Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132422

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

The influence of deuterium on sodium mobility and viscosity of colloidal

precursor suspensions yielding template-free nanosized zeolites
Mishel Markovski a, Eddy Dib a, Sajjad Ghojavand a, Abdallah Amedlous a, Valérie Ruaux a,
Aymeric Magisson a, Oleg Lebedev b, Igor E. Golub a, Francesco Dalena a, Svetlana Mintova a, *
a
Normandie Université, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 14000 Caen, France
b
Normandie Université, ENSICAEN, UNICAEN, CNRS, CRISMAT, 14000 Caen, France

G R A P H I C A L A B S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: The isotopic substitution in chemistry is characterized by two main effects, i.e., the kinetic isotope effect (KIE),
FAU associated with differences in the reaction rates, and the geometric isotope effect (GIE) related to crystallo­
Nanosized zeolites graphic features. In this work, considering the difference in the weight of deuterium (D) compared to the weight
Heavy water
of hydrogen (H), we use the isotopic substitution to investigate the crystallisation mechanism of template-free
Isotope effect
nanosized faujasite (FAU) type zeolite in colloidal precursors. Тhe basic hydrothermal synthesis solvent -
Deuterium
Organic template-free water (H2O), is substituted with heavy water (D2O), aiming to understand the isotopic influence and the effect of
Crystallisation H-bond networks on the zeolite crystallisation. The crystallinity, viscosity, conductivity, chemical composition,
morphology and local order of the FAU zeolites synthesized in both hydrated (H) and deuterated (D) medium are
evaluated with X-ray diffraction, TEM microscopy, EDX and ICP analysis, FT-IR and solid-state NMR spectros­
copy. The structural directing agent - Na+, exhibits a lower mobility in the deuterated medium, because of a
characteristic higher viscosity compared to hydrated medium. This leads to a slower nucleation and crystal­
lisation in the initial stages of hydrothermal treatment in the colloidal suspensions but also to a significant
difference in the Al distribution.

* Corresponding author.
E-mail address: [email protected] (S. Mintova).

https://doi.org/10.1016/j.colsurfa.2023.132422
Received 28 July 2023; Received in revised form 13 September 2023; Accepted 14 September 2023
Available online 19 September 2023
0927-7757/© 2023 Elsevier B.V. All rights reserved.
M. Markovski et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132422

1. Introduction LUDOX AS-30 was replaced by a solution of fumed silica with H2O or
D2O, in mass ratio 3:7 respectively to avoid the hydrogen coming from
The hydrothermal synthesis of zeolites implies the heating of aqueous the LUDOX solution in the D2O synthesis. However, NaOH was used in
suspension or gel containing the precursors to form the final crystals both media despite the presence of hydrogen. The synthesis procedure is
[1–4]. Despite many investigations, the zeolites crystallization mecha­ divided in three main steps (aging, freeze-drying and hydrothermal (HT)
nism is still blurred because of the interplay of several physical and treatment) and 2 solutions, denoted A and B were prepared for all
chemical factors [5,6]. The main attention is often paid to the exploration samples. Solution A consists of 2.5 g of NaOH dissolved in 3 g of
of synthesis parameters including the nature of the precursors [5,6], the deionized H2O or D2O with 0.297 g of Al powder under vigorous stirring.
gel composition [7,8], the order of mixture [5], the temperature [9,10] Solution B consists of a mixture of 1.1 g NaOH in 8.0 g deionized H2O or
and the aging time [11,12]. Solvothermal syntheses in the presence of D2O, in addition to 3 g of fumed silica. After 12 h under vigorous stirring
ionic liquids have also been extensively investigated in order to under­ on orbital shaker, the turbid suspension is heated for 20 min at 90 ºC to
stand the role of the solvent during the crystallization [5–7]. However, obtain a clear solution. Solution A was added to solution B under
compared to the mentioned approaches, the influence of the isotopic vigorous stirring at about 0 ºC (ice bath) that allows the formation of
substitution on zeolite crystallization was less developed [13,14]. Several highly homogeneous colloidal suspensions due to the slow rate of
studies have shown the high impact of hydrogen - deuterium isotopic polymerization. The final colloidal suspensions were left for aging for
exchange on the crystallization of organic molecules [15–21], demon­ 24 h at room temperature under vigorous stirring. After aging, the sus­
strating the importance of the hydrogen bonds networks during the pensions were freeze-dried for 6 h at − 50 ◦ C under vacuum (120 mBar).
crystallization process. Furthermore, the clustering and interactions of 6 g and 5.6 g ( ± 0.1 g) of water lost for the hydrated and deuterated
liquid water molecules is known to be highly complex and was subjected samples, respectively was measured. The difference of ~0.5 g (10%) of
to profound studies in the last decades [22–25]. The diversity of water loss approximately corresponds to difference in molar ratio (10%)
H-bonding networks leads to the formation of 19 polymorphs of ice between H2O and D2O, as the syntheses were prepared by ratio in weight
identified in the water phase diagram [26] revealing their impact on (11 g of H2O/D2O per bottle). Hydrothermal treatment of the suspen­
water properties [27]. Deuterium is two times heavier than hydrogen and sions in H and D medium was performed in 60 ml pp bottles in a static
deuterated compounds exhibit significant changes in density and viscos­ oven at 50 ºC for 2 h, 12 h, 16 h, 19 h and 23 h; the samples obtained
ity [28], boiling and freezing temperature [29], heat of fusion and were named FAU-H/D-x h, respectively (H and D corresponds to syn­
vaporization [30], osmotic coefficient [31], hydrogen and deuterium theses from H2O or D2O suspensions, respectively; x represents the hy­
potentials (pH, pD) and reduction potential (E◦ ) [32]. Kinetic isotope drothermal crystallisation time in hours). The products were purified
effects (KIE) and geometrical isotope effects (GIE) were highlighted in the using deionized H2O, until a neutral pH of 7. The final products were
presence of deuterium impacting the surface morphology and crystal dried in an oven overnight at 90 ºC.
growth of ice [33], the bond elongations [16], the SiO4 tetrahedron dis­
tortions [15], the symmetry changes of bi-deuterated ethylene [18], the
crystallisation kinetics of selectively deuterated poly(ε-caprolactone) [19] 2.2. Characterization
and the phase-transition-related physical properties of H-bonded network
[17]. Concerning confined spaces i.e. the pores of zeolites, different water Phase determination of the samples was performed by powder X-ray
cluster topologies were identified [34–37] leading to the use of an ‘ice-­ diffraction (XRD) using a PANanalytical X′Pert Pro diffractometer with
templating approach’ for mordenite (MOR) zeolite recently [38]. Cu Kα1 monochromatic radiation (λ = 1.540598 Å), within 2θ range
Therefore, the use of D2O in lieu of H2O in the hydrothermal syn­ 5–60◦ with a step of 0.0131◦ .
thesis of zeolites, seems to be a promising way that may give new in­ The chemical composition and Si/Al ratios as a function of crystal­
sights on their crystallisation mechanism involving aqueous complexes, lisation time were identified using a combination of ICP-MS (7900 ICP-
colloidal suspensions, liquid-solid and amorphous-crystalline interfaces MS from Agilent Technologies), energy dispersive X-ray (EDX) (Bruker
that determine the rate of nucleation and growth and consequently the XFLASH 6/30).
properties of zeolites. Fourier-transform infrared (FT-IR) spectra were recorded on Nexus
The isotope effect in the synthesis of zeolites was firstly presented in IR spectrometer, 265 scans were acquired in the 1200–400 cm− 1 range
1989 [13], a decelerating role was noticed in the crystallisation of with a resolution of 1 cm− 1. Standard KBr pellets, prepared by mixing of
zeolite A. Another study has shown how the crystallization of pure silica 100 mg dried KBr (ACS reagent, ≥ 99.0%, Sigma Aldrich) with 1 mg of
MFI zeolites synthesized in hydrated and deuterated medium, exhibited sample were used for all measurements.
different crystallization rates, depending on the SDA used [14]. In this Solid-state Magic-angle spinning nuclear magnetic resonance (MAS
work, template-free nanosized FAU zeolites are examined because of NMR) spectra of 27Al and 29Si nuclei were recorded with single pulse
their relatively small crystal size (hundreds of unit cells), allowing the experiments at 99.3 and 130.3 MHz, respectively on a Bruker Avance III
understanding of the isotopic effects on the first stages of nucleation and HD 500 MHz spectrometer using 4 mm-OD zirconia rotors with a spin­
growth without the use of OSDAs in colloidal precursor suspensions (e.g. ning frequency of 12 kHz. Measurements were performed using radio­
FAU zeolites) [39,40]. Furthermore, water plays a crucial role in the frequency powers of 36 and 50 kHz, for 29Si and 27Al, respectively. For
29
synthesis of FAU zeolites, their secondary building units (SBUs) being Si NMR spectra, 2560 scans were acquired with a recycle delay of 20 s.
formed during the aging stage of a viscous suspension [40–42]. For 27Al NMR spectra, 2048 scans were acquired with a recycle delay of
1.0 s
2. Experimental part The morphology and size distribution were investigated by bright
field transmission electron microscopy (TEM) using a probe and image
2.1. Synthesis aberration corrected JEM-ARM200F cold FEG microscope, operated at
200 kV and equipped with large angle CENTURIO EDX detector, Orius
The following chemicals were used for preparation of nanosized CCD camera and Quantum GIF (Gatan).
zeolites from colloidal precursor suspensions: fumed silica (~99%, Dynamic viscosity measurements of the colloidal suspensions were
Sigma Aldrich), aluminium powder (325 mesh, 99.5%, Alfa Aesar), so­ performed using a rotational rheometer Kinexus pro with a PU20
dium hydroxide (NaOH, Prolabo, 98.7%), D2O (99.9 atom D%, Sigma SC0085 SS geometry.
Aldrich) and deionized H2O (Milli-Q® water (18.2 MΩ⋅cm)). Conductivity measurements were performed by HACH SensIONTM+
The synthesis procedure for organic template-free nanosized zeolite MM150 Portable Multi-Parameter meter, Field Kit with Multi Sensor for
X reported in [39] was slightly modified in both, H2O and D2O media. pH, ORP, Conductivity and TDS.

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M. Markovski et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132422

3. Results and discussion

Synthesis and crystal evolution of nanosized FAU-type zeolite from

template-free colloidal suspensions, have been recently studied [40].
Two periods describing the crystallisation of FAU were described: the
initial nucleation period and the period of crystal ordering leading to the
crystallization of fully crystalline FAU.
In order to explore the isotope effect on the crystallization of FAU,
the conductivity and viscosity of the H- and D- colloidal suspensions
have been analysed. They differ substantially in the two media, and they
are directly related to the rates of nucleation and growth of the zeolite.
The viscosity of the colloidal precursor suspension was measured at
room temperature after the hydrothermal treatment at different crys­
tallisation times. The viscosity is higher for all of the deuterated sus­
pensions (Fig. 1). This is due to the density difference between the light
and heavy water.
The viscosity of the colloidal suspension in the initial synthesis steps
increase five times approximatively after freeze-drying, from ~2.5 cPs
(P-1 and P-2) to ~12.5 (P-3) (Fig. 1a). Significant increase of viscosity is
also observed after the HT treatment (Fig. 1b). With the increase of
crystallization time, the viscosity decreases with a similar tendency for
both H- and D- suspensions. The difference between H- and D- suspen­
sions is the highest between FAU-H-12 and FAU-D-12 and lowest when
the fully crystalline FAU-H-23 and FAU-D-23 samples are obtained. This
difference in viscosity is one of the main factors that slow down the
nucleation and crystallization of FAU zeolite in D2O media.
Fig. 2. XRD patterns of nanosized FAU-H (A): (a) FAU-H-12, (b) FAU-H-16, (c)
The conductivity of the colloidal suspensions of nanosized template-
FAU-H-19, (d) FAU-H-23 and FAU-D (B): (a) FAU-D-12, (b) FAU-D-16, (c) FAU-
free FAU zeolites in H- medium, has already been reported [40]. The D-19, (d) FAU-D-23 samples as a function of crystallisation time at 50 ºC.
decrease of the conductivity during the hydrothermal crystallisation was
related to the trapping of Na+ cations in the FAU structure. Considering
indicates the first evidence of a slower formation of FAU zeolite phase in
the water coordination sphere around Na+ as the structure-directing
D2O.
agent of FAU in the presence of OH- or OD-, we expect the bonds
The XRD patterns of the FAU-H and FAU-D series after 12 h of HT are
formed in D2O to be stronger than the ones formed in water, due to the
presented in Fig. 2. The XRD patterns of all of the samples correspond to
lower reported zero-point vibrational energy of the D-R compared to the
the FAU-type zeolite [39,40]. The degree of crystallinity of the samples
H-R bonds [43].
increases with the time up to 23 h of hydrothermal treatment (FAU-H-23
To compare the conductivities in both H- and D- media, two NaOH
and FAU-D-23).
solutions were prepared in H2O and D2O and their conductivities were
The relative crystallinity is determined by comparation of peak area
measured at 25 ºC and 50 ºC. The conductivity of 327 and 337 ms/cm for
and peak intensity, particularly for the first 3 most intense peaks as well
H2O solutions and 225 and 234 ms/cm for D2O, respectively were
as for the 7 most intense peaks between 5.20 and 13.00◦ and 2θ
measured. This shows a ~30% higher conductivity for the suspension
5.20–27.00◦ respectively, using a fully crystalline FAU-H-23 and FAU-D-
prepared in H2O. Then, the mobility of Na+, playing the role of
23 samples as references for each series (Fig. 3, Table S1, Table 1). The
structure-directing agent, is significantly slower in deuterated medium
experimental data are summarized in Table S1.
hence the crystallisation in the initial stage is delayed.
The degree of relative crystallinity of FAU-D-12 and FAU-H-12 is
The first emergence of the diffraction peaks associated with X-ray
19% and 37%, respectively (Fig. 3). This trend continues in the next four
visible FAU topology has been found after 2 h of HT treatment in the H-
hours, for FAU-H-16 and FAU-D-16 (28% and 52%, respectively). After
medium (FAU-H-2) (Fig. S1). The amorphous phase observed in the XRD
16 h, the crystallinity increased to 88% for (FAU-D) and to 74% for
pattern of the sample synthesized in the D- medium at the same time,

Fig. 1. Variation of the viscosity of FAU-H (open circle) and FAU-D (black circle) colloidal precursor suspensions (a): before HT treatment (P-1: before aging
procedure; P-2: after aging procedure; P-3: after freeze-drying water loss procedure) and (b): after HT treatment at 50 ºC.

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M. Markovski et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132422

(FAU-H) and 100% crystallinity is obtained after 23 h in both media.

The crystallization in H medium is characterized by a consistent crys­
tallization rate over the time considered. For the synthesis in the D
medium, only the initial stage of crystallization is slow and the crys­
tallization gets faster after 18 h approximatively. This behaviour may be
understood by considering both the higher alkaline strength of OD-
compared to OH- and the geometrical features of O-H and O-D com­
plexes in liquid and solid state [44]. A relatively stronger silica­
te–silicate, water–silicate and water–water interactions in deuterated
media are expected as reported earlier [45]. The analysis of the relative
crystallinity leads to the conclusion that the kinetic isotope effect (KIE)
affects the reaction’s mechanism (chemical reaction kinetic) and
consequently the crystallisation rates (growth kinetics) of FAU zeolite
Fig. 3. Relative crystallinity of FAU-H (open circle) and FAU-D (black circle) crystallized from a template-free colloidal suspension in water solution
series, determined by the area of the first 3 highest crystalline peaks between and by substitution of H2O by D2O.
2θ 5.20–13.00◦ . The crystal size and morphology of the fully crystalline FAU-H-23
and FAU-D-23 samples were examined by HR-TEM (Fig. 4). Particles

Table 1
29
Relative crystallinity and Si/Al ratio of nanosized FAU-H and FAU-D samples based on Si NMR, ICP-MS and EDX methods.
Crystallisation Crystallinity degree (%) Si/Al Si/Al Si/Al
time (h) (29Si NMR) (ICP-MS) (EDX)

FAU-H FAU-D FAU-H FAU-D FAU-H FAU-D FAU-H FAU-D

2 n.d. n.d. n.d. n.d. 1.68 1.74 1.55 1.77

12 37 19 1.27 1.31 1.15 1.22 1.30 1.28
16 52 28 1.15 1.16 1.18 1.16 1.35 1.28
19 74 88 1.16 1.20 1.24 1.24 1.25 1.28
23 100 100 1.16 1.18 1.19 1.19 1.26 1.33

Fig. 4. TEM images highlighting the morphology of fully crystalline nanosized FAU-D-23 (a-b) and FAU-H-23 (c-d) zeolites.

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M. Markovski et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132422

from both systems have a similar size between 5 and 20 nm, pronounced
lattice fringes and (111) twining. In order to understand the isotope
effects at the local order, further analyses of the samples were carried
out using FT-IR and NMR spectroscopy.
The FT-IR spectra (Fig. 5) in the mid-infrared region
(1200–400 cm− 1) show the structural bands assigned to bond vibrations
within the primary building units of FAU. Peaks corresponding to T-O
bending mode of the TO4 tetrahedra (467–441 cm− 1), symmetrical
stretching T-O-T mode (753–673 cm− 1) and asymmetrical stretching T-
O-T (1025–985 cm− 1) were observed (Table S2). The 6-membered
double ring (d6r) vibration bands appear at 12 h of crystallisation in
both series and vary in the range 569–564 cm− 1. Asymmetrical Si-O-T
(T = Al or Si) stretching bands shift in lower wavenumbers within the
crystallization time, indicating the decrease in Si/Al ratio, hence the Al
incorporation into the crystal structure [46]. The highest shift of these
Fig. 6. FT-IR asymmetrical T-O-T stretching band shifts as a function of crys­
bands has been observed in the initial crystallization stages changing by tallisation time at 50 ºC of FAU-H (open circle) and FAU-D (black circle) series.
24 cm− 1 approximatively between 2 and 12 h in both media (Fig. 6).
After 16 h all bands appear at the same frequency (~985 cm− 1).
The presence of aluminium in tetrahedral coordination is confirmed The 29Si MAS NMR spectra of the samples with different degree of
by 27Al MAS NMR spectra (Fig. 7). After 12 h of HT treatment, all crystallinity are presented in Fig. 8. Five resonance were identified in all
samples exhibit a wide distribution around ~62 ppm corresponding to of the samples between 12 h and 23 h corresponding to Q4(4Al),
tetrahedrally coordinated Al atoms. This is in line with the appearance Q4(3Al), Q4(2Al), Q4(1Al) and Q4(0Al). According to the Si/Al ratio,
of Si-O-T (T = Al or Si) stretching and vibrational bands in the FT-IR estimated using 29Si MAS NMR spectra in accordance to Engelhardt and
spectra. The relatively broad asymmetric resonance for FAU-H-12 and Michel equation [47], the FAU-H and FAU-D analogues have similar
FAU-D-12 is due to the heterogeneous Al distribution in the semi- Si/Al ratio that decrease from 1.6 (FAU-H-2 and FAU-D-2) to 1.3
crystalline FAU zeolites. (FAU-H-12 and FAU-D-12) and to around 1.2 after 16 h of crystallization
(Table 1).

Fig. 7. 27Al MAS NMR spectra of nanosized FAU-H (A): (a) FAU-H-12, (b) FAU-
Fig. 5. FT-IR spectra of the nanosized FAU-H (A): (a) FAU-H-2, (b) FAU-H-12,
H-16, (c) FAU-H-19, (d) FAU-H-23 and FAU-D (B): (a) FAU-D-12, (b) FAU-D-16,
(c) FAU-H-16, (d) FAU-H-19, (e) FAU-H-23 and FAU-D (B): (a) FAU-D-2, (b)
(c) FAU-D-19, (d) FAU-D-23 as a function of crystallisation time at 50 ºC.
FAU-D-12, (c) FAU-D-16, (d) FAU-D-19 (e) FAU-D-23 as a function of crystal­
lisation time at 50 ºC.

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M. Markovski et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132422

investigation to understand the distribution of Al, specially at the initial

stages of crystallization. The Q4(4Al)/Q4(3Al) ratio was calculated and
plotted against the crystallization time (Fig. 9).
All FAU-D samples have lower Q4(4Al)/Q4(3Al) ratio relatively to
FAU-H samples. The highest difference is observed at 12 h of crystalli­
zation (10.5 and 7.5 for FAU-H-12 and FAU-D-12, respectively). After
16 h of crystallization the difference between the Q4(4Al)/Q4(3Al) ra­
tios decreases and vanished at 23 h. The significant difference of this
ratio at 12 h indicates a big difference in the Al distribution at the early
stages of crystallization even for a comparable Si/Al ratio. The clustering
of Al is favored in H2O giving Al rich particles while in D2O, the Al seems
to be more dispersed giving rise to Si rich particles. This is in line with
the differences observed in viscosity and conductivity, the lower the
mobility of Na+, the less it is trapped in the solid particles and the more
the particles are Si rich. Along the crystallization, the cations distribu­
tion reaches a certain equilibrium giving birth to particles with similar
Si/Al ratios and similar Al and Na distributions.

4. Conclusions

The effect of the synthesis medium on the crystallisation kinetics of

nanosized FAU zeolites was studied in template-free colloidal suspen­
sions using both hydrated (H) and deuterated (D) medium (FAU-H and
FAU-D series). The chemical reaction mechanism, crystallization rate,
particle size, chemical composition and the local Al distribution were
investigated. While all samples are almost similar at the end of the
crystallization, at the initial stage of crystallization in D2O, the particles
are characterized by a slower crystallization rate compared to H2O. This
is due to a lower mobility of Na+ and a higher viscosity of D2O compared
to H2O medium. This is accompanied by a lower clustering of Al in the
crystals synthesized in D2O compared to those synthesized in H2O. This
work opens new perspectives to control the Al distribution in Al rich
zeolites by controlling the crystallization rates.

CRediT authorship contribution statement

Fig. 8. 29Si MAS NMR spectra of nanosized FAU-H (A): (a) FAU-H-12, (b) FAU-
H-16, (c) FAU-H-19, (d) FAU-H-23 and FAU-D (B): (a) FAU-D-12, (b) FAU-D-16, MM: performed the synthesis, characterization and paper prepara­
(c) FAU-D-19, (d) FAU-D-23 as a function of crystallisation time at 50 ºC. tion; ED: research idea and NMR; SG, AM, AA: synthesis and XRD; VR:
ICP analysis; OL: TEM characterization; IG and FD: IR characterization;
SM: research idea, funding and editing of manuscript. All authors were
involved in editing the manuscript.

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.

Data availability

No data was used for the research described in the article.

Acknowledgements
Fig. 9. Q4(4Al)/Q4(3Al) ratio derivate from 29Si MAS NMR spectra of nano­
sized FAU-H (open circle) and FAU-D (black circle) series as a function of
crystallisation time at 50 ºC. Co-funded by the European Union (ERC, ZEOLIghT, 101054004).
Views and opinions expressed are, however, those of the author(s) only
and do not necessarily reflect those of the European Union or the Eu­
The Si/Al ratio was additionally determined by ICP-MS and EDX
ropean Research Council. Neither the European Union nor the granting
(Table 1, Fig. S2). Based on ICP-MS and EDX, the Si/Al ratio of FAU-H-2
authority can be held responsible for them. The authors acknowledge
and FAU-D-2 is the highest (1.6–1.7 based on EDX) and decrease to 1.3
the support of the Centre for Zeolites and Nanoporous Materials, Label of
for all of the samples after 16 h of crystallization. This decrease in the Si/
Excellence, Normandy Region (CLEAR): 239216.
Al ratios is in line with the tendency observed in the FT-IR spectra
(Fig. 4).
Appendix A. Supporting information
The resolution of the 29Si NMR spectra increases with the crystal­
linity of the samples (Fig. 8). Being the most intense, the peaks corre­
Supplementary data associated with this article can be found in the
sponding to Q4(4Al) at 85 ppm and Q4(3Al) at 89 ppm deserve more
online version at doi:10.1016/j.colsurfa.2023.132422.

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