materials

Article
The Effect of Heat Treatment on the Structure of Zeolite A
Magdalena Katarzyna Król * and Piotr Jeleń

Faculty of Materials Science and Ceramic, AGH University of Science and Technology, 30 Mickiewicza Av.,
30-059 Krakow, Poland; [email protected]
* Correspondence: [email protected]

Abstract: Knowledge about the thermal properties of zeolites is extremely important due to their
potential application in the chemical industry. In this work, the thermal stability and the dehydration
process of zeolite A were investigated by in situ high temperature Fourier transform infrared spec-
troscopy. The progress of thermal decomposition that zeolite A underwent during the controlled
temperature increase in the range of 25–600 ◦ C was determined by the DRIFT spectroscopic method.
Infrared spectra are presented and discussed for this compound on the basis of the crystal structure.
Based on the courses of the obtained DRIFT spectra, it was found that, during heating, water was
gradually removed from the structure of the material, followed by dehydration and formation of
hydrogen bonds. It was established that the process of thermal degradation began as early as 550 ◦ C.
The analysis of the obtained results of structural tests can be repeated on other materials from the
zeolite group and complements the research work on the thermal analysis of these materials.

Keywords: zeolite A; thermal stability; dehydration; DRIFT spectroscopy; in situ measurement





 1. Introduction
Citation: Król, M.K.; Jeleń, P. The Zeolites are crystalline, hydrated aluminosilicates built of aluminum and silica tetrahe-
Effect of Heat Treatment on the drons (so-called primary building units—PBUs) connected at the corners to form a spatial
Structure of Zeolite A. Materials 2021, network [1]. The lattice of these aluminosilicates is composed of one or more structural
14, 4642. https://doi.org/10.3390/ units which are differently connected, which determines the different zeolite topologies.
ma14164642 The zeolite structure is formed by a system of chambers and channels [2]. The chambers
are usually in the shape of polyhedra with empty spaces inside. Their size depends largely
Academic Editor: Bruno de Gennaro on the structural arrangement of the PBUs. The size and the shape of the channels are
important in selecting cations and molecules that can enter the interior of the crystal.
Received: 19 July 2021 Due to their properties, zeolites are widely used in various branches of the chemical
Accepted: 12 August 2021
industry [3]. They can be found in areas such as microelectronics, optics, medicine, and
Published: 18 August 2021
agriculture. The physio-chemical properties that determine such a wide application range
include high adsorption capacity, molecular sieve capacity, high selectivity, ion exchange
Publisher’s Note: MDPI stays neutral
capacity, as well as resistance to acids and elevated temperatures. The high inner surface
with regard to jurisdictional claims in
area of zeolites has many types of active sites of different strength depending on the
published maps and institutional affil-
type of structure. Materials with such a large possibilities of surface and physio-chemical
iations.
properties modifications are used as adsorbents, ion exchangers, and catalysts.
Among the many known structures, zeolite A deserves special attention. It is one of
the most studied and used synthetic zeolites, the discovery of which became a breakthrough
for the petroleum processing industry. At the same time, it also became the most commonly
Copyright: © 2021 by the authors. used in many areas of everyday life (detergents, insulating glasses, etc.). It is a material
Licensee MDPI, Basel, Switzerland.
obtained by synthesis from readily available raw materials at a not too high temperature,
This article is an open access article
and the process itself is relatively simple [4].
distributed under the terms and
Zeolite A was chemically and structurally (both experimental and theoretical) investi-
conditions of the Creative Commons
gated in several early studies [5–8]. Its ideal chemical formula is Na96 [Al96 Si96 O384 ]·216H2 O.
Attribution (CC BY) license (https://
The zeolite A structure is presented in Figure 1. Its space group was determined to be
creativecommons.org/licenses/by/
4.0/).
P3, and the positions of all non-hydrogen atoms and, thus, the geometry, were provided;

Materials 2021, 14, 4642. https://doi.org/10.3390/ma14164642 https://www.mdpi.com/journal/materials

Materials 2021, 14, x FOR PEER REVIEW 2 of 9

Materials 2021, 14, 4642 2 of 9

Na96[Al96Si96O384]·216H2O. The zeolite A structure is presented in Figure 1. Its space group
was determined to be P̄3, and the positions of all non-hydrogen atoms and, thus, the ge-
ometry,
positionswere provided;
of the H-bondspositions
were onlyofinferred.
the H-bonds
Smallwere
changesonlyininferred. Small changes
cation positions in
and in the
cation
zeolitepositions
framework andwere
in the zeolite framework
observed were observed
upon dehydration [9]. upon dehydration [9].

(a) (b) (c)

Figure
Figure1.1.Zeolite
ZeoliteNa-A
Na-Acrystal
crystallattice:
lattice:(a)
(a)model
modelstructure
structureofofzeolite
zeoliteNa-A;
Na-A;(b)
(b)simplified
simplifiedrepresenta-
representa-
tion
tion of
of zeolite A crystal
zeolite A crystalstructure
structurehighlighting
highlightingthe
the atomic
atomic cavities
cavities occupied
occupied by cations
by cations (prepared
(prepared with
with
the use of VESTA software [10] based on the .cif file available on the [2]); (c) SEM image of zeolite of
the use of VESTA software [10] based on the .cif file available on the [2]); (c) SEM image A.
zeolite A.
Different techniques were applied to analysis of thermal behavior of zeolites. Among
other commontechniques
Different methods of thermal
were analysis
applied such as
to analysis of differential
thermal behaviorthermal ofand thermogravi-
zeolites. Among
metric
other analysismethods
common (DTA and of TG),
thermalheating in a such
analysis furnace attached tothermal
as differential the diffractometer can be
and thermograv-
considered
imetric as useful.
analysis (DTAIR andspectroscopy
TG), heating is one
in a of the most
furnace common
attached methods
to the for investigation
diffractometer can be
of zeolite structure.
considered as useful. Using in situ DRIFT
IR spectroscopy is onetechnique,
of the most thecommon
formation of hydroxyl
methods groups,
for investiga-
the dehydration/rehydration processes, and the interaction of OH
tion of zeolite structure. Using in situ DRIFT technique, the formation of hydroxyl groups,groups with various
encaged
the and adsorbed speciesprocesses,
dehydration/rehydration can be observed
and the [11]. For example,
interaction of OH based on the
groups areas
with under
various
the DRIFT spectra of zeolite Y, the desorption profiles was calculated
encaged and adsorbed species can be observed [11]. For example, based on the areas un- [12]. It was found that
their
der shape
the DRIFTwasspectra
principally identical
of zeolite Y, theto the desorption
desorption curves
profiles wasobtained by conventional
calculated [12]. It was
temperature-programmed
found desorption identical
that their shape was principally techniques. to the desorption curves obtained by con-
Bothtemperature-programmed
ventional adsorptive and catalytic properties
desorptionoftechniques.
zeolites depend not only on the kind of
extra-framework cations [13] but also are strongly determined
Both adsorptive and catalytic properties of zeolites depend by theirnot water
only on content. Metal
the kind of
impregnation was mainly used to improve the zeolites catalytic properties
extra-framework cations [13] but also are strongly determined by their water content. [14,15]. The aim
of thisimpregnation
Metal study was towas summarize
mainly used and obtain morethe
to improve detailed structural
zeolites catalyticinformation on the
properties [14,15].
zeolite A by studying its sodium and ion-exchanged forms. In
The aim of this study was to summarize and obtain more detailed structural informationthis study, we examined
thermal
on behavior
the zeolite A byofstudying
zeolite A itsby sodium
in situ highandtemperature
ion-exchanged spectroscopic
forms. In data and discussed
this study, we ex-
the results on the basis of the structural features.
amined thermal behavior of zeolite A by in situ high temperature spectroscopic data and
discussed theand
2. Materials results on the basis of the structural features.
Methods
Pure synthetic
2. Materials zeolite A as its sodium form was used as the starting material. Zeolite
and Methods
Na-A was synthesized under hydrothermal conditions using the procedure described
Pure
in [16]. Tosynthetic zeolite
obtain other A as its
cationic sodium
forms, form
initial wasNa-A
zeolite used was
as the starting
treated by material. Zeolite
water solution of
Na-A was synthesized under hydrothermal conditions using the procedure
Ca-, Cu-, Ni-, or Zn-nitrates. The concentration of the solutions was 0.01 mol/dm . Ion described
3 in
[16]. To obtain
exchange was other
carriedcationic
out at forms, initial
60 ◦ C for 24 h.zeolite
AfterNa-A
the ionwas treated process,
exchange by waterthe
solution
samples of
Ca-, Cu-, Ni-, or Zn-nitrates. The concentration of the solutions was
were centrifuged and washed several times with distilled water. Phase composition of 0.01 mol/dm 3. Ion

exchange
resulting was carried
samples wasout at 60 °Cusing
confirmed for 24X-ray
h. After the ion The
diffraction. exchange
resultsprocess, the samples
were obtained using
were centrifuged and washed several times with distilled water.
Empyrean diffractometer (PANanalitycal, Malvern, Great Britain) using Bragg–BrentanoPhase composition of
resulting
geometrysamples
and CuKawasradiation
confirmed using X-ray
(measuring timediffraction. The step
was 4 h, and results
overwere
wasobtained
0.05 ). using
◦
Empyrean diffractometer
The DRIFT measurements(PANanalitycal, Malvern,
were performed onGreat Britain)
a Vertex 70 vusing Bragg–Brentano
spectrometer (Bruker,
geometry and CuKa radiation (measuring time was 4 h, and step over
Billerica, MA, USA) equipped with a DTGS detector using a Praying Mantis DRIFT attach- was 0.05°).
mentThe DRIFTScientific
(Harrick measurements
Products, were performedNY,
Pleasantville, on USA).
a Vertex
The70samples
v spectrometer (Bruker,
were measured at
Billerica, MA, USA) ◦
equipped with a DTGS detector using a Praying
temperatures up to 600 C under ambient pressure in Kubelka-Munk scale [17]. Heating Mantis DRIFT at-
tachment set to 5 ◦ C
rate was (Harrick Scientific Products,
per minute. Pleasantville,
In total, NY, aUSA).
64 scans with 10 kHz Thescanner
samplesvelocity
were meas-
were
ured at temperatures
acquired each minute.up to 600 deconvolution
Spectral °C under ambient was pressure
carried outin using
Kubelka-Munk
SpectraCalcscale [17].
software
Heating
(Galacticrate was set Corp.,
Industries to 5 °CMain
per minute.
St Salem, In NH,
total,USA).
64 scans with a 10
A mixture of kHz scanner velocity
Gaussian–Lorentzian
with a starting ration of 0.5 was created. As a result, a set of fitted bands with an RMS error
below 1 was obtained.
 were acquired each minute. Spectral deconvolution was carried out using SpectraCalc
Materials 2021, 14, 4642
software (Galactic Industries Corp., Main St Salem, NH, USA). A mixture of Gaussian– 3 of 9
Lorentzian with a starting ration of 0.5 was created. As a result, a set of fitted bands with
an RMS error below 1 was obtained.
For comparative purposes, the water contents were obtained by heating 10 mg sam-
ples For comparative
in platinum purposes,
crucibles the water
at 5 °C/min in contents
air usingwere obtained
a thermal by heating
analyzer 10 mg
Netzsch STAsamples
449 F3
in platinum
Jupiter crucibles
(Netzsch, Selb,at 5 ◦ C/min in air using a thermal analyzer Netzsch STA 449 F3
Deutschland).
Jupiter (Netzsch, Selb, Deutschland).
3. Results and Discussion
3. Results and Discussion
The average particle size of zeolite A was 1 μm (as observed with SEM; Figure 1c),
The
and it didaverage particle
not contain anysize of zeolite
other A wasphases
crystalline 1 µm (asas observed
impurity with SEM;by
(checked Figure
XRD;1c), and
Figure
itS1).
didIts
not contain any other crystalline phases as impurity (checked by XRD;
dehydration behavior was investigated based on thermal analysis (Figure 2), and Figure S1). Its
dehydration behavior was investigated based on thermal analysis (Figure
selected temperature points were determined for additional structural investigations. 2), and selected
temperature
Thermalpoints were
stability is determined
traditionallyfor additionalby
determined structural
thermal investigations.
analysis. TG-DSC curves of
Thermal stability is traditionally determined
zeolite A are presented in Figure 2. Thermogravimetric by thermal analysis.
analysis showedTG-DSC curves
endothermic
of zeolite A are presented in Figure 2. Thermogravimetric analysis showed endothermic
weight loss due to dehydration. Mass loss for the quasi-pure zeolite A agreed well with
weight loss due to dehydration. Mass loss for the quasi-pure zeolite A agreed well with
other literature data [1]. At 400 °C, the major part of the dehydration was completed. The
other literature data [1]. At 400 ◦ C, the major part of the dehydration was completed.
sample also contained a small amount of surface and zeolite water, noticeable at a mass
The sample also contained a small amount of surface and zeolite water, noticeable at a
loss below 180 °C. The second step with lower slope was observed between 200 and 360
mass loss below 180 ◦ C. The second step with lower slope was observed between 200 and
°C (mass loss of 2.9 wt.%). Two step water loss was attributed to subsequent α- and β-
360 ◦ C (mass loss of 2.9 wt.%). Two step water loss was attributed to subsequent α- and
cages dehydration [6]. Complete water loss was about 20.5 wt.%, which was slightly less
β-cages dehydration [6]. Complete water loss was about 20.5 wt.%, which was slightly
than 22.2 wt.% calculated for Na96[Al96Si96O384]·216H2O empirical formula) [6]. The ob-
less than 22.2 wt.% calculated for Na96 [Al96 Si96 O384 ]·216H2 O empirical formula) [6]. The
tained value agreed well with the previous results [18,19]. It is also well known [20] that
obtained value agreed well with the previous results [18,19]. It is also well known [20] that
most zeolites are not fully hydrated at room conditions but continue to hydrate as relative
most zeolites are not fully hydrated at room conditions but continue to hydrate as relative
humidity is increased to 100%.
humidity is increased to 100%.
Decarbonation components
Decarbonation components of of the
thesample
samplecouldcouldoccur
occurfrom
fromabout
about300
300◦°C, hence,the
C, hence, the
presence provided negligible effects on the DSC curve. The zeolite
presence provided negligible effects on the DSC curve. The zeolite commonly showed commonly showed an
exothermic peak at about 900 °C ◦due to the formation of amorphous
an exothermic peak at about 900 C due to the formation of amorphous aluminosilicate aluminosilicate by
destruction
by of the
destruction zeolite
of the structure
zeolite and and
structure its subsequent
its subsequentrecrystallization into ainto
recrystallization newaphase
new
[21,22]. Dehydrated zeolite A was stable up to 800 °C, when
◦ it recrystallized
phase [21,22]. Dehydrated zeolite A was stable up to 800 C, when it recrystallized into a β-cris-
into a
tobalite-type structure
β-cristobalite-type [1]. [1].
structure

Figure2.
Figure 2. TG-DSC
TG-DSC curves
curves of
of zeolite
zeolite Na-A.
Na-A.

The −1
The FT-IR
FT-IRspectrum
spectrumof ofzeolite
zeoliteAAininthe
the4000–400
4000–400cm cm−1 range
range isis displayed
displayed in
in Figure
Figure33
(spectra of all cationic forms are presented as Figure S2). Based on the interpretation
(spectra of all cationic forms are presented as Figure S2). Based on the interpretation of both
of
the theoretical D4R units spectrum [23] as well as the spectrum of the simplified
both the theoretical D4R units spectrum [23] as well as the spectrum of the simplified periodic
model of model
periodic zeolite of
A zeolite
[24], vibrations of the following
A [24], vibrations bands were
of the following assigned:
bands were assigned:
•• 1005 cm−–11 —asymmetric stretching vibrations of bridge bonds—νas Si–O(Al)
1005 cm —asymmetric stretching vibrations of bridge bonds—νas Si–O(Al)
• 726 cm−–11 —symmetric stretching vibrations of bridge bonds—νs Si–O–Si
• 726 cm —symmetric stretching vibrations of bridge bonds—νs Si–O–Si
• 666 cm−1 —symmetric stretching vibrations of bridge bonds—νs Si–O–Al
•• 666 cm
cm−–1—symmetric stretching vibrations of bridge bonds—νs Si–O–Al
554 1 —(complex band) symmetric stretching vibrations of bridge bonds—ν
s
• 554 cm and
Si–O–Si –1—(complex
bending band) symmetric
vibrations—δ stretching vibrations of bridge bonds—νs Si–
O–Si–O
• O–Si
465 cm −1 —bending
and bending vibrations—δ
vibrations—δO–Si–O
O–Si–O, occurring in “antiphase”
• − 1
379 cm —bending vibrations—δ O–Si–O and δ O–Al–O
 • 379 cm–1—bending vibrations—δ O–Si–O and δ O–Al–O
Materials 2021, 14, x FOR PEER REVIEW 4 of 9
Additionally, in the OH stretching region (3000–4000 cm−1), very intense peaks in a
superposition of several component bands with maximum at ca. 3450 cm−1 were observed.
Materials 2021, 14, 4642 Two intense bands were also observed in the H2O bending region at ca. 1650 cm−1. A 4very
of 9
• 465 cm–1—bending vibrations—δ O–Si–O, occurring in “antiphase”
weak and broad band was finally observed around 3245 cm−1 that could be finally as-
•signed
379tocm –1—bending vibrations—δ O–Si–O and δ O–Al–O
the first overtone of the H2O bending mode.
Additionally, in the OH stretching region (3000–4000 cm−1), very intense peaks in a
superposition of several component bands with maximum at ca. 3450 cm−1 were observed.
Two intense bands were also observed in the H2O bending region at ca. 1650 cm−1. A very
weak and broad band was finally observed around 3245 cm−1 that could be finally as-
signed to the first overtone of the H2O bending mode.

Figure 3.
Figure 3. FT-IR
FT-IRspectrum
spectrumof
ofzeolite
zeoliteNa-A.
Na-A.

The DRIFT spectra

Additionally, in the were recorded region
OH stretching as a function
(3000–4000 cm−1 ), very
of temperature forintense
the sodium
peaksform
in a
superposition of several component bands withwith
maximum at ca. − 1
3450 Resulting
cm werespectraobserved.
of zeolite A and a zeolite sample exchanged different metals. are
Two
shownintense bands were also
in supplementary observed
materials inwavenumber
in full the H2 O bendingrangeregion at ca.S3–S7.
as Figures cm−1 . A
1650 Figures 4,
very weak and broad band was finally observed around 3245 cm −1 that could be finally
5, and 6 show the spectra in a smaller
Figure 3. FT-IR spectrum of zeolite Na-A. wavenumber range.
assigned to the first overtone of the H2 O bending mode.
The DRIFT
The DRIFT spectra
spectra were
were recorded
recorded as as aa function
function ofof temperature
temperature forfor the
the sodium
sodium form
form
of zeolite A and a zeolite sample exchanged with different metals. Resulting
of zeolite A and a zeolite sample exchanged with different metals. Resulting spectra spectra are
are
shown in
shown in Supplementary
supplementary Materials
materials ininfull
fullwavenumber
wavenumberrange rangeasasFigures
FiguresS3–S7.
S3–S7.Figures
Figures 4–6
4,
show
5, andthe spectra
6 show theinspectra
a smaller
in awavenumber range.
smaller wavenumber range.

(a) (b) (c) (d)

Figure 4. DRIFT spectra of zeolite A recorded at 50 °C intervals (from 50 to 400 °C, respectively, from top to bottom): (a)
Na-A; (b) Ca-A; (c) Cu-A; and (d) Zn-A.

(a) (b) (c) (d)

Figure 4. DRIFT spectra of zeolite A recorded at 50 ◦°C ◦ C, respectively, from top to bottom): (a)
C intervals (from 50 to 400 °C,
Na-A; (b) Ca-A; (c) Cu-A; and (d) Zn-A.
Na-A; (b) Ca-A; (c) Cu-A; and (d) Zn-A.
Changes in the spectral envelope to about 400 ◦ C were mainly related to water loss
(Figure 4). The zeolite dehydration took place up to the temperature of about 180 ◦ C, hence,
the intensity of the band with a large FWHM (full width at half maximum) disappeared at
about 3350 cm−1 for all measurement series. At the same time, the band at about 1600 cm−1 ,
Materials 2021, 14, 4642 5 of 9

related to the H−O−H bending vibrations, also disappeared (Supplementary Materials).

There is evidence in the literature for the correlation between the integral intensity of the
mentioned bands and the amount of adsorbed water, the so-called bulk water [12,25]. This
reduction is different for zeolites exchanged with different metals, because metals differ in
their ability to surround themselves with water molecules.
The other bands observed in this range were associated with stretching vibrations of
OH groups of structural water molecules and OH functional groups. The deconvolution
of the exemplary spectra obtained at 200 ◦ C (Figure 5) revealed that, in this range, at
least three bands could be distinguished. Two very intense and well resolved peaks at
3468 and 3282 cm−1 , respectively, were observed in the case of spectrum of zeolite Na-A
(Figure 5a). At a closer inspection, an additional two shoulders at 3552 and 3667 cm−1
were evident, especially at higher temperatures. These wavenumbers were similar to those
described in related literature [26,27]. Following the bands assignment proposed in the
work [26], the bands could be assigned successively: 3282 cm−1 to molecules arranged in a
tetrahedral “ice-like” hydrogen bonded network; 3468 cm−1 to water molecules involved
in two H-bonds; and 3552 cm−1 to molecules of monomeric structures or assembled to
form dimers by linear H-bonds. The shifting of the above-mentioned bands towards higher
wavenumbers with increasing temperature (Figure 4a) resulted from partial dehydration
and, thus, weakening of interactions between individual molecules due to the loss of some
hydrogen bonds. The band at about 3580 cm−1 disappeared completely at the temperature
of 400 ◦ C, which proved complete dehydration and agreed with the results obtained for
the TG-DSC analysis (Figure 2).
The last band (at 3667 cm−1 ) could be assigned to the Si−OH−Al group (bridging
hydroxyl groups). This band disappeared above 200 ◦ C. A similar band was attributed
to vibrations of corresponding groups in the structure of thermal activated zeolite X [28]
or mordenite [29]. By contrast, as the temperature increased, the shoulder at 3650 cm−1
was more evident in the case of Ca form (Figure 4b). Similar results were described in
the work [30]. Na-A zeolite showed the presence of small amounts of molecular water,
while Ca-A zeolite showed the presence of non-acidic CaOH+ groups and of symmetrical
carbonate ions as well as small traces of acidic OH functionalists. The band at about
3569 cm−1 in the spectrum of zeolite Ca-A presented in Figure 4b was caused by Ca(OH)+
absorbance. This phenomena can be explained by the Hirschler-Plank dissociative water
adsorption model [19]. Interestingly, this band was not observed in any other series
of measurements.
It was expected that, with the appearance of stretching vibrations originating from
OH groups in the spectrum of the zeolite, the corresponding bending vibrations would also
appear. Positions of this band were recognized in the related literature and ranged from
1060 to 1020 cm−1 [31,32]. The authors of work [12], on the other hand, noticed that the
strong overlapping of the bands due to OH bending vibrations strongly overlapped with
the Si−O stretching vibrations and could not be detected with the use of IR investigations.
In our work, there were evident bands at about 1055 and 1067 cm−1 (Figure 6), which
agreed well with the results presented in the work [32].
The copper and the nickel forms of zeolite were selected for this research due to their
potential use in catalysis [33]. The envelopes of both spectra (Figure 4c) were similar to the
sodium form of zeolite A, possibly because both Cu2+ and Ni2+ ions occupied the same
site as Na+ (the center of the six-membered ring in α-cage) [34]. The lack of acid centers
could be explained, on the one hand, by the high proportion of aluminum in the zeolite
A structure and, on the other hand, the tendency of the analyzed ions to form dimers,
e.g., Cu–Cu and Ni–Ni bonds. This property was theoretically confirmed in our previous
work [24].
The Zn form of zeolite was characterized by a modified surface charge due to the
generation of new Lewis acid sites and variable redox properties of zeolites [35], which
influenced, among other things, the selective adsorption of cationic dyes [36]. The zinc
form of zeolite A had a completely different course of the IR spectrum in the discussed
Materials 2021, 14, x FOR PEER REVIEW 6 of 9

The Zn form of zeolite was characterized by a modified surface charge due to the
Materials 2021, 14, 4642 generation of new Lewis acid sites and variable redox properties of zeolites [35], which 6 of 9
influenced, among other things, the selective adsorption of cationic dyes [36]. The zinc
form of zeolite A had a completely different course of the IR spectrum in the discussed
range (Figure
range (Figure 4d).
4d). Some
Someofofthe thezinc
zincions
ionswere probably
were probably adsorbed
adsorbedat surface-bridging
at surface-bridging hy-
droxyls ≡Si–OH–Al≡ or at surface hydroxyls ≡Si–OH, ≡Al–OH with
hydroxyls ≡Si–OH–Al≡ or at surface hydroxyls ≡Si–OH, ≡Al–OH with the formation the formation of
Me(OH)(OZe) complex [37]. Hydroxycomplexes Zn(OH) pZe2−p Zn,
− p
of Me(OH)(OZe) complex [37]. Hydroxycomplexes Zn(OH)p Ze2 Zn, similarly to zinc similarly to zinc hy-
droxides, were
hydroxides, weremore insoluble
more insolublethan the the
than hydroxycomplexes
hydroxycomplexes of the
of remaining investigated
the remaining investi-
metals,
gated whichwhich
metals, resulted in a large
resulted amount
in a large of structured
amount water.
of structured This This
water. hypothesis was was
hypothesis con-
firmed by the appearance of a band at ca. 3649 cm −1, analogous
− 1 to that visible
confirmed by the appearance of a band at ca. 3649 cm , analogous to that visible in the in the spec-
trum of the
spectrum of Ca-form.
the Ca-form.

(a) (b)
Figure 5.
Figure 5. Decomposition
Decomposition of
of the
the spectra
spectra recorded
recordedat
at200 ◦ C: (a) Na-LTA; and
200°C: and (b)
(b) Ca-LTA.
Ca-LTA.
Figures 6 and 7 show the DRIFT spectra of zeolite A in the range of Si–O–Al vibration
modes. Figure
In the 6 and
initialFigure
zeolite 7 show
(zeolitethe DRIFT
Na-A; spectra
Figure 6a),of zeolite A bands
absorption in the were
rangeobserved
of Si–O–Al at
vibration
1010 cm−1modes. (with aIn the initial
shoulder at zeolite
1150 cm(zeolite
−1 ), 950,Na-A;
669, Figure
556, and 6(a)),
470 absorption
cm−1 . The bandsband at were
ca.
observed
950 cm−1 was at 1010 duecm
−1 (with a shoulder at 1150 cm−1), 950, 669, 556, and 470 cm−1. The band
to stretching Si–OH, and its change in intensity corresponded well with
at ca.
the 950 cm was
observations
−1
forduethetoSiO–H
stretching
bandSi–OH,
(at ca. and3600itscm change
−1 ); it in intensitydisappeared
gradually corresponded as well
the
with the observations for the SiO–H band (at ca. 3600
temperature rose. At higher values of the wavenumber, there was a broad band with a cm −1); it gradually disappeared as

the temperature
maximum at 1010 rose.
cm−At higher
1 and values ofatthe
a shoulder 1150wavenumber,
cm−1 . Boththere 1150 was
and a1010
broad cmband with
−1 bands
a maximum
were attributed at 1010 cm and a stretching
−1
to asymmetric shoulder atvibrations
1150 cm of −1. Both
Si–O. 1150
Theand 1010 cm
shoulder wasbands
−1 were
attributed
attributed to asymmetric stretching vibrations of Si–O. The
to the location of silicon atoms on different oxygen atoms in the framework. The (Si–O–(Al) shoulder was attributed to the
location of silicon atoms on different oxygen atoms in the
band shifted to the lower wavenumber as the temperature increased. The probable reason framework. The (Si–O–(Al) band
shifted
is that theto cation
the lower lacking wavenumber
a hydrationasshell the more
temperature
stronglyincreased. The probable
attracted silicon, which led reason
to anis
that the cation lacking a hydration shell more strongly attracted
elongation of the Si–O bond (lowering its force constant). The same interpretation could silicon, which led to be
an
elongation to
transferred of other
the Si–O forms bond (lowering
of zeolite, e.g.,itsCu-A
forceinconstant).
Figure 6b.The same interpretation could
be transferred
The spectra to of
other forms
zeolite of zeolite,
Ca-A in Figure e.g.,7a,
Cu-A in Figure
especially 6b. in Figure 7b, showed a
Zn-A
The spectra
significantly of zeolite
different courseCa-A in Figure
compared to the7a,other
especially
forms.Zn-A in Figure 7b,however,
The differences, showed came a sig-
nificantly different course compared to the other forms. The
down to the shifting of some bands in relation to each other, which gave the visual effect differences, however, cameof
down to the shifting of some bands in relation to each other,
splitting the bands. Theoretical studies on the structure of the anhydrous form of zeolite which gave the visual effect
Aof[24]
splitting
showed the bands.
that such Theoretical
an effectstudies on the
is a direct structure ofof
consequence thethe
anhydrous
position form of zeolite
of individual
A [24] showed that
extra-framework such(in
cations anrelation
effect istoathe direct consequence
six-membered ringof(Bthe
siteposition
according of individual
to [7,38])).
extra-framework
The cations that bound cationsmore (in relation
strongly totothe
thesix-membered
skeleton (e.g.,ring (B sitecations
d-block according Zn2+ )
suchtoas[7,38])).
The cations
distorted that bound
it more, resulting more strongly
in the formation to the ofskeleton
more than (e.g.,
oned-block
type of cations such as Zn2+)
Si–O bond.
According to literature [23,39], the band at about
distorted it more, resulting in the formation of more than one type of Si–O bond.555 cm − 1 corresponded to symmetric

stretching
Accordingvibrations of double
to literature four-membered
[23,39], the band at about rings in 555thecmLTA structure. Its
–1 corresponded to complex
symmet-
envelope
ric stretchingindicated
vibrationsthat it ofwas a superposition
double four-membered of several
rings incomponent bands. Calculated
the LTA structure. Its complex
spectra
envelope indicated
indicated thethat
typical ringa vibration
it was superposition (PO—pore opening
of several vibration)
component gaveCalculated
bands. a band at
lower
spectra wavenumbers.
indicated theThe presence
typical of this band
ring vibration in discussed
(PO—pore spectra
opening indicated
vibration) thatathis
gave bandunitat
(double four-membered ring) was maintained in the entire
lower wavenumbers. The presence of this band in discussed spectra indicated that this analyzed temperature range.
unit (double four-membered ring) was maintained in the entire analyzed temperature
range.
Materials 2021, 14, 4642 7 of 9
Materials 2021, 14, x FOR PEER REVIEW 7 of 9

(a) (b)
Figure 6.
Figure 6. DRIFT
DRIFT spectra
spectra of
of zeolite
zeolite A
A recorded
recordedat 50◦°C
at50 intervals (from
C intervals (from50
50to 600◦°C):
to600 (a)Na-A;
C): (a) Na-A;and
and
(b)Cu-A.
(b) Cu-A.

(a) (b)
Figure 7.7. DRIFT
Figure DRIFTspectra
spectraofofzeolite
zeoliteAArecorded
recorded
at at ◦ C°C
5050 intervals
intervals (from
(from 50 600
50 to ◦ C):°C):
to 600 (a) Ca-A;
(a) Ca-A; andand
(b)
(b) Zn-A.
Zn-A.
It is well known that zeolite A is not as thermally stable as other zeolites. For example,
It is well known that zeolite A is not as thermally stable as other zeolites. For example,
zeolite Ca-A loses its sorptive ability towards organic vapors if the temperature exceeds
zeolite Ca-A loses its sorptive ability towards organic vapors if the temperature exceeds
350 ◦ C [40]. At 500 ◦ C, first indications of partial collapse of a zeolite A structure (regardless
350 °C [40]. At 500 °C, first indications of partial collapse of a zeolite A structure (regard-
of the cationic form) were evident in DRIFT spectra (Figure 6). Discussed zeolite structural
less of the cationic form) were evident in DRIFT spectra (Figure 6). Discussed zeolite struc-
collapse was followed by formation of an amorphous matter, resulting in an increase in the
tural collapse was followed by formation of an amorphous matter, resulting in an increase
bands FWHM. It agreed well with the results of X-ray powder diffraction experiments [41]
in the
that bands
such FWHM. amorphous
a prepared It agreed well with thesubstance
NaAlSiO results of X-ray powder
was stable diffraction
between 850 ◦experi-
C and
4
ments ◦ [41] that such a prepared amorphous NaAlSiO 4 substance was stable between 850
900 C. As part of this study, further heating of the system was not possible due to the
°C and 900limitations
apparatus °C. As partresulting
of this study, further
from the heatingofofthe
specificity themethod.
system was not possible due to
the apparatus limitations resulting from the specificity of the method.
4. Conclusions
4. Conclusions
The DRIFT technique is used to test powders and rough surfaces of various materials.
The DRIFT technique
Its unquestionable advantageis used toability
is the test powders andspectra
to collect rough in
surfaces of variousespecially
situ conditions, materials.
Its unquestionable
useful advantage
in the analysis is the
of reactions ability
with to collect
the use spectraThe
of catalysts. in situ conditions,
technique can beespecially
applied
useful in theinanalysis
successfully studiesof
ofreactions with the use of catalysts. The technique can be applied
zeolite catalysts.
successfully in studies of zeolite catalysts.
Materials 2021, 14, 4642 8 of 9

In this study, we confirmed the course of zeolite A spectra using the DRIFT technique.
There were no clear differences in the FT-IR spectra of non-dehydrated selected samples
(room temperature) exchanged with different ions. Measurements as a function of tempera-
ture allowed a new insight into the zeolite structure. Using DRIFT technique, observations
could be made of dehydration and dehydroxylation processes of zeolites as well as some
structural changes at higher temperatures.
The essential changes connected with the presence of non-tetrahedral cations could be
observed in the expanded spectra in the OH stretching mode region. It was confirmed that,
based on this spectral range, three types of water may be recognized in zeolite structure:
typical zeolite water, water with crystal-water-like bonds, and water bound to the lattice
by OH-bonds.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/

10.3390/ma14164642/s1, Figure S1: XRD patterns of various cationic form of zeolite A, Figure S2:
FT-IR spectra of various cationic form of zeolite A, Figure S3: DRIFT spectra of zeolite Na-A recorded
at 50 ◦ C intervals (from 50 to 600 ◦ C), Figure S4: DRIFT spectra of zeolite Ca-A recorded at 50 ◦ C
intervals (from 50 to 600 ◦ C), Figure S5: DRIFT spectra of zeolite Cu-A recorded at 50 ◦ C intervals
(from 50 to 600 ◦ C), Figure S6: DRIFT spectra of zeolite Ni-A recorded at 50 ◦ C intervals (from 50 to
600 ◦ C), Figure S7: DRIFT spectra of zeolite Zn-A recorded at 50 ◦ C intervals (from 50 to 600 ◦ C).
Author Contributions: Conceptualization, M.K.K.; methodology, M.K.K. and P.J.; software, M.K.K.
and P.J.; validation, M.K.K. and P.J.; formal analysis, M.K.K.; investigation, M.K.K.; resources, M.K.K.;
data curation, M.K.K. and P.J.; writing—original draft preparation, M.K.K.; writing—review and
editing, M.K.K.; visualization, M.K.K.; supervision, M.K.K.; project administration, M.K.K.; funding
acquisition, M.K.K. Both authors have read and agreed to the published version of the manuscript.
Funding: This work was financially supported by The National Science Centre Poland under grant
no. 2016/21/D/ST8/01692.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data presented in this study are available on request from the corre-
sponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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