Towards understanding mesopore formation in zeolite Y crystals using alkaline additives via in situ small-angle X-ray scattering

Microporous and Mesoporous Materials 338 (2022) 111867

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Microporous and Mesoporous Materials
journal homepage: www.elsevier.com/locate/micromeso

Towards understanding mesopore formation in zeolite Y crystals using
alkaline additives via in situ small-angle X-ray scattering
Junwen Gu a, Jiaqi Lin a, Andrew J. Smith b, Siriwat Soontaranon c, Supagorn Rugmai c,
Chanapa Kongmark d, Marc-Olivier Coppens e, Gopinathan Sankar a, *
a

Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, United Kingdom
Diamond Light Source Ltd, Harwell Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom
Synchrotron Light Research Institute, Muang, Nakhon Ratchasima, 30000, Thailand
d
Department of Materials Science, Faculty of Science, Kasetsart University, 50 Ngam Wong Wan Road, Ladyaow Chatuchak, Bangkok, 10900, Thailand
e
Department of Chemical Engineering and Centre for Nature-Inspired Engineering, University College London, Torrington Place, London, WC1H 0AJ, United Kingdom
b
c

A R T I C L E I N F O

A B S T R A C T

Keywords:
Microporous
Mesoporous
SAXS

Hierarchical and in situ

The formation of micro/mesoporous zeolites by treating zeolite crystals with alkaline hydroxides has received a
lot of interest, but fundamental understanding is still lacking. Here, we study the reactivity of a crystalline
zeolitic material with various alkaline hydroxides, to close this knowledge gap. The use of ex situ and in situ smallangle X-ray scattering has allowed us to determine the reactivity of faujasite (FAU) type zeolite Y at different pH
and Si/Al ratio (SAR), with a variety of different organic ammonium hydroxides. Supplemented with ex situ XRD
and BET isotherm measurements, we show that the pH of the starting mixture and SAR of the zeolite significantly
influence the stability of the microporous structure and the extent of formation of mesoporous material.

1. Introduction
Porous materials are subdivided into three different groups accord­
ing to IUPAC (International Union of Pure and Applied Chemistry):
microporous (dp < 2 nm), mesoporous (2 nm ≤ dp ≤ 50 nm) and mac­
roporous (dp > 50 nm), where dp is the pore diameter of the dominant
pore system. They are widely used for a range of applications in areas as
diverse as nuclear waste remediation, catalysis, gas separation, agri­
culture, and as a component of household detergents [1–3]. Zeolites,
which are microporous crystalline materials, can afford high size and
shape selectivity in catalytic reactions and molecular separations.
However, the extreme nano-confinement effects in extended networks of
micropores limit the full potential of zeolites, as they lower diffusion
rates and hereby promote side reactions, including those that lead to
accelerated catalyst deactivation [4]. To overcome these intrinsic dis­
advantages of zeolites, many modification processes have been intro­
duced in recent years. The most popular approach is to create
hierarchically structured zeolitic solids, consisting of a combination of
larger pore systems (meso- and/or macroporous) with micropores;
together, this pore size range improves the observed, effective catalytic
function of the material [5–9].

Porous solids with multi-sized pore architectures offer several ad­
vantages over those which are predominantly microporous in character.
The combination of micro-, meso- and macropores facilitates molecular
transport by shortening the diffusion path length and thereby increasing
the observed activity of the catalysts, as well as decreasing the chance of
undesired side reactions [8,10–13]. Among various methods of incor­
porating a mesoporous structure along with the micropores, there are
two popular approaches widely investigated by the scientific community
in producing hierarchically structured porous materials. First, the
bottom-up approach, which is performed by introducing an additional
soft or hard templating agent in the initial synthesis of microporous
materials. Here, the strategy is to grow the microporous structure over
the template (molecule, supramolecular assembly or nanoparticle) that
creates meso- or macroporosity. The second method is the top-down
approach, wherein a microporous material is taken as the starting
point and molecular units within it are removed to create additional
pores. In both cases, once the process is completed, removal of any
occluded template molecules, usually by calcination, is necessary to
obtain porous hierarchical structures for further applications.
In the bottom-up approach, some commonly employed methods
include the use of a secondary (inert) template, which can be easily

* Corresponding author.
E-mail address: (G. Sankar).
/>Received 30 July 2021; Received in revised form 23 March 2022; Accepted 24 March 2022
Available online 13 May 2022
1387-1811/© 2022 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license ( />

J. Gu et al.

Microporous and Mesoporous Materials 338 (2022) 111867

removed by post-synthesis thermal treatment in air/oxygen or via
chemical treatment [11,14–18]. Examples of hard templates include
carbon-based materials, such as carbon black [11], carbon nanotubes
[16] and carbon nanofibres [15]. Due to the toxic nature and/or high
cost of many such templates, alternative materials, which are less toxic
and cost effective have been explored. To this end, a low-cost chitosan, a
non-toxic co-polymer derived from deacetylation of chitin has been
considered [19] to create hierarchical porous materials [16,20–22].
As top-down approach, demetallation (both desilication and/or
dealumination) is the most common method. The selective extraction of
aluminium or silicon from the zeolite framework through acid, alkali or
steaming treatment has been widely reported [23–27]. Recently, Gar­
cía-Martinez and co-workers [28,29] introduced a novel method of su­
pramolecular templating [30]. They use cetyltrimethylammonium
bromide (CTAB), along with a base as pH modifier (the optimum pH
reported to be in the range of 9 and 12), to promote mesoporosity via the
surfactant-templated synthesis [30]. This technique has been applied to
various types of zeolites with different Si/Al ratio (SAR), such as Fau­
jasite (FAU), Mordenite (MOR) and Mobil Five (MFI), leading to a
mesoporous structure, whilst maintaining the microporous character of
the zeolite and its associated desirable properties for catalysis [30]. The
influence of CTAB on the formation of mesopores in zeolite Y has also
been studied by Silva et al. [31] in a similar method where the con­
centrations of surfactant and base were varied. A positive correlation
was observed between higher concentrations of CTA+ cations and the
increased total mesopore volume of the modified zeolite Y [31].
To understand the reactivity and formation of mesoporous material,
it is necessary to use techniques related to diffraction methods, in

particular low-angle or small-angle X-ray scattering (SAXS) methods
[32–34]. By an appropriate choice of sample-detector distance in SAXS,
it is possible to interrogate the mesopore formation in the range of 2–10
nm. Here, we report the use of both in situ and ex situ methods to
determine the effect of hydroxide as pH modifier, in a pH range between
9 and 11, and the SAR on the mesopore formation and the stability of the
microporous structure during hydrothermal reaction.

glass capillary and measured using a step size of 0.5◦ and data collection
time of 5 s per step.
The ex situ Small Angle X-ray Scattering (SAXS) characterisations
were carried out using a SAXSLAB (now Xenocs) Ganesha instrument
with Cu-Kα source (λ = 0.15406 nm). The Q range employed in this work
is between 0.025 nm − 1 and 30 nm − 1. Samples were loaded in a 0.15
mm diameter glass capillary for these measurements. All the data were
background subtracted using an empty capillary of the same dimensions
used for loading the measured samples, under the same conditions that
were applied for recording the data of the samples.
The surface area and porosity measurements were carried out using a
QUADRASORB evo surface area and pore size analyser (Anton Paar). In
a typical experiment, ca 30 mg of the sample was loaded into the ana­
lyser, which was degassed overnight under vacuum at 673 K. After this
process, the samples were cooled to liquid nitrogen temperature (77 K),
before carrying out adsorption and desorption of N2.
A JEOL JSM-6701 F with cold field emission (<310> W crystal) as
electron source was used to carry out Field Emission Scanning Electron
Microscopy (FESEM) studies. The samples were prepared by gold
coating under argon and the SEM images were processed by employing
JEOL. PC-SEM software.
The Transmission Electron Microscopy (TEM) characterisations were

performed by using a JEOL JEM-2100 F with a Schottky field emission
gun at 200 kV. This instrument is equipped to combine routine atomic
resolution imaging of the crystal lattice achieved by coherent electron
scattering or phase contrast with incoherent electron scattering in STEM
(scattering transmission electron microscope) mode. The samples were
prepared by dissolving the fine powder in methanol; then, 2 or 3 drops of
suspension were loaded onto a copper grid mesh and left to evaporate in
air. The TEM images were taken using a Gatan Onevier Camera with full
4 k x 4 k resolution.
3. In situ characterisation
In situ SAXS data were collected at Beamline 1.3 W at the Synchro­
tron Light Research Institute (SLRI) in Thailand. Different from the ex
situ SAXS, the radiation source is a multipole wiggler and the Q range
used in this work is between 0.19 and 5.45 nm− 1 (corresponding to a 2θ
range of 0.27–7.66◦ ; hereafter, we discuss our results based on 2θ) by
using the energy of the incident X-rays corresponding to the wavelength
of 0.13776 nm. A sample-detector distance of 1202.62 mm, which
covers a range of measurable characteristic d-spacing of 1–33 nm was
used for these experiments. For in situ studies, we used protonated forms
of zeolite Y having a Faujasite (FAU) structure; they are CBV712 (FAUSAR6), CBV720 (FAU-SAR15), CBV760 (FAU-SAR30) and CBV901
(FAU-SAR40), as received from commercial supplier Zeolyst Interna­
tional. In a typical preparation for in situ studies, 1 g of zeolite Y and 0.7
g of CTAB were mixed in a beaker with 32 mL of distilled water.
Ammonium hydroxide or the organic analogue were added dropwise
until the required pH was achieved and this mixture was stirred for ca
20 min (we maintained the procedure and amount of chemicals
described in the synthesis section, above, as closely as possible), just
prior to the in situ SAXS measurement. About 15 drops of this mixture
were introduced into the in situ cell (see Fig. S1 given in the supple­
mentary information). The cell was heated from room temperature to ca

403 K at 5 K/min and the SAXS data were collected during the ramp to
the specific temperature and at 403 K for about 120 min. Each SAXS
pattern was recorded for 10 min to achieve good-quality data. SAXS data
were pre-processed initially using the SAXSIT program to obtain cor­
rected data and, subsequently, normalised data were obtained (with
respect to a point just after the direct beam position); this procedure was
necessary, as the amount of sample in the illuminated area appears to
change due to sample movements in the solution. Further analyses of the
data were conducted using DAWN software [35] available from Dia­
mond Light Source to extract the areas under the peaks representing the
mesopores and micropores in the material. Peak fitting was performed

2. Experimental
2.1. Synthesis
The experimental procedure was adapted from García-Martinez et al.
[30] Commercial zeolite Y, with different SAR (30, 15 and 2.55), ob­
tained from Zeolyst International was used for further ex situ studies.
Materials used in this investigation are (sample identity representing
them in this work is given in parenthesis): CBV720 (FAU-SAR15),
CBV760 (FAU-SAR30) and CBV400 (FAU-SAR2.55). In a typical syn­
thesis, ca 1.00 g zeolite and ca 0.70 g CTAB, obtained from Fisher Sci­
entific, were mixed in 60 mL water. Dropwise addition of a hydroxide –
Ammonium Hydroxide (NH4OH, Sigma Aldrich), Tetramethyl Ammo­
nium Hydroxide (TMAOH, Sigma Aldrich), Tetraethyl Ammonium Hy­
droxide (TEAOH, Sigma Aldrich) or Tetrapropyl Ammonium Hydroxide
(TPAOH 40 wt% in H2O, Fisher Scientific) – was carried out until the
desired pH (pH 9, 10, 11) was consistently reached, whilst stirring for ca
20 min at room temperature, before introducing the samples in a poly­
tetrafluoroethylene (PTFE) lined autoclave for hydrothermal treatment
at 423 K for 10 h. The products were filtered and washed with water,

then dried overnight. To remove the template, the dried products were
calcined under a nitrogen atmosphere for 2 h at 873 K, then in air for a
further 2 h at 873 K.
2.2. Ex situ characterisation
The Powder X-ray Diffraction (PXRD) measurements were conducted
using a STOE STADI P diffractometer equipped with Cu-Kα source (λ =
0.15406 nm) which operates at 40 kV and 30 mA. In a typical XRD
measurement, fine powder samples were packed in a 0.5 mm diameter
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Microporous and Mesoporous Materials 338 (2022) 111867

taking specific regions to define the background and gaussian peak
shape was chosen to extract the area under the peak.

identify the mesopore formation [37,38]. This appearance of the mes­
opore peak is similar to the observation made by Garcia et al. [30,39],
who proposed that the formation of mesopores is due to the breaking of
Si–O bonds within the microporous zeolite structure.
Nitrogen adsorption and desorption isotherms of these materials
support the mesopore formation suggested by the SAXS data (Fig. 2(b)).
The isotherms of the modified samples are a combination of type I and IV
isotherms, as observed in previous studies [40,41]. Different from the
unreacted FAU-SAR15 sample, the modified mesoporous zeolite samples
show a sharp rise in nitrogen adsorption between ca 0.05 to 0.3 relative
pressure and then follow a horizontal hysteresis loop, which is typical
for ordered mesoporous materials [42].

Typical SEM and TEM images of sample FAU-SAR15 reacted with
TPAOH and CTAB at pH 10 are shown in Fig. 3. They reveal that the
morphology of the zeolite crystal is maintained after the modification.
There are no obvious amorphous areas around the zeolite crystals. The
TEM image in Fig. 3(b) shows evidence for the mesopores being inside
the zeolite crystals.
To determine whether this observation of mesopore formation and
retention of microporous structure is specific to TPAOH, we investigated
the reactivity with FAU-SAR15 of other similar organic hydroxides, as
well as NH4OH at closely similar pH values. The CTAB concentration
was maintained through this investigation.
Fig. 4 shows low angle XRD patterns, in the top (high angle part
showing remaining Bragg reflections of FAU structure are given in
Figs. S4 and S5) and SAXS data (in the bottom) of the same FAU-SAR15
samples that were hydrothermally reacted with different hydroxides at
three different pH values of the starting mixtures. A low-angle peak in
the XRD patterns can be seen between 2θ = 1.0◦ and 3.0◦ , specifically
around 2θ = 2.0◦ for the samples treated at pH 10 or 11; for the samples
reacted at pH 9, a shoulder is visible around 2θ = 1.7◦ . Although we see a
peak-like feature (sometimes with a shoulder) in the XRD patterns at
very low angles, it is not reliable to interpret, as the data is incomplete,
due to the interference with the beam stop used in XRD measurements.
However, this may be related to the formation of mesopores in the
materials.
To clearly determine the presence of a low-angle peak, SAXS patterns
(bottom part of Fig. 4) were recorded for each of the FAU-SAR15 sam­
ples, after reacting with hydroxides and CTAB at different pH values.
These show a clear peak at q = 1.42 nm− 1 (2θ = 2.0◦ ), corresponding to
a mesoporous structure that is not present in the starting zeolite Y ma­
terial. For each hydroxide reacted at pH 10 and 11, a peak is more visible

and can be seen at q = 1.42 nm− 1 (2θ = 2.0◦ ) which corresponds to a dspacing of ~4.4 nm, however, for pH 9, the peak appears at q = 1.28
nm− 1 (2θ = 1.8◦ ) indicating an increase to ~ 4.9 nm. It is possible that
not only the CTA+, but also the organic cations occlude within the
zeolite Y [43], leading to an increase in mesopore volume through a
desilication process assisted by OH− anions. This is potentially due to the
TMA+/TEA+/TPA+ ions protecting the zeolite structure from attack, as
their large bulky volume prevents OH− from disrupting the Si–O–Si
bonds [43]. Irrespective of the type of hydroxide used in the reaction, a
peak around q = 4.48 nm− 1 (2θ = 6.3◦ ) is clearly seen, which is also
present in the parent unreacted FAU-SAR15, suggesting that this is
related to the presence of microporous zeolite Y, as in the XRD data.
However, we note that the intensity of the peak representing the
microporous phase appears to change with pH. The change in intensity
could also be related to the amount of sample present in the beam. To
overcome this discrepancy, we show the ratio of areas under the peaks
for q = 1.42 nm− 1 (2θ = 2◦ ) representing the mesopores and q = 4.48
nm− 1 (2θ = 6.3◦ ) belonging to the microporous zeolite in Fig. 5. The
ratio of the peaks was determined using DAWN software [35] for peak
fitting – see supplementary material in Fig. S2 and Table S1.
Fig. 5 illustrates the positive trend between an increase in pH and an
increase in SAXS peak area at q = 1.42 nm− 1 (2θ = 2◦ ), normalised to the
first Bragg’s peak for faujasite at q = 4.48 nm− 1 (2θ = 6.3◦ ). This cor­
responds to an increased induced mesoporosity when pH is increased for

4. Results and discussion
First, we discuss the ex situ XRD, SAXS data, BET measurements and
SEM, followed by the in situ SAXS measurements.
Ex situ studies: Fig. 1 shows the XRD patterns of the zeolite Y with
SAR = 15 (referred to as FAU-SAR15) reacted with CTAB and TPAOH at
three different pH values (pH 9, 10 and 11), which were subjected to

hydrothermal conditions at ca 423 K. It is clear from the XRD patterns
that all the reflections belonging to the faujasite structure are retained,
irrespective of the pH at which the initial reaction mixture was stirred.
However, the peak intensities corresponding to the FAU phase appear to
decrease as the pH of the starting solution increases. A background
corresponding to an amorphous phase is present in all the samples. As
the diffractograms were recorded using glass capillaries, it is difficult to
infer whether this background is a result of some of the crystalline
material being converted to amorphous phase or from the glass capil­
lary. However, the loss in intensity related to the faujasite reflections,
together with an increase of the low-angle peak around between 1.0◦
and 2.0◦ in 2θ, suggests that some amount of crystalline faujasite phase
is converted to amorphous, mesoporous material.
In Fig. 2(a), we compare the SAXS patterns of FAU-SAR15 reacted
with TPAOH at different pH, along with mesoporous silica MCM-41,
prepared using a standard procedure [36]. Two prominent peaks
appear in the SAXS patterns of the FAU-SAR15 samples, irrespective of
the pH of the reaction. A first, broad peak appears around q = 1.42 nm− 1
(2θ = 2.0◦ ); this peak is absent in the unreacted starting material (only
one peak at higher angle is present for the unreacted FAU-SAR15 sam­
ple) and is comparable to the one present in MCM-41. However, the first
peak for MCM-41 is slightly shifted to a lower d-value (estimated using
Bragg’s law) of ca 4.0 nm compared to 4.8 nm for the modified zeolite
samples. A weaker reflection around q = 2.85 nm− 1 (2θ = 4.0◦ ) is pre­
sent which is likely to be associated with the mesopore structure. Further
at q = 4.48 nm− 1 (2θ = 6.3◦ ), a narrower peak appears in the SAXS
patterns (see Fig. 2(a)), which is related to the first reflection in crys­
talline zeolite Y; this peak is absent in the MCM-41 sample. Therefore,
the peak around q = 1.42 nm− 1 (2θ = 2.0◦ ) should be related to the
mesoporous structure formed after the hydrothermal reaction with

CTAB and TPAOH, and its intensity appears to increase with an increase
in pH. This intensity and the area around this peak were utilised to

Fig. 1. XRD patterns of FAU-SAR15 samples reacted with CTAB and TPAOH
under different pH conditions. The XRD pattern for the parent starting FAUSAR-15 is also shown. On the left, low-angle peaks, and, on the right, a
stacked plot covering the region from 7◦ to 45◦ in 2θ is shown, highlighting
changes in the low-angle region and a loss in intensity in the high-angle region,
when reacting at higher pH.
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Microporous and Mesoporous Materials 338 (2022) 111867

Fig. 2. (a) SAXS patterns of zeolite FAUSAR15 modified with TPAOH and CTAB at
different pH conditions, and mesoporous
silica MCM-41. All SAXS data were collected
using a 0.15406 nm wavelength. The SAXS
data are stacked by multiplying × 2 (FAUSAR15 – pH 9), × 4 (FAU-SAR15 – pH 10),
× 6 (FAU-SAR15 – pH 11) and × 8 (meso­
porous MCM-41 SiO2) for clarity. (b) Nitro­
gen adsorption and desorption isotherms at
77 K of the same FAU-SAR15 samples reac­
ted at different pH. NOTE: in (b), starting
material, pH 9, pH 10 and pH 11 are stacked
by adding 0, 100, 200 and 300 cm3/g,
respectively.

Fig. 3. Typical (a) SEM and (b) TEM images of zeolite FAU-SAR15 modified at pH 10.

Fig. 4. XRD and SAXS patterns, measured ex situ, of FAU-SAR15 reacted with CTAB and different hydroxides (TMAOH, TEAOH, TPAOH and NH4OH) at different pH
values: (a) pH 9, (b) pH 10 and (c) pH 11. We show the low-angle peak from XRD data on the top and corresponding stacked SAXS patterns of the same samples. The
SAXS patterns in the bottom are stacked by × 2 (TEAOH), × 4 (TPAOH) and × 6 (NH4OH) for all the three pH values reported here, for clarity.

all hydroxides used. Using TMAOH as a hydroxide provides the highest
meso/microporous peak area ratio, followed by NH4OH at pH 11.
NH4OH induces less steric limitations, compared to the other, bulky
hydroxides. Because NH4OH is less bulky, there is less chance for the
−
NH+
4 cation to protect the zeolite structure from OH desilication. This
suggests that ammonium hydroxide is purely acting as a base: the NH+
4
ions are unlikely to provide a protecting effect, as these ions are too
small [31,44,45].
An attempt was made to rationalise this ratio, and why some hy­
droxides lead to higher mesoporosity, based on their pKa value. No

consistent correlation was found between pKa and the amount of mes­
oporosity in the material. The observations might be explained by the
effect of the molecular size of the base, rather than just its basicity. Also,
the concentrations of hydroxides used in the starting solutions were
different. However, pH was maintained as close as possible (within
±0.2) to the values mentioned.
Analysis of zeolites reacted at pH 9, regardless of the organic hy­
droxide base used, showed similar N2 adsorption and desorption iso­
therms to unreacted zeolite or reactions without hydroxides (where only
CTAB was mixed with the zeolite). Isotherms of samples of unreacted
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Microporous and Mesoporous Materials 338 (2022) 111867

and exit the hierarchical pore network [42,46,47].
Based on the ex situ work described above, it appears that different
hydroxides and pH influence the formation of the mesopores to a
different extent; surface area and pore volume of samples prepared using
pH 10 of the starting gel with different hydroxides are given in Table 1.
From the ex situ work and the comparison between different pH values
and different hydroxide reactions (Fig. 6), we can deduce that the best
pH for mesopore creation is 11. Therefore, a rational starting point for
the in situ work was to deduce the most effective, ammonium-based
hydroxide for mesopore synthesis at pH 11.
To do so, we carried out in situ SAXS measurements to determine: (a)
at what stage the mesopore formation takes place, (b) the effect of the
pH modifier at a given pH of 11 on the mesopore formation within FAUSAR15 and, in addition, we examined (c) the effect of the SAR on the
stability of the microporous structure at pH 10 (based on ex situ studies
presented above, where pH 10 is slightly less reactive compared to 11
and more reactive compared to 9), whilst maintaining the reaction
temperature. SAXS is preferable over conventional XRD to follow the
mesopore formation, as it allows the user to select a suitable sampledetector distance and wavelength of the incident beam, to obtain re­
flections corresponding to both mesopores and micropores, and to
monitor their evolution, in detail.
Different alkaline additives pH 11: The choice of base is closely
related to the formation of the mesopores reported earlier [30], and, so,
it is an essential parameter in the synthesis process. Deeper insight in its
function is obtained from in situ studies. This base can be either organic

or inorganic, but the alkalinity of the mixture containing zeolite, CTAB
and hydroxide should be controlled to avoid severe desilication under
alkaline pH conditions. Thus, the mixture containing water and CTAB
was controlled to pH 11 using either TPAOH, TEAOH, TMAOH or
NH4OH. The FAU-SAR15 reaction gel was then heated, from room
temperature to ca 403 K with a 5 K/min ramp, and, during this process,
SAXS data were collected for 10 min for each complete scan to obtain a
good signal-to-noise ratio. As mentioned before, the wavelength and
sample-detector distance were selected to provide data for q < 4.98
nm− 1 (2θ < 7.0◦ ), so that both the meso- and first micropore reflections

Fig. 5. The extent of mesopore formation, estimated using the ratio of the areas
under the SAXS peaks (ex situ recorded data) representing mesopores (at q =
1.28 nm− 1 (2θ = 1.8◦ )) and micropores (at q = 4.48 nm− 1 (2θ = 6.3◦ )), as a
function of the pH and hydroxide used in the reaction. Note that the hydro­
thermal reaction was carried out over 10 h and the dried samples after this
reaction were used to obtain ex situ SAXS data.

zeolite and zeolite reacted only with CTAB are shown in Fig. S3 (Sup­
plementary Information). This implies that the concentration of OH−
ions at pH 9 is insufficient to desilicate the original zeolite framework
and create mesopores. However, a less intense peak around 1.28 nm− 1
(2θ = 1.8◦ ) in the SAXS patterns is observed, suggesting that a small
amount of mesoporous structure might be formed within this micropo­
rous material, for the reaction conditions used in this work. This agrees
with the mesopore mechanism proposed by Silva et al. [31], where an
increase in pH is said to facilitate the mesopore formation.
Where there is hysteresis between the adsorption and the desorption
pathways in Fig. 6, this indicates that there is adsorption metastability
and/or network effects [42,46]. This is typical of open-ended pores, such

as in zeolite crystals with integrated mesopores, as there is metastability
of the adsorbed multilayer, which causes a delayed condensation effect
[42]. In addition, the data show that the hysteresis loop decreases in size
as pH increases, implying that there is more reversibility of the
adsorption-desorption pathways in hierarchically structured zeolites
formed at higher pH. This reversibility shows that there is an increase in
mesopore size and/or distribution, as N2 is more readily able to enter

Table 1
BET surface area data of synthesised hierarchical zeolites Y (FAU-SAR15) at pH
10.

TPAOH pH 10
TEAOH pH 10
TMAOH pH 10
NH4OH pH 10
As received
FAU-SAR15

Total BET surface
area (m2/g)

Micropore specific
area (m2/g)

Micropore volume
(cm3/g)

741
768

723
765
781

262
258
310
219
588

0.114
0.111
0.134
0.095
0.232

Fig. 6. Stacked BET data of FAU-SAR15 reacted with different organic hydroxides (TMAOH, TPAOH and TEAOH) and ammonium hydroxide at three different pH
values: (a) pH 9, (b) pH 10 and (c) pH 11. The amount of CTAB in this reaction was kept constant. Hydroxide amounts vary, as they were used to control the final pH.
All the samples were hydrothermally reacted at 423 K for 10 h. The isotherms for samples using NH4OH, TMAOH, TEAOH and TPAOH are stacked by adding 0, 100,
200 and 300 cm3/g, respectively.
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Microporous and Mesoporous Materials 338 (2022) 111867

can be observed, simultaneously. As can be seen from Fig. 7, the mes­
opore peak formation started just around the time when the temperature
was raised to 373 K, before reaching the final temperature.

The mesopore peaks in Fig. 7(a), (b), (c) and (d) are centred around,
respectively, q = 1.13 nm− 1 (2θ = 1.59◦ ) (d = 5.56 nm), 1.16 nm− 1 (2θ
= 1.63◦ ) (d = 5.40 nm), 1.17 nm− 1 (2θ = 1.64◦ ) (d = 5.36 nm) and 1.15
nm− 1 (2θ = 1.62◦ ) (d = 5.45 nm). They continue to increase in intensity
and slightly shift, but this shift remains within a range of ca 0.2–0.3 nm
of the average. Because d ~5.4 nm for each sample, the pore sizes are
similar to what one would expect for a material formed around selfassembled CTAB molecules, similar to the proposed MCM-41 formation.
Different pH with NH4OH: Based on this and the ex situ study re­
ported earlier, we focussed our attention on the use of NH4OH as the pH
modifier for FAU-SAR15. Although, to some extent, all the base modi­
fiers enabled a successful introduction of mesopores, the NH4OH base
appears to show a distinct increase in mesopores and is unlikely to add
any additional templating effect.
Fig. 8 shows the SAXS patterns recorded during reaction with
NH4OH and CTAB, while maintaining the starting mixture at pH 9, 10 or
11. The heating and measurement procedure was similar to that
described earlier in the study of the effect of different bases. The
mesoporous.
Peak around q = 1.15 nm− 1 (2θ = 1.62◦ ) (d = 5.45 nm) in Fig. 8(c)
suggests the existence of ordered mesopores. However, scattering peaks
in Fig. 10(a) (pH 9) and (b) (pH 10) were found to be weak, indicating
that there are less mesopores present in reactions conducted at lower
pH.
Different SAR with NH4OH at pH 10: Based on the above obser­
vation of reactivity at different pH using NH4OH, pH 10 appears to
provide a moderate conversion in terms of maintaining the microporous
structure component with a small amount of mesopore formation in
FAU-SAR15. For otherwise similar conditions, the effect of the SAR on
the formation of mesopores and the stability of the microporous struc­
ture was examined. Commercially available zeolite Y samples with a

SAR of 6, 15, 30 and 40 were used, and NH4OH was added as the pH
modifier, since the reactivity appears to be enhanced compared to other

bases, in particular in the formation of mesoporous structure. The
measurement procedures and reaction.
Conditions were identical to those described earlier, except for
varying the SAR. Fig. 9 shows the SAXS patterns recorded during the
reaction. The main observation is that, as the SAR increases, mesopore
formation seems to be generally higher and, at the same time, the
microporous phase becomes less stable.
We determined the amount of mesoporosity formed as a function of
time, during the reaction, by extracting the area under the mesopore and
micropore reflections seen in the in situ SAXS data. One issue we
encountered in our measurements, which is typical of an in situ study
when solid and liquid reactant mixtures are present, is that the solid
samples begin to settle on the bottom of the cell, and this affects the
intensities of the scattering patterns. Although the X-ray beam was kept
close to the bottom of the window, it was not possible to go further than
~1 mm above the bottom, as the beam spot on the sample is ca 1 × 2 mm
in size (see the picture shown in Supplementary Fig. S1) and some of the
components in the in situ cell could interfere and produce not only re­
flections from those components, but also attenuate the beam. To
overcome the changes in intensity due to sample movement, we took the
ratio of the areas under the reflections that belong to mesopores and
micropores, as both areas should decrease or increase together if the
changes are due to the amount of sample in the beam. We plotted the
ratio of the areas under the reflections representing mesopores and
micropores in Fig. 10 as the “Extent of mesopore formation”.
Extent of mesopore formation =

Area under mesopore peak at q = 1.2 nm−
Area under micropore peak at q = 4.5 nm−

1
1

Clearly, we can see that the increase in the amount of mesopores over
a period of 2 h with NH4OH as pH modifier is the highest, closely fol­
lowed by TPAOH, in comparison to the others. However, the values
appear to be similar at the start of the reaction, irrespective of the base
we used in this work. The ratio of areas under the reflections repre­
senting mesopores and micropores, given in Fig. 10(b), suggests that at
pH 11 the mesopore formation is significantly higher compared to pH 10
or 9. A reaction mixture at pH 9 did not produce any noticeable

Fig. 7. In situ stacked 3D SAXS patterns of FAU-SAR15 reacted with different organic hydroxides at pH 11: (a) TPAOH, (b) TEAOH, (c) TMAOH and (d) NH4OH. The
amount of CTAB in this reaction is kept constant. All the samples were hydrothermally reacted from room temperature to ca 403 K and, during this process. SAXS
data were collected every 10 min.
6


J. Gu et al.

Microporous and Mesoporous Materials 338 (2022) 111867

Fig. 8. In situ stacked SAXS patterns of FAU-SAR15 reacted with NH4OH at (a) pH 9, (b) pH 10 and (c) pH 11. All the samples were hydrothermally reacted from
room temperature to ca 403 K and during this process SAXS data were collected every 10 min.

Fig. 9. In situ SAXS patterns of (a) FAU-SAR6, (b) FAU-SAR15, (c) FAU-SAR30, and (d) FAU-SAR40 reacted with NH4OH at pH 10. All the samples were hydro­
thermally reacted from room temperature to ca 403 K and, during this process, SAXS data were collected every 10 min.

mesoporosity. Fig. 10(c) clearly indicates mesopore formation in both
the SAR30 and SAR40 samples, when using NH4OH at pH 10. Whilst the
FAU-SAR30 sample shows a slightly larger mesoporosity-tomicroporosity ratio in the initial stages of the reaction compared to

SAR40, the order is reversed over the course of the 2 h of reaction time.
This is because, in the FAU-SAR40 sample, all the reflections related to
the microporous structure were lost, while the FAU-SAR30 sample
showed an initial loss of intensity in the reflection related to micropores,
7


J. Gu et al.

Microporous and Mesoporous Materials 338 (2022) 111867

Fig. 10. The extent of mesopore formation (a) (FAU-SAR30) with different organic hydroxides, (b) FAU-SAR15 reacted with NH4OH at different pH and (c) Different
SAR values reacted with NH4OH at pH 10, over time is estimated by taking the ratio of the areas of the peaks representing mesopores around q = 1.2 nm− 1 (2θ =
1.7◦ ) and micropores around q = 4.5 nm− 1 (2θ = 6.3◦ ). Note that the reaction time is only ca 2.5 h, compared to 10 h for the ex situ studies. Therefore, more
mesopore formation could have occurred for the ex situ samples. The estimated errors were within 10% of the values for each of the determined peak area.

but then stabilised over time. This observation demonstrates the
complexity of the mesopore formation and its dependence with the
nature of the pH modifier as well as the pH and silica-alumina ratio of
the sample.
All these samples studied in situ were further reproduced in the
laboratory and characterised ex situ by XRD, and the results were found
to confirm the in situ observation, for the microporous part that is more
easily evaluated by XRD in particular. In addition, all these samples were
dried and calcined at ca 873 K and they were all found to retain both

their microporous and/or mesoporous structure without any further
modifications after calcination (see Supplementary Fig. S5).

Acknowledgements
We thank EPSRC and the Department of Chemistry at UCL for
financial support. MOC and GS acknowledge funding from EPSRC via
‘Frontier Engineering’ and ‘Frontier Engineering: Progression’ awards
(grant numbers EP/K038656/1 and EP/S03305X/1) to the CNIE. GS
thank SLRI for provision of beam time and other facilities within the
system. We thank Dr Han Wu for training JG for SAXS data collection in
the CNIE’s laboratory-based system. We thank the CNIE for the use of
the SAXS instrument.
Appendix A. Supplementary data

5. Conclusions

Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2022.111867.

This study has demonstrated the insights provided by SAXS mea­
surements, employing both in situ and ex situ methods, to follow the
reactivity of zeolite Y with various bases in the presence of CTAB and at
alkaline pH of 9, 10 or 11, which are typically recommended based on
earlier studies to produce hierarchically structured micro/mesoporous
faujasite zeolite crystals [30,31]. The results identified that NH4OH is
the better reactant base, compared to tri-alkyl ammonium hydroxides,
possibly because it is best at inducing the desilication process to intro­
duce mesoporosity. Similarly, the choice of pH and, more importantly,
the silica/alumina ratio is critical, if it is necessary to maintain the
microporous structure whilst some mesoporosity is introduced in the

system. The latter is vital in the design of hierarchically structured
materials for catalysis and other applications affected by molecular
transport limitations.

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CRediT authorship contribution statement
Junwen Gu: Formal analysis, Methodology, Writing – original draft.
Jiaqi Lin: Writing – original draft, Methodology. Andrew J. Smith:
Data curation, Formal analysis, Methodology. Siriwat Soontaranon:
Methodology, Formal analysis, Data curation. Supagorn Rugmai:
Methodology. Chanapa Kongmark: Methodology. Marc-Olivier Cop­
pens: Supervision, Writing – original draft, Writing – review & editing.
Gopinathan Sankar: Writing – review & editing, Writing – original
draft, Supervision, Methodology, Conceptualization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

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