N
3
2
n
MWW , MIT-1
MWW , UJM-1P
a. Faculty of Chemistry, Jagiellonian University in Kraków, Gronostajowa 2, 30-387
Kraków, Poland e-mail: wieslaw.roth@uj.edu.pl
Department of Physical and Macromolecular Chemistry, Faculty of Sciences,
Figure 1. Bifunctional surfactant templates used for the synthesis of MFI and
2
MWW layers by design. N atoms are connected by 4-6 CH groups. The 'n' in the
b.
side chain are usually 20 for MFI and 14 for MWW with the total length of 22 and
16 carbon atoms.
Charles University, Hlavova 8, 128 43 Prague 2, Czech Republic
EaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST,
c.
UK
The bifunctional SDAs, shown in Fig. 1, consisted of a
quaternary ammonium head group templating the framework
and a long hydrocarbon tail designed to prevent framework
Electronic
DOI: 10.1039/x0xx00000x
Supplementary
Information
(ESI)
available:
See
This journal is © The Royal Society of Chemistry 20xx
J. Mater. Chem. A , 2018, 00, 1-3 | 1
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 2 of 9
ARTICLE
Journal of Materials Chemistry A
rd
propagation in the 3 dimension. By using various head groups variation of crystal habits. Zeolite MWW was initially obtained
View Article Online
with tails of different length and changing synthesis conditions by direct synthesis in 5 different forms, DclOeIa: r1l0y.10d3is9t/iCn8gTuAi0s9h8a2b6lCe
two basic types of layered MFI materials were obtained: an by visibly different XRD patterns, shown in Fig 3. MFI
1
8
11
apparent house-of-cards structure consisting of mono-layers
contributes additional 3 different forms. Thus, various
and multi-layered crystals with interlayer gallery heights of layered zeolites and their different forms that can be
1
9
approximately 2-4 nm. These were breakthrough results synthesised directly represent an important group worth
fundamentally and very promising for catalysis.
separate attention. They are expected with other topologies
besides MWW and MFI but so far have been limited to
basically one 2D precursor and the 3D form. The paper
Initial
mono-layered
product
Final
25
as-synthesized
product
100
proposes formally defined various layered zeolite forms based
on recognised differences. It can be used for further analysis
and validation, possible expansion into new forms and
replication with other topologies. Aside from the fundamental
importance, the directly synthesised zeolite materials are
significant as potentially more convenient and economical for
scale-up and development in clear self-evident preference to
more laborious and often expensive post-synthesis
New (002)
UJM-1
MIT-1
UJM-1P, 2D
UJM-1
multi-layered, Calcined,
UJM-1P
d>2.6 nm
d=2.5 nm
prolonged
synthesis
MIT-1
MIT-1 calc
MCM-56 (as synth.)
prolonged
synthesis
2
6
MCM-56
modifications.
MCM-49
D condensed
d=2.5 nm
3
MCM-49 (as synth.)
5
10
15
20
25
30
2
theta, deg.
Figure 2. Representative XRD patterns showing transformation of MIT-1 to UJM-
1
P, indicated by the new (002) peak, and comparison with MCM-56. MIT-1
shows onset of the (002) reflection at 6.5°2-θ as possible UJM-1P 'impurity'. The
broad peak at ca. 4.5°2-θ for calcined MIT-1 is assigned to kenyaite impurity.
4
peaks
3 peaks
This strategy was extended recently to the synthesis of mono-
layers of zeolite MWW, which produced a material with the
house-of-cards structure, denoted MIT-1 by Roman-Leshkov et
5
6
7
8
9 10 11 12
5
6
7
8
9 10 11 12
2
0
al. Zeolite MWW contains 2 independent medium size
channels with large cavities and is an outstanding catalyst used
2
peaks
1 peak
2 peaks
8.5°band
8-10°band
8-10°band
2
1
commercially for aromatic alkylation. It provided the initial
2
2
discovery of layered zeolites and, as elaborated later, has
produced several layered forms by direct synthesis, including
5
6
7
8
9 10 11 12
5
6
7
8
9 10 11 12
5 6 7 8 9 10 11 12
8
the mono-layer material designated MCM-56. MIT-1 showed
promising activity as a catalyst for alkylation of benzene with
benzyl alcohol, which was better in comparison to other MWW
2
0
materials including layered. We have found that MIT-1 is a
transient product. As its crystallization is prolonged, a new
peak begins to grow in the XRD of the solid product at 6.5° 2-θ forms: the initial five with UJM-1P and MIT-1 at the bottom. The XRD
5
6
7
8
9 10 11 12
5 6 7 8 9 10 11 12
Figure 3. XRD patterns differentiating various as-synthesized MWW layered
comparison with the calcined versions, i.e. finally used catalyst, is provided in
(Cu Kα radiation, used throughout) as shown in Fig. 2. It can be ESI.
recognised as the (002) reflection characteristic for expanded
multi-layered MWW materials, such as MCM-22P and EMM-
1
0P. We denoted this product UJM-1P. Just like these two
Experimental
expanded multilamellar MWW materials it contracts upon
calcination to about 2.5 nm, which is indicated by
disappearance of the peak at 6.5° 2-θ;
is named UJM-1. In this case the bifunctional SDA fulfils its role
to thwart expansion of the framework structure in the 3
2
3,24
the calcined product
Synthesis
rd
15
Preparation of the structure directing agent (SDA) – C10H -
+
+
3 2 4 8 3 2
dimension, but it does not inhibit layer stacking. This is similar N (CH ) -C H -N (CH ) -C16H33 (Ada-4-16)
to the MFI syntheses except that with UJM-1P the interlayer
distance is much smaller.
The synthesis was carried out in three steps according to the
published procedure. In the first step, 1-adamantylamine (15
20
This report has two objectives. First, specific, is to present the
synthesis, properties and catalytic activity of UJM-1P as a new
member of the MWW zeolite family. Second, more general,
has to do with the fact that because zeolites can grow as layers
they can be obtained in different (layered) forms by direct
synthesis, as illustrated by MWW and MFI. Conventional
zeolites afford only one type of structure – 3D framework
extended continuously in all directions with the possible
g, 97%, Sigma Aldrich) was dissolved in formaldehyde (23.42 g,
3
7%, Sigma Aldrich) and heated to 373 K under reflux. Formic
acid (14 g, 95%, Sigma Aldrich) was added to this mixture
dropwise with an addition funnel in the span of 2 hrs and the
mixture refluxed for another 3 hrs. The solution was allowed
to cool to room temperature and adjusted to pH = 12 with
sodium hydroxide solution (50%, Sigma Aldrich). The product,
2
| J. Mater. Chem. A, 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal of Materials Chemistry A
ARTICLE
dimethyl-1-adamantylamine (Ada-N(Me)
extracted from the mixture with diethyl ether and dried with collected with steps of 0.02 .
2
View Article Online
), was liquid-liquid radiation (ʎ = 0.154 nm). The XRD patterns were usually
o
DOI: 10.1039/C8TA09826C
potassium carbonate (99 wt.%, Sigma Aldrich). The ether Nitrogen adsorption isotherms were determined by the
solvent was removed by rotary evaporation. The obtained standard method at 77 K (liquid nitrogen temperature) using
white solid was dried overnight at room temperature, yield an ASAP 2025 (Micromeritics) static volumetric apparatus.
1
8
4%. Its composition as Ada-N(Me)
NMR. Next, 14.48 g of Ada-N(Me)
157.9 g, 99%, Sigma Aldrich) were dissolved in 362 ml of TEM images and SAED diffraction patterns were recorded
acetonitrile (anhydrous 99.8%, Sigma Aldrich) and refluxed at using Titan Themis 200 transmission equipped with an X-FEG
55 K for 16 h. The solvent was removed by rotary Schottky field emission gun at 200 keV. The microscope is
2
was confirmed by H Before adsorption the samples were outgassed at 623 K using
2
and 1,4-dibromobutane turbomolecular pump to remove adsorbed water.
(
3
+
-
2
evaporation. The product (Ada-N (Me) -4-Br,Br ) was equipped with 16 mega-pixel CMOS camera and was aligned
recrystallised from dichloromethane and washed with diethyl using standard gold sample methods.
ether. It was a white solid obtained with 56% yield. Relative content of Al and Si was determined in the samples
+
-
1
Ada-N (Me)
2
-4-Br,Br composition was verified by H NMR. formulated into pellets, 20 mm in diameter, with the use of
+
-
1
7.97
g
of
2
Ada-N (Me) -4-Br,Br
and Energy-Dispersive XRF spectrometer (Thermo Scientific, ARL
N,N-dimethylhexadecylamine (37.39 g, 95%, Sigma Aldrich) QUANT’X). The X-rays of 4-50 kV (1 kV step) with the beam size
were dissolved in 450 ml of acetonitrile, and refluxed at 355 K of 1 mm were generated with the Rh anode. The detector used
for 18 h. The solvent was removed by rotary evaporation and was a 3.5 mm Si(Li) drifted crystal with a Peltier cooling (ca.
the product in bromide form was washed with diethyl ether. 185 K). For quantitative analysis, calibration with a series of
1
13
Ada-4-16 composition was verified using H and C NMR. The metallic standards and UniQuant software were used.
final product was converted from the bromide to hydroxide The concentration of Lewis (LAS) and Brønsted (BAS) acid sites
form using hydroxide exchange resin (Ambersep 900 OH, Alfa was determined using adsorption of pyridine (Py) followed by
Aesar) in water. A small portion was titrated using HCl to IR spectroscopy (Tensor 27 from Bruker, MTC detector,
-
-1
determine OH concentration.
spectral resolution 2 cm ). Zeolites were pressed into self-
2
supporting wafers with a density of ca 8 mg/cm and activated
-5
in situ at 723 K for 1 hour at high vacuum (10 mBar). Excess of
pyridine vapour was adsorbed at 443 K followed by desorption
for 20 min at 442 K. Spectra were recalculated to a wafer mass
equal 10 mg. Concentration of Lewis (LAS) and Brønsted (BAS)
acid sites were evaluated from the intensities of bands at 1454
(LAS) and at 1545 cm
coefficients determined earlier in our laboratory using external
standards, ε(LAS) = 0.165 cm /μmol, and ε(BAS) = 0.044
cm /μmol, and the intensities of corresponding pyridine
Preparation of zeolites
Both MWW materials, MIT-1 and UJM-1P, were obtained from
similar mixtures of composition 1SiO
Al(OH) /0.2 NaOH/45 H O by the standard hydrothermal
procedures.
As the first step, a weighted amount of the template was
dissolved in water and converted to the hydroxide form by
mixing with ion exchange resin. The obtained aqueous solution
of Ada-4-16 (in hydroxide form) was combined with NaOH
2
/0.1 OSDA/0.05
3
2
−1
−1
cm
(BAS) using absorption
29
2
2
maxima after pyridine desorption at 443 K to ensure complete
removal of weakly adsorbed species.
(
50%, Sigma Aldrich), aluminium hydroxide (Sigma Aldrich),
colloidal silica (LUDOX® LS 30) and stirred over 4h at room
temperature. The gel was transferred to a Teflon liner, sealed
in the pressure bomb and held at 433 K with rotation for 7-10
and 14 days, respectively. The solids were recovered by
Catalytic testing
filtration, washed with deionised H
overnight.
2
O, and dried at 338 K for Preparation of catalysts
+-form, with 1
4
Calcined samples were ion exchanged into NH
3
M solution of NH NO (Avantor Poland, p.p.a.) for 1 h at room
The syntheses of MCM-22P and MCM-5628 were reported
27
4
elsewhere.
temperature (20 ml of solution per 0.5 g of zeolite), repeated
three times, filtered, washed with deionised water, dried, and
activated at 723 K for 5 h.
Solids were calcined by heating under flowing N
K/min with a 1 h hold at 423 K, a 2 h hold at 573 K, and a 3 h
hold at 813 K. The flowing gas was then switched to dry air and
the temperature was held at 813 K for another 6 h.
2
at a rate of
2
Catalytic tests
The test reaction - liquid phase benzylation of mesitylene with
benzyl alcohol (Fig. 4) was carried out in a three-necked round-
bottom flask equipped with a reflux condenser with heating in
a multi-experiment workstation StarFish (Radleys Discovery
Technologies) under atmospheric pressure. The reaction
temperature was 353 K. Typically, 130 mmol of mesitylene
Characterization methods
The structure and crystallinity of obtained zeolites were
evaluated by X-ray powder diffraction (XRD) using a Bruker
AXS D8 Advance diffractometer equipped with a graphite
monochromator and a position sensitive detector (Våntec-1)
using CuK radiation in Bragg–Brentano geometry and Rigaku
α
MiniFlex diffractometer in reflection mode, using CuK
(15.5 g) was combined with 50 mg catalyst and dodecane as an
internal standard. The reaction mixture was maintained for 30
α
This journal is © The Royal Society of Chemistry 20xx
J. Mater. Chem A, 2013, 00, 1-3 | 3
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 4 of 9
ARTICLE
Journal of Materials Chemistry A
min at the required reaction temperature and then 1 mmol of produce the complete 3D framework13 with 3ViewpAeraticklesOnlilkinee
benzyl alcohol was added. This was regarded as the start of above. The precursor is the most commoDnOaI:n1d0.1u0s3u9a/Clly8TtAh0e98o2n6lCy
reaction time. Liquid samples were withdrawn at regular layered form known with other frameworks (about 20).
intervals and analysed by the gas chromatography Agilent Sometimes simple calcination does not give an ordered
7
820A GC with an FID detector using a 30 m packed DB-5 complete framework but often the precursors can be modified
3
1
column. The conversion of alcohol was calculated as follows:
by intercalation and then may condense giving a zeolite. The
remaining 3 MWW species have broad bands instead of the
S
alcohol
(101) and (102) peaks, which is interpreted as due to lateral
conversion = k ∙
∙ 100%
S
standard ∙ n
0
layer disorder.
The known layered forms of ZSM-5/MFI are different from the
where S is the area of respective peak in the chromatogram, k 4 layered MWW ones discussed above. Unlike MWW, MFI has
is the calibration coefficient (mol), n
alcohol (mol).
0
is the starting amount of no comparable XRD features for structure differentiation, so
the definitions are based on additional evidence. None of the 3
MFI materials is a 'layered MFI zeolite precursor' sensu stricte,
i.e. condensing into complete framework. Two are recognised
as produced from a novel type of building blocks, namely
1
6
layers incorporating the special bifunctional SDA intended to
prevent structure propagation in 3D. As mentioned above they
1
8
are the unilamellar 'house-of-cards' and multilayered stacks
1
6
rd
of MFI nanosheets. The 3 unique product called self-
3
2
pillared, consists of MFI sheets intergrown at right angles. It
is produced due to the ability of MFI and MEL framework to
form continuous combinations. Post-synthetic modifications
afford additional layered zeolite derivatives, quite valuable,
like pillared, delaminated, stabilised precursors and others, but
those obtained by one-pot syntheses are particularly
significant. As mentioned they are important fundamentally
and may be more attractive for practical implementation and
therefore deserve special attention.
3
3
Figure 4. Alkylation of mesitylene with benzyl alcohol.
Results and discussion
The description of the various MWW/MFI structures can be
summarized in the following way clarifying their
order/disorder. When a definable (00l) reflections, especially
Various layered zeolite forms by direct synthesis
The MWW and MFI frameworks provide collectively 8 various (002) for MWW, are observed (MCM-22P/22, MCM-49, EMM-
layered forms by direct synthesis, not overlapping except for 10P, SSZ-70, UJM-1P/1, multi-layered MFI) an equidistant
the 3D framework. They always contain the same basic unit, a stacking with obvious fluctuations indicated by the width of
layer with the MWW of MFI structure, with different order and these reflections, is assumed. The a-b order (MCM-22, -49) and
packing in the a-b and c-directions. Five different layered pseudo-order, defined in relation to the complete 3D
MWW forms were obtained in the past by slight changes in the framework, is indicated by the distinct (101) and (102)
synthesis mixture compositions, like changing Al and base reflections near 8 and 10 deg. 2-theta. The alternative profiles
8
, 30
content, and sometimes with different templates.
They can in this range (broad and triangular peaks) are interpreted as
be clearly differentiated based on visually different XRD signs of disorder or stacking faults. MIT-1 and unilamellar MFI
patterns, especially in the range 6-10 deg. 2-theta, with are disordered in all directions and MCM-56 to some extent. It
various combinations of discrete peaks and broad bands, as must be appreciated that these interpretations are qualitative
shown in Fig. 3 and the Table 1. This is possible due to and the simplest ones explaining the observed XRD features.
fortuitous location of intra- and inter-layer peaks in this range The proposed structures are idealised models and in the case
and may not be so easy with other zeolites. The proof that of MWW are consistent with the observed XRD features. They
these materials are indeed MWW layers is provided by the are effectively end-members, while in practice formation of
characteristic intralayer reflections (100), (220) and (310) at mixture is likely and is to be expected. On the other hand
7
.1 (strong), 25 (medium), and 26 (strong) degrees 2-θ. The conditions for producing fairly pure phases are known. The
XRDs can be rationalised starting from the basic MWW zeolite proposed rationalization for the MWW family is qualitative
2
2
structure (MCM-49, MCM-22 calcined). It shows 3 peaks: one and self-consistent but alternative explanations are not ruled
is composed of the overlapping pure interlayer (002) and out. Calculations of XRD patterns for mixtures of ordered and
3
4
intralayer (100) and the others are (101) and (102). The randomly dis-ordered layers in-plane were carried out
expanded MCM-22P layered precursor shows 4 peaks as the confirming some the experimentally observed features, but
002) is shifted to lower 2-θ (d-spacing >2.6 nm). It is formally this work did not include the expanded MMW structures.
(
recognised as 'layered (zeolite) precursor', a slightly expanded
structure, which condenses topotactically with contraction to
4
| J. Mater. Chem. A, 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal of Materials Chemistry A
ARTICLE
Based on the XRD pattern shown in Fig. 3, and by comparison
to MCM-22P the as-synthesised UJM-1P is identified as
disordered (unaligned vertically) multi-layered MWW zeolite
UJM-1P and MIT-1 as new types of MWW
materials
View Article Online
DOI: 10.1039/C8TA09826C
UJM-1P and MIT-1 show XRD patterns qualitatively similar to with expanded interlayer spacing, around >2.6 nm, revealed by
th
the (002) reflection at ca 6.5° 2-θ. In short, it is roughly like the
'layered MWW precursor' MCM-22P but with disordered layer
EMM-10P and MCM-56 but can be counted as distinct 6 and
7
th
MWW representatives forming by direct synthesis. This is
justified by their formal similarity to the MFI analogues, i.e. stacking. Based on the reported model for MIT-1, the layers
being composed of the particular type of building units – layers are assumed to be lined with organic parts of the SDAs
with embedded bifunctional surfactant SDAs. This may be resulting in greater lateral disorder and easier swelling (vide
revised in the future but so far there are no well-defined or supra) in comparison to the other multilayered expanded
formal criteria for distinguishing/classifying various new MWW (MCM-22P, EMM-10P). Just like the latter, it also
layered materials and structures. Qualitative XRD contracts to ca. 2.5 nm repeat upon calcination. The broad
differentiation seems inadequate in this situation when little is band at 8-10° 2-θ remains with no dip in the middle indicating
2
3
known about layered zeolites in general so additional factors preservation of the original layer stacking disorder.
can be considered and greater latitude for interpretation UJM-1P is obtained from the mono-layered MIT-1, which has
should be allowed. In, addition, as described below, both of XRD pattern similar to MCM-56. As-synthesized MIT-1 shown
these materials show some unique properties, especially with here (only calcined pattern provided in the original Roman-
regard to layer disorder and swelling capacity, which further Leskov article) has a small, broad peak around 6.5° 2-θ
justifies separate treatment until all MWW species are better reminiscent of the (002) reflection present in as-synthesised
characterised.
It should be mentioned that other materials equivalent to of MIT-1 because simulations of the XRD patterns of MWW
multilayered MWW zeolites. It is unlikely an inherent feature
2
0
EMM-10P/-10 were reported with other SDAs and include: IPC- single-layer have no such feature, nor is it seen with MCM-
56. It should be assumed that this is an emerging peak due to
3
5
36
37
3
P, ITQ-30, and hexamethonium MCM-22. There is a
report of direct synthesis of a swollen MWW material with the onset of UJM-1P formation. The conversion of MIT-1,
mono-layers separated by surfactant with interlayer distance which is apparently an intergrowth of mono-layers, to UJM-1P
of ca 2 nm.38 However, the preparation entails dissolution of
occurs most likely by recrystallization and not by layer
another MWW material (ITQ-1) as substrate so it is not strictly restacking. It resembles the transition from MCM-56 to MCM-
a genuine one-pot preparation from scratch, but a 2-step 49, see Fig. 2, with some differences. The latter is a transition
procedure, so it will not be considered for now. MWW from mono-layers to complete 3D framework, while MIT-1
material denoted DS-ITQ-2, similar to MIT-1 was also converts not into a framework but the multi-layered expanded
reported.39
product UJM-1P. It can be again attributed to the bulky SDAs
preventing framework propagation in the 3 dimension.
rd
UJM-1P structure and its formation from MIT-1
Table 1. Layered zeolite forms synthesised directly based on MWW and MFI frameworks. Letter 'P' for 'precursor' or uncalcined forms is not used universally and consistently in
the literature. The red line vertical line marks the (100) reflection. Abbreviations: SDA – structure directing agents, HMI – hexametheleneimine, diquat – diquaternary ammonium
XRD-MWW
MWW
Other
zeolites
Building Layeredzeolite form - proposed
blocks (‘→’ - change upon calcination)
Structure
as-synth. calc.
XRD 6-10°,
MWW interlayer distance (nm);
MFI
as-synthesized
materials;
typical SDA
MWW as-synth. vertical layer alignment, bonding
materials
(100)
3
-D framework by direct
3 peaks
4 peaks
2.5 – not expanded; aligned and
fused, continuousin 3D
MCM-49 as,calc;
ZSM-5,
silicalite-1
>230
frameworks
synthesis;layers fused congruent.
C
6
H
12NH -HMI
Pseudo-ordered multi-layered
precursor →ordered 3D structure
Partly-ordered multi-layered
→
>2.6 - expanded; aligned; H-bond
connected
MCM-22P/22;
HMI
>15
frameworks
-
-
-
-
2 peaks
+broad at 9°
>2.6 - expanded; shifted
1/3x+2/3y; H-bond connected
SSZ-70; ICNP-5;
imidazolium
FER (ECR-12)
NSI (EU-20)
incomplete or disordered
Disordered multi-layered
disordered
Disordered mono-layered
unilamellar); delaminated,
Multi-layered with surfactant
single-unit-cell nanosheets)
2 peaks
>2.6 - expanded, misaligned; H-
EMM-10P/10;
UZM-8; diquat
-
-
-
-
-
→
+broad at 8-10° bond connected
1 peak
2.5 - not expanded; unaligned;
MCM-56; HMI
(
+broad at 8-10° not connected
2 peaks,
+broad at 8-10° organiclined
>2.6 - expanded, misaligned;
UJM-1P/1;
bifunctional
Multilamellar
nanosheets
(
Mono-layered with surfactant;
house-of-cards
1 peak
2.5; random layers - intergrown
MIT-1;
bifunctional
Unilamellar
nanosheets
+broad at 8-10° organiclined
Self-pillared
MFI-MEL
Self-pillared
MFI – intergrown at 90°
None
The present material UJM-1P is considered to be an analogue
1
6
of the multi-layered MFI because of similarly designed
template resulting in similar 'layer-with-surfactant' building
blocks. There are differences between them, which is
UJM-1P vs. the MFI analogue
This journal is © The Royal Society of Chemistry 20xx
J. Mater. Chem A, 2013, 00, 1-3 | 5
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 6 of 9
ARTICLE
Journal of Materials Chemistry A
appropriate to discuss now. There are vastly different This is a standard tool for proving layered nature of 2D
View Article Online
DOI: 10.1039/C8TA09826C
6
interlayer distances in UJM-1P and layered MFI, i.e. 0.2 nm vs. materials and to obtain more porous pillared products. The
-4 nm, respectively. The former is comparable to the other swelling of layered zeolites generally requires high pH but
layered MWW precursors (MCM-22P, EMM-10P). In MIT-1 the differences can be observed when using surfactant hydroxide
2
4
0
adamantyl groups, which appear too big for the intralayer or surfactant salt plus NaOH. For MCM-22P swelling with the
2
0
sinusoidal channels, were proposed to fit in the surface latter was poor. MCM-56 was swollen with both media, and
pockets while the tails were lining the surface. This explains this was construed as indicating its better internal accessibility
small layer separation in UJM-1P compared to MFI but must and easier layer separability due to lose mono-layered nature.
also entail lower organic content. This is indeed the case as The behaviour of UJM-1P is closer to MCM-56, see Table 2. In
UJM-1P contains about 30% organic and has shorter tail (C-16) fact it showed the most facile swelling of all MWW materials
than the MFI analogues (~45% organic and C-22). Elemental so far. It is judged based on the relative intensity of the (003)
analysis of UJM-1P indicated partial degradation of the reflection at ca. 5.5° 2-θ, which has been empirically
template (C/N ratio 13.5 vs. 17 calculated), which is common established as a unique feature arising upon swelling of MWW
in hydrothermal syntheses with quaternary ammonium materials.4
compounds. It is also possible that the real MIT-1 and UJM-1P
may be somewhat different from the proposed models in
terms of template location and distribution. The suggested
location of adamantyl groups was inside the MWW surface
pockets (cavities) but being neutral and hydrophobic,
adamantyls cannot serve as counterions to acidic Al sites. Does
it mean that there are no Al atoms in these cavities or
something else can balance them? This question remains open
and may need further study.
1, 42
It is reflected in the patterns shown in Fig. 6.
0
03 swollen, ~5 nm interlayer d-spacing
0
02 unswollen, 2.7 nm interlayer d-spacing
00 intralayer peak
1
UJM-1
Pillared
MIT-1 sw
C16-OH
MCM-22P sw
C16Cl/NaOH
MCM-56 sw
C16Cl/NaOH
UJM-1P sw
C16Cl/NaOH
UJM-1P sw
C16-OH
UJM-1P
1
0
2
20
30
-theta, deg.
Figure 5. SAED patterns of EMM-1023 and UJM-1P (uncalcined). Additional
images are included in ESI.
Figure 6. XRD pattern of as-synthesized layered MWW materials after swelling
with HDTMA with hydroxide (C16-OH) and with chloride and NaOH (C16Cl-
NaOH).
The lack of swelling of MCM-22P treated with HDTMA-
Cl/NaOH is indicated by the (002) peak at >6° 2-θ and 2
separated peaks at ~8 and 10° 2-θ. We recognize that other
factors may influence this intensity as well as the extent of
swelling, which may depend for example on incidental layer
TEM imaging and SAED of layer disorder
SAED patterns (Fig. 5) and TEM images (in ESI) for UJM-1P
show significant lateral disorder. They are basically hexagonal
but with extensive scatter of spots around the points outlining
the hexagon. This significant lateral disorder is probably due intergrowth. Nonetheless UJM-1P is the best so far and a new
lining of the layers with parts of the template extending from benchmark, thus may be viewed as attractive for layer
the pores to the surface. The available images of calcined manipulation/swelling/delamination with high efficiency. MIT-
EMM-10, which has similar XRD to UJM-1, indicate disorder as
1
showed poor swelling even with the surfactant hydroxide,
2
3
well but much less extensive. The majority phase shows
disordered hexagonal electron diffraction patterns typical for
MWW crystals viewed face-on, but with arcing indicative of
layer misalignment, e.g. of the turbostratic nature. These
differences between UJM-1P and EMM-10P may be due to
particular samples that were tested and in the future may turn
out to be less pronounced. This may be resolved as more
information on more representatives of both materials
becomes available.
which confirms significant intergrowths within the ‘house-of-
cards' architecture.
Low angle (001) peaks at ca. 5 nm d-spacing are also observed
(see SI) for swollen MWW structures but their intensity is
sensitive to many factors so it is less reliable for quantitative
estimation. Additional validation of swelling is based on
pillaring and textural properties of the product. In the case of
UJM-1P the pillared product showed greatly enhanced BET and
pore volume, shown in Table 3, consistent with high degree of
expansion and pillaring. The capacity of UJM-1P for facile
swelling, even with HDTMA-Cl/NaOH, and formation of highly
Swelling with cationic surfactants
6
| J. Mater. Chem. A, 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal of Materials Chemistry A
ARTICLE
porous pillared structures, indicates overall weak layer Both the textural and acidity characteristics of UJM-1 should
View Article Online
DOI: 10.1039/C8TA09826C
connection, probably because of its unique structure.
be viewed as similar to MCM-22 and MCM-56 despite
numerical differences.
2
8,29
They may be real but MWW
Table 2. Swelling of as-synthesized layered MWW materials with cationic surfactants
and different OH sources.
materials are very sensitive to activation and post-synthesis
treatments. To establish intrinsic activity differences may
require elaborate testing. The acid site concentration in MIT-1
and pillared UJM-1 are viewed as really lower and fully
justifiable with the latter due to the presence of inert silica
pillars. The low value of MIT-1 may be caused by many factors
such the sample not being fully crystalline, more degraded
during processing because of mono-layer nature and even this
may be the property of MIT-1 that not all Al becomes acidic as
described for MCM-56. The reported catalytic activity of MIT-
Swelling solution
MWW material
MCM-22P
MCM-56
UJM-1P
HDTMA-OH
HDTMA-Cl+NaOH
Yes
Yes
Yes
No
No
Yes
Yes
n/a
MIT-1
2
0
1
was higher per active centre than MCM-22 and MCM-56. In
Physical and catalytic properties of UJM-1
our tests, shown in Fig. 7, it was less active than the other
UJM-1 and MCM-56, which again could be due to lower
sample quality.
UJM-1 was characterised by nitrogen sorption at 77K, FTIR
with pyridine adsorption (the data are presented in Table 2.)
and in model catalytic reaction (mesitylene alkylation with
benzyl alcohol, Figure 7.) to establish its basic properties in
comparison to other MWW materials.
UJM-1 showed high activity comparable to MCM-56 in a model
reaction, benzylation of mesitylene, which reflects accessibility
of acid sites to bulky molecules, with nominally higher
selectivity to 2-benzyl-1,3,5-trimethyl-benzene (100% vs. 94%,
see ESI). So it suggests that the accessibility is similar in UJM-1
and MCM-56, despite the latter having higher overall acid site
concentration. The MCM-22 tested here was probably not
optimal and it can be as active as MCM-56 in model reactions.
We will not rank these MWW materials as has been done in
2
0,39
the past,
with MCM-56 being often the benchmark, to
show beneficial effects of expansion and openness on catalytic
activity. There are various factors playing a role in such
appraisals, many unknown and nothing short of dedicated
systematic study can provide conclusive answers. For now we
can only treat it on an individual basis (reactions) and hope
that a coherent picture will emerge. As a new material, easy to
exfoliate and with surface lined with organics, UJM-1P is an
4
3
Figure 7. Benzyl alcohol conversions in reaction of mesitylene alkylation.
attractive candidate for controlled drug delivery studies.
Table 3. Comparison of the properties of UJM-1 with selected MWW materials with different layered structure after calcination, cation exchange with NH
4
3
NO and activation.
Si/Al,
XRF
Si/Al(IR)
BAS+LAS
Effective Si/Al
BAS
BAS(IR)
μmol/g
LAS(IR)
μmol/g
S
BET
2
S
out
2
V
micro
V
meso
3
Zeolite
3
m /g
m /g
cm /g
cm /g
MIT-1
UJM-1
18
18
8
45
16
14
24
45
53
18
15
31
53
307
899
55
86
500
500
240
135
140
76
0.086
0.114
0.119
0.109
0.322
0.02
0.03
0.02
0.01
0.09
MCM-56
1028
599
114
67
474
MCM-22
16
21
375
UJM-1 (pillared)
307
57
1063
154
structure with disordered stacking and expanded interlayer
spacing (>2.6 nm). This type of zeolitic architecture was
described before for the MFI topology as a multi-layered
structure with surfactant (single-unit-cell-thick nanosheets).
UJM-1 has properties of a high quality MWW zeolite: high
concentration of Brønsted acid sites (about 900 μmol/g), and
Conclusions
In this paper, we present a new multilamellar MWW zeolite –
UJM-1P – that has been obtained from the mono-layered
MIT-1 by one-pot synthesis. The distinct X-Ray diffraction
pattern of UJM-1P has confirmed its unique MWW layered
2
BET area of about 500 m /g with preservation of microporosity
This journal is © The Royal Society of Chemistry 20xx
J. Mater. Chem A, 2013, 00, 1-3 | 7
Please do not adjust margins

J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Page 8 of 9
ARTICLE
Journal of Materials Chemistry A
3
(
0.114 cm /g) which altogether makes it an attractive material 7.
L. Schreyeck, P. Caullet, J. C. Mougenel, J. L.ViGewuAthrticlaenOdnlinBe.
Marler, Microporous Materials, 1996, 6D,O2I:5190-.2107319./C8TA09826C
W. J. Roth and D. L. Dorset, Microporous Mesoporous Mater.,
for catalysis. Moreover, the unusual, adamantyl-containing
structure directing agent results in UJM-1P zeolite exhibiting
weak interlayer interaction, which allows generation of open
architecture that may be useful in catalytic reactions involving
bulky molecules. Catalytic activity of the calcined form (UJM-1)
was examined in the mesitylene alkylation with benzyl alcohol.
The results showed conversions of benzyl alcohol comparable
to another MWW family member with high activity, MCM-56,
and was significantly higher than their unilamellar form –
MIT-1.
Based on the confirmed high activity it may be expected that
UJM-1 will also show high mono-selectivity, stability and long
catalyst life exhibited by the other active MWW. To obtain
further meaningful confirmation and ranking, i.e. with
implications for practical use, make sense primarily with
catalysts approaching commercial formulation and conditions.
The novel MWW layered zeolite architecture is interesting
from the very fundamental point of view. Its catalytic
properties together with relatively simple (one-pot) method of
synthesis make UJM-1P attractive for further study and
8
.
2
011, 142, 32-36.
9
1
.
J. V. Smith, Chemical Reviews, 1988, 88, 149-182.
0. W. J. Roth, B. Gil and B. Marszalek, Catalysis Today, 2014, 227,
-14.
9
1
1
1. W. J. Roth, B. Gil, W. Makowski, B. Marszalek and P. Eliasova,
Chemical Society Reviews, 2016, 45, 3400-3438.
2. W. J. Roth, P. Nachtigall, R. E. Morris and J. Čejka, Chemical
Reviews, 2014, 114, 4807–4837.
13. B. Marler and H. Gies, European Journal of Mineralogy, 2012,
24, 405-428.
1
4. M. Mazur, P. S. Wheatley, M. Navarro, W. J. Roth, M. Položij,
A. Mayoral, P. Eliášová, P. Nachtigall, J. Čejka and R. E. Morris,
Nature Chemistry, 2016, 8, 58-62.
1
5. P. Eliášová, M. Opanasenko, P. S. Wheatley, M. Shamzhy, M.
Mazur, P. Nachtigall, W. J. Roth, R. E. Morris and J. Čejka,
Chem. Soc. Rev., 2015, 44, 7177-7206.
1
1
6. M. Choi, K. Na, J. Kim, Y. Sakamoto, O. Terasaki and R. Ryoo,
Nature, 2009, 461, 246-U120.
7. K. Na, C. Jo, J. Kim, K. Cho, J. Jung, Y. Seo, R. J. Messinger, B. F.
Chmelka and R. Ryoo, Science, 2011, 333, 328-332.
comparison with other MWW materials in catalysis and maybe 18. K. Na, W. Park, Y. Seo and R. Ryoo, Chemistry of Materials,
drug delivery applications.
2011, 23, 1273-1279.
9. K. Na, M. Choi, W. Park, Y. Sakamoto, O. Terasaki and R. Ryoo,
Journal of the American Chemical Society, 2010, 132, 4169-
1
4
177.
2
2
2
0. H. Y. Luo, V. K. Michaelis, S. Hodges, R. G. Griffin and Y.
Román-Leshkov, Chemical Science, 2015, 6, 6320-6324.
1. T. F. Degnan, Jr., C. M. Smith and C. R. Venkat, Applied
Catalysis, A: General, 2001, 221, 283-294.
2. S. L. Lawton, A. S. Fung, G. J. Kennedy, L. B. Alemany, C. D.
Chang, G. H. Hatzikos, D. N. Lissy, M. K. Rubin, H. K. C. Timken,
S. Steuernagel and D. E. Woessner, Journal of Physical
Chemistry, 1996, 100, 3788-3798.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Authors would like to acknowledge: National Science Centre
Poland grants no 2016/21/B/ST5/00858 (JG, BG) and
2
2
3. W. J. Roth, D. L. Dorset and G. J. Kennedy, Microporous and
Mesoporous Materials, 2011, 142, 168-177.
4. R. H. Archer, J. R. Carpenter, S. J. Hwang, A. W. Burton, C. Y.
Chen, S. I. Zones and M. E. Davis, Chemistry of Materials,
2
014/15/B/ST5/04498 (WJR, AK); OP VVV "Excellent Research
Teams", project No. CZ.02.1.01/ 0.0/0.0/15_003/0000417 –
CUCAM (MM, JČ); EPSRC grant EP/K025112/1 and Capital for 25. J. Čejka, W. J. Roth and M. Opanasenko, in Comprehensive
2
010, 22, 2563-2572.
Great Technologies grant EP/L017008/1 (MM); Czech Science
Foundation P106/12/G015 (JČ). We thank Dr. D.N. Miller for
help with the TEM and SAED.
Supramolecular Chemistry II, eds. G. W. Gokel, L. Barbour and
J. L. Atwood, Elsevier Science, 2017, vol. 7, ch. 7.18, pp. 475-
5
01.
6. S. I. Zones, Microporous and Mesoporous Materials, 2011,
44, 1-8.
2
2
2
1
7. W. J. Roth, W. Makowski, B. Marszalek, P. Michorczyk, W.
Skuza and B. Gil, J. Mater. Chem. A, 2014, 2, 15722-15725.
8. B. Gil, W. Makowski, B. Marszalek, W. J. Roth, M. Kubu, J.
Čejka and Z. Olejniczak, Dalton Transactions, 2014, 43, 10501-
References
1
2
3
4
5
6
.
.
.
.
.
.
J. Čejka, A. Corma and S. I. Zones, eds., Zeolites and Catalysis:
Synthesis, Reactions and Applications, Wiley, 2010.
A. F. Masters and T. Maschmeyer, Microporous and
Mesoporous Materials, 2011, 142, 423-438.
1
0511.
2
3
9. B. Gil, B. Marszalek, A. Micek-Ilnicka and Z. Olejniczak, Topics
in Catalysis, 2010, 53, 1340-1348.
0. S. Smeets, Z. J. Berkson, D. Xie, S. I. Zones, W. Wan, X. D. Zou,
M. F. Hsieh, B. F. Chmelka, L. B. McCusker and C. Baerlocher,
Journal of the American Chemical Society, 2017, 139, 16803-
I. Fechete, Y. Wang and J. C. Védrine, Catalysis Today, 2012,
1
89, 2-27.
J. Weitkamp and L. Puppe, eds., Catalysis and Zeolites:
Fundamentals and Applications, Springer, Berlin, 1999.
M. E. Leonowicz, J. A. Lawton, S. L. Lawton and M. K. Rubin,
Science, 1994, 264, 1910-1913.
1
6812.
3
3
1. T. Moteki, W. Chaikittisilp, A. Shimojima and T. Okubo, Journal
of the American Chemical Society, 2008, 130, 15780-15781.
2. X. Y. Zhang, D. X. Liu, D. D. Xu, S. Asahina, K. A. Cychosz, K. V.
W. J. Roth, C. T. Kresge, J. C. Vartuli, M. E. Leonowicz, A. S.
Fung and S. B. McCullen, Catalysis by Microporous Materials,
1
995, 94, 301-308.
8
| J. Mater. Chem. A, 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
Journal of Materials Chemistry A
ARTICLE
Agrawal, Y. Al Wahedi, A. Bhan, S. Al Hashimi, O. Terasaki, M.
Thommes and M. Tsapatsis, Science, 2012, 336, 1684-1687.
3. M. Opanasenko, W. Roth and J. Cejka, Catalysis Science &
Technology, 2016, 6, 2742-2753.
4. M. Položij, H. V. Thang, M. Rubeš, P. Eliášová, J. Čejka and P.
Nachtigall, Dalton Transactions, 2014, 43, 10443-10450.
5. M. Kubů, W. J. Roth, H. F. Greer, W. Zhou, R. E. Morris, J.
Přech and J. Čejka, Chemistry - A European Journal, 2013, 19,
View Article Online
DOI: 10.1039/C8TA09826C
3
3
3
1
3937-13945.
3
3
3
3
6. A. Corma, M. J. Diaz-Cabanas, M. Moliner and C. Martinez,
Journal of Catalysis, 2006, 241, 312-318.
7. S. Goergen, E. Fayad, S. Laforge, P. Magnoux, L. Rouleau and J.
Patarin, Journal of Porous Materials, 2011, 18, 639-650.
8. L. Xu, X. Ji, S. Li, Z. Zhou, X. Du, J. Sun, F. Deng, S. Che and P.
Wu, Chemistry of Materials, 2016, 28, 4512-4521.
9. V. J. Margarit, M. E. Martinez-Armero, M. T. Navarro, C.
Martinez and A. Corma, Angewandte Chemie-International
Edition, 2015, 54, 13724-13728.
4
4
0. W. J. Roth and J. C. Vartuli, Catalysis by Microporous
Materials, 2002, 141, 273-279.
1. S. Maheshwari, E. Jordan, S. Kumar, F. S. Bates, R. L. Penn, D.
F. Shantz and M. Tsapatsis, Journal of the American Chemical
Society, 2008, 130, 1507-1516.
4
4
2. W. J. Roth, J. Čejka, R. Millini, E. Montanari, B. Gil and M.
Kubu, Chemistry of Materials, 2015, 27, 4620-4629.
3. G. Wyszogrodzka, P. Dorożyński, B. Gil, W. J. Roth, M.
Strzempek, B. Marszałek, W. P. Węglarz, E. Menaszek, W.
Strzempek and P. Kulinowski, Pharmaceutical Research, 2018,
3
5.
This journal is © The Royal Society of Chemistry 20xx
J. Mater. Chem A, 2013, 00, 1-3 | 9
Please do not adjust margins