Analysis and Control of Acid Sites in Zeolites

Applied Catalysis A, General 606 (2020) 117795
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Applied Catalysis A, General

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Analysis and control of acid sites in zeolites T

a, b,c,
Ana Palčić **, Valentin Valtchev *
a
Ruđer Bošković Institute, Division of Materials Chemistry, Laboratory for Synthesis of New Materials, Bijenička cesta 54, Zagreb, Croatia
b
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Song Ling Rd Qingdao, Shandong, 266101, PR China
c
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 Boulevard Maréchal Juin, Caen, France
ARTICLE INFO ABSTRACT
Keywords: The exceptional catalytic performance of zeolites is due to the presence of active sites in a shape-selective
Zeolites environment, i.e., in micropores with molecular dimensions. The present review provides a comprehensive
Acid sites analysis of active sites in zeolite frameworks. It is focused on the active sites generated by the Al incorporation in
In situ and post-synthesis methods the framework. The inclusion of other heteroatoms in the zeolite framework is also addressed. After the in-
Aluminum location
troduction of zeolite-type materials and a discussion of the structure-properties relationship in zeolites the
central part of the review is devoted to i) the analytical methods and their complementarity for the evaluation of
the number, strength, and position of active sites and ii) the in situ and post-synthesis methods of acid sites
assessment and control. The data presented herein provide guidelines for making zeolite materials by design in
terms of acidity.
1. Introduction range from heterogeneous catalysis, ion and molecular separations to

drug delivery and sensing [5,6]. The selection of a zeolite for a parti-
Zeolites are defined as crystalline alumosilicate microporous mate- cular use is decided on the grounds of its pore system, chemical com-
rials. The designation microporous denotes material comprising pores position, hydrophobicity/hydrophilicity, acidic properties, and (hydro)
smaller than 2 nm based on the IUPAC convention [1]. In the past thermal stability. The industrial impact of zeolites in the field of het-
decades, the term zeolite has been extended to designate materials erogeneous catalysis is enormous. Firstly, they are used in fluid cata-
having a more diverse chemical composition, for instance, there are lytic cracking (FCC) and hydrocracking technology, a vital process in
(silico)aluminophosphate, germanosilicate, zincosilicate, gallosilicate, the oil-refining industry based on FAU-type zeolite [7]. Furthermore,
etc., zeolite-type (zeotype) materials. Presently, the key feature which is they are used in a number of petrochemical processes. A sound example
taken as an essential criterion to classify a material as “zeolitic” is its is the methanol-to-olefins (MTO) technology, where CHA-type and MFI-
structure. A zeolite is built of tetrahedra having a central T atom (T]Si, type zeolites compete as the principle part of the catalyst [8]. It is worth
Al, Ge, Ga, P, B, …) and oxygen at the vertices [2]. The tetrahedra noting the production capacity of olefins of currently the largest MTO
connected by sharing vertex oxygen atoms build a three-dimensional unit in the world is 833,000 metric tons per year [9]. Since 2010 Cu-
system of voids and channels (Fig. 1). Considering the possible building SSZ-13 (CHA-type zeolite) is commercially employed as an emission
units, T–O–T angles and distances, over two million hypothetical zeolite control catalyst in diesel automotive exhaust after-treatment systems
structures have been predicted [3]. However, the zeolite crystallization [10]. The significance of synthetic zeolites in the global market is re-
is a rather complex process (Fig. 1), and presently, there are solely flected through the production of above 3000 kilotons per year (data
about 250 known zeolite framework types approved by the Structure 2014), which continues to grow [11]. The synthetic zeolite market
Commission of the International Zeolite Association [4]. The number of value in 2017 was USD 13.67 billion, and the global zeolite market will
new framework types is continuously increasing, yet there is a big gap reach USD 33.8 billion by 2022 [12].
between predicted and obtained materials. On the other hand, a fra- The acidic properties of zeolitelargely determine their success as
mework can be synthesized with different compositions, thus increasing heterogeneous catalysts. Namely, the conversion degree of the reaction,
the diversity of zeolite properties and potential applications. product yield, selectivity, catalyst lifetime, susceptibility to coking, and
Zeolites are technological materials with diverse applications that regeneration potential is directly related to the nature, number, and
⁎
Corresponding author at: Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 Boulevard Maréchal Juin, Caen, France.
⁎⁎
Corresponding author.
E-mail addresses: [email protected] (A. Palčić), [email protected] (V. Valtchev).
https://doi.org/10.1016/j.apcata.2020.117795
Received 6 May 2020; Received in revised form 18 July 2020; Accepted 15 August 2020
Available online 30 August 2020
0926-860X/ © 2020 Elsevier B.V. All rights reserved.
A. Palčić and V. Valtchev Applied Catalysis A, General 606 (2020) 117795
Fig. 1. Schematic representation of zeolite

structure formation.
distribution of acid sites within the zeolite crystals. In turn, the acidity framework increases.
of zeolites is a function of their structure type and the chemical com- The widespread application of zeolites is a direct consequence of
position of a particular material. In aluminosilicate zeolites, acid sites their properties, and by tuning their features, zeolites become acces-
are associated with the aluminium present in the zeolite material. sible to exhibit the desired performance in a specific application. The
Aluminium can occupy different positions in the framework, which possibilities of zeolite usage in catalysis and gas separation with novel
impacts zeolite acidity. Furthermore, zoning in the aluminium dis- substrates are intensively investigated, and every several years a new
tribution throughout the crystal is observed, which can influence the process is reported [14–16]. Hence, zeolites are undoubtedly going to
catalytic performance of a particular material due to the difference in continue to be broadly employed and, accordingly, improving their
the effective diffusion path of reactants prior to reaching the active site properties to enhance their performance is imperative.
[13]. Hence, the preparation of the materials having well-defined Al
siting is of paramount importance for controlling zeolite acidity. Be-
3. Analysis of acid sites in zeolites
sides aluminium, we have included boron and germanium substitutions
in zeolite framework, which are largely used to generate new zeolite
3.1. Acid sites in zeolites
structures. The Sn-containing zeolites were included in the review to
exemplify the importance of Lewis sites in catalytic reactions. We limit
In the IUPAC Gold book, a Brønsted acid is defined as “a molecular
our review to Sn since the Lewis acidity is a vast topic, which cannot be
entity capable of donating a hydron (proton) to a base (i.e., an acid is a
fully covered in the framework of the present review.
“hydron donor”) or the corresponding chemical species” [17]. On the
Our objective is to present a comprehensive overview of the ad-
other hand, Lewis acid is “a molecular entity, and the corresponding
vances in zeolite acid sites controls with an accent on the recent de-
chemical species, that is an electron-pair acceptor and therefore able to
velopments of the in situ and post-synthesis methods. The zeolite acidity
react with a Lewis base to form a Lewis adduct, by sharing the electron
control would not be possible without an advanced analysis of acid
pair furnished by the Lewis base.” Both types of acid sites may be
sites. Therefore, the methods of analysis of active zeolite sites will be
present in zeolites; hence they are solid acid materials. Purely siliceous
revised as well. The ultimate objective of our review is to provide
zeolite framework is electrically neutral, and its surface is not acidic.
practical guidance for tuning zeolite acidity.
Nevertheless, in such a lattice, the acid sites may arise at structural
defects. Isomorphous substitution of Si4+ with trivalent cations such as
2. Structure - properties relationship in zeolites Al3+ results in the development of Brønsted acid sites since Al3+ gen-
erates negative charge in the framework, which is then compensated by
The structure of zeolites can be represented by various building the presence of a proton. Generally, the Brønsted sites in zeolites ensue
units, the most common way is by rings having a different number of at oxygen atoms of a hydroxyl group bonded to a metal atom of one
central tetrahedral (T) atoms. The oxygen atoms are neglected in this type coordinating to an atom of another type, which acts as the
kind of depiction. Connecting of building units leads to the formation of Brønsted base – the bridging hydroxyls [18]. Recently, in amorphous
the framework with a defined array of voids and channels within the silica-alumina was observed an interaction of penta-coordinated Al
structure. Materials comprising 8-membered ring (8MR) as limiting with adjacent silanols, which act as Brønsted acid sites [19]. Lewis acid
pore opening are defined as small pore zeolites. The pore openings of sites are related to coordinatively unsaturated cations that can accept
medium pore zeolites are restricted by 10-membered rings (10MR), electrons. In zeolites, Lewis acid sites may develop at the external
while large pore zeolites constitute a 12-membered ring (12MR). In surface or extra-framework moieties, for instance, extra-framework
extra-large pore zeolites, the pore openings are larger than 12MRs. aluminium (EFAl) [20]. Also, a recent study suggests that Lewis sites
Furthermore, the zeolites are sub-divided to materials with one-, two- can occur at framework tetrahedral Al atoms [21]. Another explanation
and three-dimensional channel systems. of framework Al possibly acting as Lewis acid site could be the existence
As mentioned, zeolites with the same framework type, but different of Al(OH)Si bridge in the Si–O−(H+)–Al− or SiOH→Al resonance form
composition exhibit different properties. For instance, pure silica ma- [22,23]. In this case, the aluminium coordination is not complete, and
terials have an electrically neutral framework and hydrophobic prop- the base can be adsorbed on this site.
erties. Introducing other T atoms such as trivalent aluminium changes Most zeolite materials applied as catalysts have both Brønsted and
the charge of the framework to negative and makes the material more Lewis acid sites. Besides, the conversion between Brønsted and Lewis
hydrophilic. In this case, the presence of charge-compensating cations acid sites can sometimes take place in zeolites. Namely, at high tem-
in the cavities is required. The charge-compensating alkali and alkali- peratures, the dehydroxylation of zeolite Brønsted sites may occur, and
earth cations are exchangeable, which makes zeolites important ion Lewis acid sites with Si and Al of coordination number three can be
exchangers used for water softening, removal of heavy metal ions, formed [24]. Moreover, during high-temperature treatment, the fra-
radioactive waste storage, etc. When proton is the charge-compensating mework dealumination often occurs, thus generating octahedral alu-
cation, the zeolite exhibits acidic properties that are largely explored in minium species, which act as Lewis acid sites [25]. Accordingly, in such
the heterogeneous catalysis. Furthermore, the diversity in the dimen- a case, the Brønsted acidity decreases. Likewise, upon ammonia ad-
sions and the shape of voids in zeolite frameworks enables the se- sorption, the aluminium coordination can be reversed to tetrahedral
paration of molecules based on size exclusion – molecular sieving effect. [26].
Two parameters determine zeolite (hydro)thermal stability, the fra- The upper limit of the number of protonic sites in zeolites is the
mework type, and the chemical composition. In general, high silica number of framework Al atoms, more precisely ratio of the framework
zeolites exhibit relatively high (hydro)thermal stability. On the con- atoms T4+/T3+ [27]. According to Lowenstein's rule, the maximal Si/
trary, the zeolites become less thermally stable as the Al content in the Al ratio in zeolites equals 1, hence the highest number of protons
2
Another framework-related effect is that the strength of each proton

site decreases with increasing Al content, more specifically when there
are more aluminum atoms in the next nearest neighbor position (NNN)
of this particular atom. Hence, the proton attached to isolated Al with
no close Al neighbor is the stronger acid site [35]. The bridging hy-
droxyl group has higher ionic character and hence a stronger acidity.
Further, for the certain chemical composition of the zeolite, the polarity
of the lattice becomes more significant as the framework density re-
duces. In general, the electronegativity of the T atom is affecting the
zeolite acid strength and it is decreasing in series Al(OH)Si > Ga(OH)
Si > Fe(OH)Si > In(OH)Si > B(OH)Si [36,37].
On account of the complexity of zeolite synthesis systems, the dis-
tribution of aluminium may vary from crystal to crystal and even can
differ within a single crystal; presenting regions of higher or lower Al
concentration [38,39]. The Al atoms sitting within the individual zeo-
lite framework T sites can be considered in terms of its location in the
network of channels and cages. The position of Al tetrahedron de-
termines the accessibility of the active sites and metal counter cations.
Fig. 2. Zeolite Brønsted acid sites strength as a function of the TeOeT bond
Moreover, the location of Al directs the formation of reaction inter-
angle.
mediates in the enclosing void volume of the charge balancing cations.
The two most frequent types of Al arrangements are paired (sequence
possibly present in zeolites is 8.3 mmol H+ g−1 zeolite [28]. However, AleO(eSieO)x −Al, x = 1, 2), and single Al atoms (sequences AleO
usually, the number of protons is lower because of the dealumination of (eSieO)x−Al, x ≥ 3) [40,41]. Particularly noteworthy is the location
zeolite framework during the high-temperature treatment. of Al pairs in the six-membered rings (6MRs) (Fig. 3). Various studies
Zeolite solid acids exhibit similar behavior as acids in a solution, reported that the siting and distribution of Al atoms in the zeolite lattice
and the strength of zeolite Brønsted acid sites is comparable to sulfuric are neither random nor statistically controlled [42–44]. It was found
acid [29,30]. In general, the strength of a Brønsted acid is defined via that the Al distribution over the T-sites is kinetically controlled and
deprotonation energy (DPE) required to dissociate the proton from markedly changes depending on the synthesis conditions [42,43].
conjugate anion to an infinite distance [31]. DPE values of zeolites can The protonic forms of aluminosilicate zeolites have found more
be estimated via computational chemistry methods, yet the results vary extensive use as solid acid catalysts than any other materials. In cata-
depending on the used model. In practice, the Brønsted acid strength is lysis by Brønsted acids, the protonation is the crucial step, where the
indirectly observed using adsorbed probe molecules able to interact activation energy barrier is reduced [45]. In Lewis acid catalysis, the
with acid sites. For instance, the chemical shifts of the carbonyl group activation energy is lowered by polarising molecules, thus making them
of acetone adsorbed on the zeolite in 13C NMR spectrum is related to the more reactive. The main reason for the broad usage of zeolites lies in
acid strength as the higher chemical shift corresponds to stronger site the fact that in their frameworks, the number, nature, position, and the
[32]. Further, in comparison to amorphous aluminosilicates of similar strength of the acid sites can be precisely adjusted. Besides, they re-
chemical composition, crystalline protonic zeolites exhibit stronger present stable and environment-friendly solid catalysts that can be
acidity. The explanation stems from their structure, notably geometric prepared at a large scale with a high degree of reproducibility. The
constraints imposed on TeOeT bond angles (Fig. 2) [22]. Namely, an following sections will address the recent results of controlling the
increase in the bond angles leads to higher acidity per acid site since the siting of Al atoms in zeolites by employing various synthesis ap-
deprotonation of bridging OH groups requires less energy [33]. For this proaches. It should be noted that papers reporting procedures of zeolite
reason, the acid sites of H-MOR (bond angle range of 143–180°) and H- acid sites control by in situ and post-synthesis methods are revised. First,
MFI (133–177°) zeolites are stronger than of H-FAU (133–147°). Ab the basics of the experimental and theoretical methods for zeolite
initio models of alumosilicate clusters revealed the most stable angles acidity assessment are addressed. Further, the strategies of controlling
for protonated and deprotonated bridging hydroxyls are 134° and 179°, the acid sites location within the zeolite framework by direct synthesis
respectively [34]. In amorphous materials, the lattice can relax, re- approach as well as by post-synthesis isomorphous substitution with Al
sulting in bond angles with less related strain, and consequently, they are reviewed. The possibilities of tailoring of zeolites with specific
possess weaker acid sites. acidic properties are exemplified on industrially relevant materials, as
Fig. 3. Depiction of the most common distributions of Al atoms in zeolite 6MRs.
3
well as some promising new framework types. In addition, altering the

acidity of the zeolites in the presence of several T atoms other than Al is
demonstrated.
3.2. Experimental methods for zeolites’ acidity evaluation
Since Al is related to the acid sites in zeolites, information on its

position and distribution, as well as its coordination number, gives an
indication of the nature and distribution of acid sites within the studied
materials. Thus, the initial estimation of the acidity of zeolites can be
made on the grounds of the elemental analysis of the materials, which
provides the Si/Al ratio of the material. Inductively coupled plasma-
emission spectroscopy (ICP-ES), X-ray fluorescence (XRF) and X-ray
photoelectron spectroscopy (XPS) are the most common methods ap-
plied for this purpose. Further, the spectroscopic techniques based on
the interactions of the sample with the X-rays generated by various
sources (synchrotron, electron microscope, etc.) afford data on the
metals present in the sample as well. X-ray absorption spectroscopy
(XAS) probes the local structure and Al coordination. The AleOeSi
bridging angle affects the Al K-edge absorption spectra and thus in a Fig. 4. 27Al MAS NMR spectrum of MFI-type zeolite material which possesses Al
atoms of various coordination environments.
recent study was possible to determine the local Al structure associated
with the Brønsted acid sites by EXAFS (extended X-ray absorption fine
structure) analysis [46]. Moreover, EXAFS made possible the analysis of spectra. 29Si MAS NMR spectra of all-silica zeolites consist of re-
scattering from atoms up to 6 Å away from the absorbing Al. Besides, in sonances at different chemical shift values which stem from crystal-
this study the quantification of both framework and extraframework lographically non-equivalent tetrahedrally bonded Q4 Si atoms, Si
aluminium species has been performed [47]. Similarly, the Al K-edge X- (OSi)4 [56]. Q3 Si atoms appear at structural defects. They are con-
ray absorption near edge structure (XANES) spectra exhibits features nected to one silanol group and three other tetrahedra. Their re-
that indicate the elongation of one of the four AleO bonds about the Al sonances in 29Si MAS NMR spectra are shifted downfield in comparison
induced by the formation of Si(OH)Al species upon the dehydration of to Q4 species. In the case when Al is present within the zeolite frame-
hydronium ions [48]. In addition, micro X-ray diffraction (μXRD) work, the signals in 29Si MAS spectra become broadened, resulting in
crystallography imaging study of ZSM-5 single crystal uncovered dif- overlapping of the Q4 Si resonances. Besides, this generates different
ferences in aluminium concentration [39], while scanning transmission environments of Si since it may have different numbers of Si and Al
X-ray microscopy (STXM) at a resolution of 30 nm enabled the dis- atoms in their second coordination sphere. Each Al atom in the next
tinction among different Al coordination environments and determi- coordination shell causes an additional downfield chemical shift, thus
nation of regions rich in more highly coordinated aluminium atoms enabling the calculation of the framework Si/Al ratio [56]. The tech-
[49]. Various other methods, which are addressed in the following nique of cross-polarization (CP) is based on the exciting spin system by
sections, afford information on the acid properties from different per- transferring the magnetization from another nucleus. This approach is
spectives. In conjunction, they allow a rather clear assessment of zeolite used for identifying some NMR signals. For instance, in the case of
acid sites' nature, strength, and distribution over the framework posi- {1H}29Si CP MAS NMR, the signal of Q3 silicon atoms attached to a
tions. hydroxyl group, (SiO)3SiOH, is enhanced over Q4 Si atoms and/or Si
The natural abundance of 27Al nucleus is nearly 100 %, and thus (3Si,1Al) peak in comparison to the signal intensity in the standard 29Si
27
Al NMR spectra with high signal-to-noise ratios can be acquired MAS NMR spectrum.
1
within a short period of time [50]. Generally, approximate chemical H MAS NMR spectroscopy of dehydrated zeolite materials is one of
shifts in zeolites in 27Al magic angle spinning (MAS) NMR spectra are at the techniques which can provide information on the hydroxyl groups.
50–60 ppm for tetrahedral oxygen-coordinated aluminium, at 30–50 The signals of hydroxyl groups arise in a range of chemical shifts of δ1H
ppm for tetrahedral non-framework Al species, 30 ppm for five-fold = 0–16 ppm. The metal (cation) OH groups, e.g., AlOH, LaOH, and
coordinated species and 0 ppm for octahedral aluminium in experi- MgOH groups located in the large cages of dehydrated zeolites or at the
ments where [Al(H2O)6]NO3 is employed as a reference (Fig. 4) [51]. outer surface of solid particles display the chemical shifts ranging from
The quadrupolar character of the 27Al nucleus (I = 5/2) results in −0.5 to 1.0 ppm. The resonances of the terminal silanol SiOH groups at
broader peaks than those obtained for 29Si due to the interactions with the external surface of the zeolite particles and framework defects ap-
the external magnetic field as well as with the electric field gradient pear at 1.3–2.2 ppm [57]. The signals with chemical shifts up to 16 ppm
generated by its surrounding environment. In zeolite science, often, the originate from the silanol groups forming strong hydrogen bonds. In
issue of “invisible” or “hidden aluminium” is put forward. Namely, dealuminated zeolites are frequently present signals at δ1H = 2.4–3.6
highly distorted low symmetry sites can give rise to very broad signals, ppm, which are assigned to the hydroxyl protons at extra-framework
which often is completely unobservable [51]. Recent technological aluminum species (AlOH) [58]. The bridging Al(OH)Si groups exhibit
progress combined with higher magnetic fields, faster magic angle signals at 3.6–5.5 ppm, whereas the resonances at chemical shifts of 5–7
spinning rates, and newly developed measurement techniques (se- ppm indicate these groups are involved in the hydrogen bonding with
quences) was found efficient neighboring framework oxygens. Methods such as 1H–1H, 27Al–27Al and
31
to circumvent this problem [52–54]. Sample hydration is also a P–31P double-quantum (DQ) magic-angle spinning (MAS) NMR
useful approach in reducing the contribution of the invisible Al to the spectroscopy techniques as well as 1H–27Al DQ MAS NMR have been
overall 27Al MAS NMR [55]. developed to study the spatial proximity between different acid sites in
29
Si NMR spectra afford information on the zeolite acidic properties zeolite samples. An example of 2D NMR spectra of zeolite materials is
in terms of the connectivity within the zeolite framework, i.e., on the given in Fig. 5.
types of Si(nAl) sites, and on the mean TeOeT angles. 29Si nucleus has Infrared spectroscopy provides valuable information on the acidic
a spin ½ and owing to rather low natural abundance (< 5 %) and slow properties of materials. In the spectral region (3800–3000 cm−1),
relaxation, long acquisition times are necessary to collect a resolved
4
Fig. 5. 27Al MAS and double-quantum MAS NMR spectra of zeolite Y (a) before and after calcination in air at (b) 500, (c) 600, and (d) 700 °C. One-dimensional 27Al
MAS spectra are plotted on the top of 2-dimensional spectra.
Reproduced with permission from reference [59].
cm−1, while the broad band at about 3500 cm−1 arises due to silanol
nests [61].
3.3. Zeolites’ acidity assessment by probe molecules
The very definition of the acids involves the exchange of H+ or

electrons between the acid-base pair, therefore employing molecules
that get adsorbed and interact with acid sites is a standard method to
get insight on the acidic properties of the zeolites. The perturbations of
the spectra of both the zeolite surface groups and the probe molecule
upon the interaction can provide qualitative and quantitative in-
formation on the acid site. This approach is particularly convenient for
the investigations of Lewis acid sites as they cannot be directly detected
by IR since a coordinatively unsaturated site does not undergo vibra-
tions [62].
Fig. 6. FTIR spectra in the OH region of the ZSM-5 materials of different Si/Al
ratios. Pyridine is a commonly employed probe molecule for zeolite acidity
assessing since it interacts with both Brønsted and Lewis acid sites. The
band at ≈1540 cm−1 is associated with pyridine on Brønsted acid sites,
which corresponds to stretching vibrations of hydroxyl groups, typical whereas that at ≈1450 cm−1 arises from pyridine adsorbed on Lewis
infrared spectra of activated (calcined in vacuo) zeolites feature several acid sites. Furthermore, the multi-bands in the region 1580–1660 cm−1
bands. The bands corresponding to the silanol groups appear at can be useful to make a distinction between pyridine adsorbed on dif-
3710–3760 cm−1 (Fig. 6), as the contributions of isolated silanols at the ferent acid sites [63]. Pyridine can penetrate pores of most catalytically
external surface, weakly interacting internal silanols possibly near important zeolites as its kinetic diameter is 0.57 nm. Bulkier molecules
structural defects (intracrystalline SieOH), and internal silanols in have limited access to micropores and are used to probe acid sites on
zeolite channels vary in a particular sample [60]. The stretching mode the external surface of the zeolite crystals. E.g., the kinetic diameters of
of the bridging hydroxyl groups gives rise to a band at 3600–3650 methyl-substituted
5
Fig. 7. FTIR spectra of ZSM-5 zeolite in the region 1720–1420 cm−1 with ad-
sorbed pyridine, 2,6-dimethylpyridine, and 2,4,6-trimethylpyridine.
Table 1
Common basic probe molecules used for the evaluation of the acidity of zeolite
materials by infrared spectroscopy. Their kinetic diameter and typical band
region in the spectrum of a probe molecule adsorbed on the zeolite corre-
sponding to interactions with acid sites are also presented.
Probe molecule Reference
H2
kinetic diameter/Å 2.9
band position/cm−1 4150–4090 [64,65]
interaction with site cations Fig. 8. (a) Optimized structures of trialkylphosphine oxide (TMPO, TEPO,
N2 TBPO, and TOPO – trioctylphosphine oxide) probe molecules. (b) A plot of
kinetic diameter/Å 3.6 calculated 31P chemical shift of adsorbed R3POH+ complexes and proton affi-
band position/cm−1 2360–2345 2335–2330 [66] nity envisaged on the grounds of the 8MR zeolite cluster model. Reprinted with
interaction with site Lewis Brønsted permission from reference [83]. Copyright (2017) American Chemical Society.
CO
band position/cm−1 2240–2190 2180–2155 [67,68] molecules for the assessment of the acidity of zeolitic materials by in-
interaction with site Lewis Brønsted
frared spectroscopy. The kinetic diameter of the probe molecule and
d3-acetonitrile
kinetic diameter/Å 3.8–4.2
typical band region in the spectrum of a zeolite material with adsorbed
band position/cm−1 2335–2325 2300–2295 [69,70] particular probe molecule is presented too. In the past years, many
interaction with site Lewis Brønsted comprehensive reviews on probing zeolites by infrared spectroscopy
NH3 have been published, and it is recommended to consult them when
looking for more details on the matter [62,79,81,82].
band position/cm−1 1630–1620 1450–1410 [71,72]
interaction with site Lewis Brønsted Phosphine molecules have been proved to be particularly useful to
pyridine probe acid sites investigated by NMR (Fig. 8) [83]. The MAS-NMR
kinetic diameter/Å 5.7 spectra of trimethylphosphine (TMP) adsorbed on zeolites enables clear
band position/cm−1 1545 1450 [73]
distinguishing between the acid sites. Acidic protons react with the
interaction with site Brønsted Lewis
2,6-dimethylpyridine (lutidine)
strong Lewis base forming [(CH3)3P–H]+ adducts that exhibit a 31P
kinetic diameter/Å 6.7 chemical shift of ca. −3 ppm and a JP-H coupling constant of ca. 500
band position/cm−1 1650–1625 1620–1595 [74,75] Hz. The TMP bonded to Lewis sites has resonances at notably higher
interaction with site Brønsted Lewis fields (−30 to −70 ppm), and when Al is present, a JP-Al coupling of ca.
2,4,6-trimethylpyridine (collidine)
300 Hz may result in a multiplet of six lines [84]. Employing tri-
band position/cm−1 1650–1635 1633 [76,77] methylphosphine oxide (TMPO) and tributylphosphine oxide (TBPO)
interaction with site Brønsted Lewis facilitates distinction among the acid sites located in the internal voids
di-tert-butylpyridine and on the external surfaces of zeolites. The kinetic diameter of TMPO
(ca. 0.55 nm) is smaller than the pore opening of the ten-membered
band position/cm−1 1615 1450 [78]
interaction with site Brønsted Lewis
ring (ca. 0.60 nm) of zeolite ZSM-5; hence TMPO can diffuse in the
channels and pores of the zeolite and get bonded to both the internal
and external acid sites. On the other hand, TBPO of a kinetic diameter
pyridines 2,6-lutidine (2,6-dimethylpyridine) and 2,4,6-collidine of ca. 0.82 nm is too large to penetrate into the channels. Only the acid
(2,4,6-trimethylpyridine), are 0.67 nm and 0.74 nm, respectively, and sites located on the external surface of the zeolite crystals are accessible
thus their penetration ability to some micropores is reduced (Fig. 7) to TBPO [85].
[62]. Accordingly, they are used to distinguish the silanols located in- Isotopic labeling was also found to be useful in distinguishing var-
side or outside the micropores and consequently to establish their ac- ious acid sites in zeolite materials. For instance, 17O NMR resonance
cessibility [79,80]. Other probe molecules used to evaluate the zeolite from oxygen directly bound to the Brønsted acid site has been observed
acidity are CO, NO, CO2, N2, H2, O2, NH3, CH3CN, benzene, alkanes, in 17O-enriched zeolite NH4Y [86]. Measuring of the adsorbed 15N-
etc. (Table 1). These probe molecules have different basicities and can pyridine by 15N MAS NMR spectroscopy enabled assessing the strength
be used under various experimental conditions providing information and number of isolated framework metal sites (Sn, Ti, Zr, Hf, Nb, Ta, B,
on the nature and strength of the acid sites in the zeolite framework. Ga, and Al) in Beta zeolite materials [87]. Similarly, H/D isotope ex-
Table 1 summarizes the most frequently employed basic probe change was utilized to quantify the total number of Brønsted acid sites
6
as well as their distribution throughout zeolite crystals of different sizes Brønsted acid sites strength within the FCC particle [94].
[88]. Besides, the hoping of protons (limited delocalization – moving of In temperature-programmed desorption (TPD) experiments, the
protons in regions wider than over the surrounding four lattice oxygen sample is heated while the pre-adsorbed probe molecules get gradually
atoms) at temperatures above 300 °C was confirmed by the H/D isotope desorbed [95]. Ammonia is the most frequently used probe molecule in
exchange between acidic OD groups of several zeolites (CHA, MFI, TPD technique (NH3-TPD), yet the usage of CO, amines, alcohols,
MOR) and methane [89]. The isotope exchange between acidic OD acetonitrile, has also been reported [96–100]. The desorption curve is
groups and H in ethane provided information on the strength of acid plotted as the rate of the gas desorption versus the temperature [101].
sites in various zeolites [90]. Further, the addition of 99.69 % 29Si Generally, the desorption peak maximum position is a function of the
enriched 29SiO2 in the SAPO-34 synthesis system resulted in a material acid site strength, whereas the peak area is correlated with the amount
with present Si islands as detected by 29Si NMR [91]. In SAPO mate- of acid sites. One should note that the experimental conditions may
rials, Si is associated with Brønsted acidity and shows a direct re- influence the peak positions. Besides, the TPD profiles may comprise
lationship with the coke deposition. multiple overlapping peaks. In such a case, the curve deconvolution is
The UV/Vis spectroscopy is another method used to account for the applied to attain information on the total quantity of the acid sites as
acid sites in heterogeneous catalysts. Measuring the UV/Vis spectrum of well as the amount of the particular acidic site [102]. The major dis-
pyridine interacting with the zeolite was found to be a promising tool advantage of the TPD method is that Brønsted and Lewis acid sites
for investigating the acidic properties of zeolites [92]. The technique cannot get distinguished. Besides, the desorbed probe molecules can get
relies on the fact that the electronic properties of pyridine get altered re-adsorbed while they are coming out of the pores and thus can affect
upon the interaction with acid sites, and thus pyridine bonded to var- the final results [103]. TPD technique has been upgraded by developing
ious sites can be distinguished. One of the most notable advantages of an NH3 IRMS-TPD (infrared/mass spectroscopy TPD) method based on
this method is the possibility to discriminate the different surface OH the operando instrumentation set-up, which allowed to ascertain the
groups. Namely, the UV/Vis bands position is mostly affected by the nature of acid sites (Fig. 10) [104].
species Microcalorimetry is a direct method for measuring the heat of ad-
adjacent to the hydroxyl group. In addition, the study of the acidic sorption of probe molecules on zeolites. The experiment is performed
strength of the hydroxyl groups is attainable as well (Fig. 9). Also, a by dosing the aliquots of the probe molecule onto the sample held at the
staining method employing thiophene to visualize the zeolite particu- chosen temperature until reaching full surface coverage. Indeed, a large
lates, FCC catalyst components, was developed. On the grounds of the variety of probe molecules such as NH3, pyridine, amines, H2O, N2O,
fluorescence microscopy images, the maps of Brønsted acid sites in a etc. has been studied [106–108]. The results are plotted as the ad-
single zeolite particle were created. The method is based on the thio- sorption enthalpy as a function of the coverage. Usually, in the case of
phene oligomerization catalysed by Brønsted acid sites [93]. Similarly, high-silica zeolites that possess strong Brønsted acid sites, the higher
the liquid-phase oligomerisation of styrene monitored by UV/Vis differential adsorption enthalpy at low coverage is measured. The mi-
spectroscopy enables the investigation of the Brønsted acid sites in crocalorimetry results of the ammonia adsorption at 150 °C have shown
zeolite constituent of the FCC particles. Besides, the usage of the styr- a marked influence of the local geometry of bridging hydroxyl groups
enes of different reactivity allows the determination of the zeolite within the zeolite framework (bond angles and distances) on their acid
strength. Namely, zeolites of similar Si/Al ratio, yet different structure
types present differences in adsorption heats up to ≈50 kJ mol−1
[109]. One should be aware of many limitations this method is facing.
From a practical point of view, it takes a long period of time to achieve
the complete equilibrium. Also, similar differential heats of adsorption
can be measured from the strong Lewis centers and strong Brønsted
sites. Finally, the adsorption could be limited by diffusion [110]. Still, it
Fig. 9. UV/Vis spectra after pyridine adsorption on hypothetical solid acids

possessing (a) Brønsted and Lewis acid sites, (b) Brønsted acid sites and hy-
droxyl surface groups, and (c) Lewis acid sites and hydroxyl surface groups.
Reproduced from reference [92] with permission from the PCCP Owner So- Fig. 10. NH3 IRMS-TPD spectrum of SSZ-13 zeolite. Reprinted with permission
cieties. from reference [105]. Copyright (2011) American Chemical Society.
7
is a powerful technique for zeolite acidity evaluation. Table 2

Recently, a new method for measuring Brønsted acid site densities Deprotonation energies of different T sites in some zeolite structures calculated
based on reactive gas chromatography has been developed [111]. The using the QM-Pot approach. Adapted from reference [140] - Published by The
technique relies on alkylamine decomposition to selectively count the Royal Society of Chemistry.
Brønsted acid sites within zeolite lattice. The molecule decomposition Zeolite FAU MFI CHA FER FAU
occurs within the inlet of gas chromatograph, and a flame ionization
site O1H O7–H O1H O7–H O3–H
detector quantitatively measures the products. The values on the
Edp / kJ mol−1 1206 1235 1225 1218 1203
Brønsted acid site densities obtained by the reactive gas chromato-
graphy are in good agreement with the acidity results collected by the
conventional TPD mass spectrometry as well as with the in situ pyridine strength becomes higher because the AleO distance is shorter [123].
titration of isopropanol dehydration. The technique allows reliable Namely, the stronger acid sites are generated when the AleO bond is
measurement of the Brønsted acid site densities of siliceous materials as shorter, and the SieOeAl angle larger [124]. On the other hand, it was
low as ≈1.0 μmol gcat−1. calculated by QM-Pot approach (Table 2) that the difference in the
The proposed method to assess the distance between the Al atoms deprotonation energies of zeolites having different frameworks is
that are facing the same channel and have a cooperative effect on the within a range of < 30 kJ mol−1 [125]. Further, in 2015 Jones and
charge-balancing cation site occupation is related to the zeolite ex- Iglesia used a periodic DFT method and reported that in MFI, BEA,
change capacity for the divalent metal hexa-aqua-complex cation, [Co MOR, FER, CHA, and FAU zeolite frameworks the ensemble-averaged
(H2O)6]2+ [112]. Namely, there are three cation sites in the six-mem- deprotonation energies are invariable on the Al location [126]. These
bered rings (α-, β- and γ-types) of the MOR, FER, MFI, and BEA zeolite energies reveal that conjugated anions are similarly stable in-
frameworks. The α-type 6MR comprises two 5MRs and is twisted, β- dependently on both Al siting as well as zeolite framework type, i.e.,
type site is planar, whereas γ-type 6 MRs build a complex boat-shaped OeH bond lengths and SieOeAl angles. For that reason, the acid
structure. Upon ion exchange with the [Co(H2O)6]2+, the cations oc- strength is determined only by the type of the T-atom incorporated
cupy the 6MRs with paired Al atoms, and the bands in the UV/Vis within the framework regardless of its position, number, and distribu-
spectra of a specific sample can be decomposed to get the concentration tion. Ergo, the catalytic activity of the zeolite materials is determined
of the Co2+ at a particular cation site. The sum of the molar con- by the confinement effects that stabilize the transition states and ad-
centrations of Co2+ at the individual sites is directly proportional to the sorbed intermediates through dispersion forces. Further, in a recent
concentration of the paired Al sites. The concentration of the unpaired study, Rybicki and Sauer proposed the decomposition of the deproto-
sites is calculated indirectly as a difference between the concentration nation energy into two components: intrinsic deprotonation energy and
of the Co2+ needed for complete ion exchange and the concentration of a proton “solvation” energy, which is a function of the dielectric con-
Co2+ at the α-, β- and γ-type cationic sites of mordenite, ferrierite, stant of the material. Namely, the ab initio studies have shown a linear
ZSM-5 and Beta zeolites [42]. Recently, this approach has been applied correlation of the deprotonation energies of zeolites with the reciprocal
to CHA-type materials, as well [113]. value of the average dielectric constant [127]. Again the intrinsic de-
protonation energies of most of the zeolites have very similar values,
3.4. Theoretical methods for zeolites’ acidity evaluation and thus, in line with the conclusion of Jones and Iglesia, all zeolites
present almost identical acid strength regardless of their structure.
The theoretical methods have developed substantially in the past As already mentioned, in practice, the acidity of zeolites is esti-
years and are now commonly used in zeolite science. They provide a mated on the grounds of their interactions with various probe mole-
complementary viewpoint that helps to get insight into zeolite prop- cules. However, from a theoretical chemistry point of view, this is a
erties in general, addressing them from different perspectives. In terms complex matter, and there is a distinction between the results of the
of zeolite acidity, it allows studying the Al distribution and proton acidity quantification using a simulation of the probe molecules ad-
sitting in the zeolite framework. Various approaches have been em- sorption and calculations of the deprotonation energies [128]. The si-
ployed to simulate the active zeolite sites in many cases neglecting the multions indicate that in this case not only intrinsic acidity should be
confinement effects [114–116]. In general, the calculated spectra fit taken into account, but bu also, the stabilization of the adsorbed mo-
well with the experimentally measured spectra [47,117]. In addition, a lecule or its conjugated acid confined within the zeolite voids by dis-
plethora of theoretical studies dealing with modeling interactions/ad- persion forces. The concept of the effect of confinement in zeolite rests
sorption of molecules of different character and zeolite materials have on the long-range attractive van der Waals interactions and contributes
been conducted [118]. For example, the shifts in the stretching fre- to the adsorption energy of a molecule on a surface [129]. Initial results
quencies in the IR spectra of zeolite materials with adsorbed CO have indicated the enhancement of the (van der Waals) adsorption energy on
been calculated [119]. The results are in fair agreement with the ex- concave surfaces, while further studies showed there is a surface barrier
perimental findings. Furthermore, the heats of ammonia desorption to sorption into cylindrical pores in the zeolite channels. Indeed, the
from zeolite materials measured by the TPD frequently coincide with computational methods facilitated quantitative assessment of the con-
the theoretical calculations using different functionals [120,121]. finement effects in zeolite materials and led to a better understanding of
Deprotonation energy (i.e., the proton affinity) of the Brønsted acid adsorption and catalysis processes in zeolites by modeling sites with
sites is a feature denoting the zeolite acidity. Often the computational high adsorption affinity for certain gases [130], active site structures
approach is more convenient for the determination of deprotonation [131], the reaction coordinates [132,133], transition states and inter-
energy than complicated experimental methods. Thus embedded cluster mediates [134,135], encapsulated particles/clusters [136], reaction
systems have been used to model zeolites H-Y and H-ZSM-5 and study barrier predictions [137], etc. Besides, as OSDA molecule may be
the deprotonation energy differences between the structures. No matter considered as a physisorbed sorbate molecule, this approach enabled a
the exchange-correlation functional, the deprotonation energy of FAU better understanding of zeolite synthesis and even designing the tran-
zeolite is the lowest followed by ZSM-5 acid sites located in the sinu- sition state mimicking OSDA, which yielded target zeolite with im-
soidal channel, in the intersections, and finally in the straight channel proved catalytic performance in the target reaction [138]. Finally, the
[122]. Besides, the local geometry around the acid site (bond lengths most recent trend in computational chemistry is developing operando
and angles among atoms), which determines its acid strength, can be theoretical methods which describe the catalytic processes [139].
correlated with energy parameters. DFT investigation on cluster models
of Brønsted acid of FAU, BEA, MFI, FER, MWW, and MOR frameworks
suggests that when the Si(OH)Al unit is pushed from both sides, the acid
8
4. In situ control of acid sites in zeolites
The two avenues of incorporating Al into zeolite framework posi-

tions are the in situ synthesis route and the post-synthesis modification.
The two different approaches are illustrated in the next sections of the
paper through examples of directing the Al sitting within the zeolite
framework by changing the synthesis or post-synthesis treatment
parameters. Further, the essential aspects of zeolite synthesis procedure
are given in the light of preparing materials of required properties.
The post-synthesis treatment is discussed in detail since there are a
plethora of conditions under which the post-synthesis treatment of
zeolites can be performed. For instance, the choice of the treating agent,
pH, temperature, duration of the procedure, and the number of the
treatment steps are provided. All these parameters impact the proper-
ties of the final material, and the outcome of the post-synthesis treat-
ment of zeolite in terms of chemical composition, the number of in-
Fig. 11. MFI zeolite framework with labels of crystallographically non-
troduced Al, and its position may vary to a large extent. Briefly, the
equivalent T sites.
post-synthesis Al incorporation is sensitive to the micro/macroscopic
properties of the initial material or minor fluctuations in the treatment
conditions. starting compounds, pH, and reaction temperature [151–153]. In such a
Generally, the zeolite synthesis mixture contains a few essential heterogeneous system, many possible processes may occur: condensa-
elements. Each chemical containing silicon or aluminum can be con- tion of silicate species, polymerization, depolymerization, dissolution,
sidered as a potential T atom source. The physicochemical properties gel formation, gel reorganization, etc. Most of these reactions, equili-
and solubility of the initial T atom source affect the overall reaction bria, and interactions are correlated and can change as the reaction
kinetics and crystal growth process. Moreover, different zeolite types or advances [154,155]. The outcome of the process is a result of small
crystal morphologies can be obtained when the T atom source is differences in the thermodynamic parameters of the competing pro-
changed [141]. Water is the most common solvent in zeolite prepara- cesses and kinetic barriers [156].
tion, but other solvents such as ionic liquids and ethylene glycol have
also been successfully employed, providing new opportunities in the 4.1. In situ controlling the Al location in the zeolite framework
zeolite syntheses [142,143]. Hydroxide and fluoride anions are used as
mineralizers (mobilizers) in preparing of zeolites. Mineralizer solubi- 4.1.1. MFI-type materials
lizes the reactants forming complexes of various polycondensation de- MFI-type material is a medium pore zeolite possessing a three-di-
grees depending on the mineralizer concentration. Crystals prepared in mensional channel system of intersected straight and sinusoidal 10MR
hydroxide media have more defects than fluoride route materials [61]. channels with the diameter of the intersection cavity of about 9 Å.
Furthermore, all-silica counterparts of some zeolite materials have been There are 12 crystallographic non-equivalent T-sites (Fig. 11), and the
prepared in fluoride systems [144]. Also, when fluoride ions have been aluminium atoms can occupy a range of T-sites within the MFI frame-
used, several previously unknown zeolite frameworks have been dis- work, hence affecting the material’s performance in a particular ap-
covered [145,146]. plication. The materials with Si/Al ratio ranging from infinity to 10
Structure directing agents are moieties that assemble the array of have been synthesized in the presence of various OSDAs (tetra-
zeolite voids and channels. They are confined within the zeolite fra- ethylammonium, di-n-propylamine, 1,5-diaminopentane, tripropyla-
mework, yet not a part of it. Inorganic cations such as alkali and alkali- mine, ethyldiamine, morpholine, propanolamine, ethanolamine, di-
earth cations with their hydration spheres are considered as structure- propylenetriamine, triethylenetetramine, diethylenetetramine,
directing agents for natural and low-silica synthetic zeolites. It was glycerol, n-propylamine, hexanediol, di-n-butylamine, propylamine,
found that particular cations prefer certain positions within the fra- etc. [157]), but generally, the tetrapropylammonium (TPA) cation is
mework [147]. Accordingly, they can yield different structure types, utilized. In addition, there are many reports on OSDA-free syntheses of
thus exhibiting the structure-directing effect [148]. The inorganic ca- ZSM-5, very often in the narrow range of composition of the starting
tions present within the voids are exchangeable, whereas the organic reaction mixtures with rather long crystallisation times and with stir-
species in the final product are occluded within the pores and are ring [158–161].
predominantly decomposed by calcination. Certain efforts have been Furthermore, MFI-type materials have been prepared from OSDA-
made towards designing of degradable and recyclable organic struc- free synthesis mixtures with added seed crystals [162–166]. It is ne-
ture-directing agents (OSDAs), thus eliminating the combustion step cessary to note that all silica MFI-type material is termed silicalite-1,
[149]. The aftermath of using OSDAs was an increase of the Si/Al ratio while the Al-containing materials are referred to as ZSM-5. Besides Al,
of the zeolites due to their larger size, which limits the amount of OSDA heteroatoms such as Ti, B, Fe, Sn, V, Zn, Ga, As, Mn, etc. have been
molecules that can be confined inside the zeolite. Hence, less Al is in- introduced into the MFI zeolite framework [167–175].
corporated into the framework. Finally, the geometry (size and shape), To account for the acidic properties of ZSM-5, Yokoi et al. used
electronic properties, rigidity, polarity, and hydrophobicity of the or- tetrapropylammonium hydroxide (TPAOH), dipropylamine (DPa), cy-
ganic molecules will exhibit an effect on the final zeolite formed [150]. clohexylamine (Cha) and hexamethylenimine (HMi) with or without Na
The initial zeolite synthesis reaction mixture is prepared when the cations as summarized in Table 3. The prepared materials have nearly
reaction components get admixed. Two main events take place during equal Si/Al ratio (≈ 50) and, thus, a similar number of acid sites [176].
any new solid phase formation – nucleation and (crystal) growth. The Nevertheless, the activities of these ZSM-5 materials in 3-methylpen-
nucleus is the smallest entity within a system that brings structural tane cracking and catalyst lifetimes in methylcyclohexane cracking
information and can yield the final product at given reaction condi- differ noticeably. Such behaviour was reasoned by constraint index
tions. As the nutrient pool determines the reaction kinetics and, sub- analysis, and it was concluded that the bimolecular cracking in the 3-
sequently, its termination, the number of viable nuclei directly affects methylpentane cracking proceeds via a bulky transition state over the
the final size of the crystals. Zeolite synthesis system is particularly acid sites located at the channel intersections. Consequently, it has been
complex, and the distribution of the species mainly depends on the estimated that in the sample prepared using TPA+ in the presence of
9
Table 3
Gel composition and the initial silica and alumina sources in the starting zeolite synthesis mixture; Si/Al ratio and preferredAl location in the final high silica zeolite
products yielded from respective synthesis mixtures.
Molar oxide composition with OSDA* Al source Si source Zeolite framework Preferred Al location Si/Al Reference
1 SiO2:0.01Al2O3:0.5 TPAOH:8.3 H2O Al(NO3)3‡ 40 wt% SiO2† MFI intersections 53 [176]

1 SiO2:0.01 Al2O3:0.25 TPAOH:0.1 NaCl:8.3 H2O Al(NO3)3 40 wt% SiO2 MFI channels + intersections 52 [176]
1 SiO2:0.01 Al2O3:0.4 Dpa:0.1 Na2O:25 H2O Al(NO3)3 40 wt% SiO2 MFI intersections 42 [176]
1 SiO2:0.01 Al2O3:0.4 Cha:0.1 Na2O:25 H2O + Al(NO3)3 40 wt% SiO2 MFI intersections 51 [176]
1 SiO2:0.01 Al2O3:0.5 HMi:0.1 Na2O:25 H2O:0.07H2SO4 Al(NO3)3 40 wt% SiO2 MFI intersections 48 [176]
OSDA:TPA+ + Na+ Al(NO3)3 MFI single Al 13 [177]
OSDA:TPA+ + Na+ Al(NO3)3 MFI single Al 20 [177]
OSDA:TPA+ + Na+ AlCl3 MFI single Al 30 [177]
1 SiO2:0.02 Al2O3:0.5 PET:0.125 Na2O:25 H2O Al(NO3)3 40 wt% SiO2 MFI channels 24 [178]
1 SiO2:0.02 Al2O3:0.25 TPAOH:0.1 NaCl:8.3 H2O Al(NO3)3 40 wt% SiO2 MFI channels + intersections 24 [178]
1 SiO2:0.02 Al2O3:0.25 TPAOH:8.3 H2O Al(NO3)3 40 wt% SiO2 MFI intersections 24 [178]
1 SiO2:0.02 Al2O3:0.25 TPAOH:60 H2O:0.25 H F Al(NO3)3 40 wt% SiO2 MFI intersections 26 [179]
1 SiO2:0.02 Al2O3:0.25 NaCl:0.25 TPAOH:60 H2O Al(NO3)3 40 wt% SiO2 MFI channels + intersections 28 [179]
1 SiO2:0.02 Al2O3:0.5 PDO:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels + intersections 23 [179]
1 SiO2:0.02 Al2O3:0.5 HDO:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels + intersections 22 [179]
1 SiO2:0.02 Al2O3:0.5 GLY:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels 23 [179]
1 SiO2:0.02 Al2O3:0.5 DEG:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels + intersections 21 [179]
1 SiO2:0.02 Al2O3:0.5 TEG:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels 21 [179]
1 SiO2:0.02 Al2O3:0.5 TBO:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels 21 [179]
1 SiO2:0.02 Al2O3:0.5 TME:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels 22 [179]
1 SiO2:0.02 Al2O3:0.125 Na2O:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels 19 [179]
1 SiO2:0.025 Al2O3:0.25 TPA:27 H2O Al(NO3)3 40 wt% SiO2 MFI intersections 20 [180]
1 SiO2:0.020 Al2O3:0.50 PET:0.025 NaOH:27 H2O Al(NO3)3 40 wt% SiO2 MFI channels 28 [180]
1 SiO2:0.033 Al2O3:0.5 TPAOH:50 H2O Al(NO3)3 40 wt% SiO2 MFI intersections 31 [181]
1 SiO2:0.033 Al2O3:0.98 NBA:0.08 Na2O:10 H2O NaAlO2 fumed SiO2 MFI channels + intersections 27 [181]
1 SiO2:0.025 Al2O3:0.5 TPAOH:50 H2O Al(NO3)3 40 wt% SiO2 MFI intersections 39 [181]
1 SiO2:0.025 Al2O3:0.98 NBA:0.08 Na2O:10 H2O NaAlO2 fumed SiO2 MFI channels + intersections 37 [181]
OSDA:TPA + Al-butoxide‡ 30 wt% SiO2† MFI intersections, paired Al 15 [184]
OSDA:TPA + poly-AlCl‡ 30 wt% SiO2 MFI intersections, single Al 15 [184]
0.94 SiO2:0.03 Al2O3:0.54 PYR:0.48 H F:4.6 H2O Al-isopropoxide‡ TEOS FER T3 site – [202]
0.94 SiO2:0.03 Al2O3:0.06 TMA:0.48 PYR:0.48 H F:4.6 H2O Al-isopropoxide TEOS FER T1 site – [202]
SiO2:0.033 Al2O3:0.54 PYR:0.5 H F:5 H2O alumina 40 wt% SiO2 FER 8MR 13 [204]
SiO2:0.033 Al2O3:0.06 TMAOH:0.48 PYR:0.5 H F:5 H2O alumina 40 wt% SiO2 FER 8MR 17 [204]
SiO2:0.033 Al2O3:0.06 TMAOH:0.48 HMI:0.5 H F:5 H2O alumina 40 wt% SiO2 FER 10MR 17 [204]
SiO2:0.133 Al2O3:0.5 TMAdaOH:44 H2O Al(OH)3 40 wt% SiO2 CHA single Al 15 [217]
1 SiO2:0.133 Al2O3:0.3 TMAdaOH:0.2 NaOH:44 H2O Al(OH)3 40 wt% SiO2 CHA increased fraction of paired Al 15 [217]
1 SiO2:0.033 Al2O3:0.25 TMAdaOH:0.25 KOH:44 H2O Al(OH)3 40 wt% SiO2 CHA small fraction of paired Al 15 [220]
1 SiO2:0.033 Al2O3:0.125 TMAdaOH:0.375 KOH:44 H2O Al(OH)3 40 wt% SiO2 CHA single Al 14 [220]
1 SiO2:0.033 Al2O3:0.024 TMAdaOH:0.476 KOH:44 H2O Al(OH)3 40 wt% SiO2 CHA single Al 10 [220]
1 SiO2:0.0125 Al2O3:0.35 TMAdaOH:18 H2O Al(OH)3 40 wt% SiO2 CHA single Al 30 [221]
1 SiO2:0.0125 Al2O3:0.35 TMAdaOH:18 H2O FAU‡ FAU† CHA increased fraction of paired Al 36 [221]
1 SiO2:0.0125 Al2O3:0.45 TMAdaOH:12.3 H2O FAU FAU CHA increased fraction of paired Al 40 [221]
20.5–21 SiO2:1 Al2O3:1.8 Na2O:1 TEAOH:15.2 H2O NaAlO2 SiO2 spheres† MOR 8MR 10 [233]
120 SiO2:1 Al2O3:8.6 Na2O:12 TBAOH:1420 H2O NaAlO2 40 wt% SiO2 MEL 10MR 121 [271]
120 SiO2:0.5 Al2O3:8.6 Na2O:12 TBAOH:1420 H2O NaAlO2 40 wt% SiO2 MEL 10MR 213 [271]
80 SiO2:Al2O3:46.4 TBAOH:1280 H2O Al(NO3)3 TEOS MEL increased fraction at intersections, 35 [272]
paired Al
80 SiO2:Al2O3:32 TBAOH:1280 H2O:NaCl Al(NO3)3 TEOS MEL intersections, paired Al 34 [272]
80 SiO2:Al2O3:32 TBAOH:1280 H2O:NaCl:0.07 LiCl Al(NO3)3 TEOS MEL intersections, increased fraction of 35 [272]
paired Al
1 SiO2:0.0025 Al2O3:0.125 B2O3:0.1 Na2O:0.5 PMP:2 Al2(SO4)3 fumed SiO2 RTH T1, T2 and/or T3 207 [273]
EDA:100 H2O
1 SiO2:0.0025 Al2O3:0.125 B2O3:0. 1 Na2O:0.5 M P:2 Al2(SO4)3 fumed SiO2 RTH T1, T2 and/or T3 190 [273]
EDA:100 H2O
* OSDA: pyrrolidine – PYR; tetramethylammonium cation – TMA+; hexamethyleneimine – HMI; tetrapropylammonium cation – TPA+; dipropylamine – DPA;
cyclohexylamine – Cha; pentaerythritol – PET; 1,3-propanediol – PDO; 1,6-hexanediol – HDO; 1,6-hexanediol – HDO; glycerol – GLY; diethylene glycol – DEG;
triethylene glycol – TEG; tert-buthanol – TBO; trimethylolethane – TME; n-butylamine – nBA; N,N,N-trimethyl-1-admantylammonium cation – TMAda+; 1,2,2,6,6-
pentamethylpiperidine – PMP; 1-methylpiperidine – MP; ethylenediamine – EDA.
‡
Al(NO3)3 – Al(NO3)3·9H2O; Al-butoxide – aluminium butoxide; poly-AlCl – polyaluminium chloride PAX-18; Al-isopropoxide – aluminium isopropoxide; FAU –
FAU-type zeolite.
†
40 wt% SiO2 – 40 wt% colloidal SiO2; 30 wt% SiO2 – 30 wt% colloidal SiO2, FAU – FAU-type zeolite; SiO2 spheres – porous silica spheres.
10
[180]. In another set of experiments, ZSM-5 materials have been syn-

thesized in the presence of TPAOH, pentaerythritol, and n-butylamine.
Once again, the acid sites reside in the MFI framework channels when
PET is used and in the channel intersections in the case of TPAOH,
while the n-butylamine yielded material that possesses Al distributed in
both of these environments [181]. Upon modification with Pt, the
samples with acid sites in the channel intersections produced more
aromatic compounds and less methane in the reaction of ethane ar-
omatization than that of a ZSM-5 with acid sites located in the channels.
Two sets of ZSM-5 zeolites having Si/Al ratio ranging from 13 to 30
and with the distribution of framework Al as paired and single atoms
were prepared by Bernauer et al. employing various Si and Al sources
[182]. The protons on the paired Al atoms are regarded as close protons
while the isolated protons are bonded to distant single Al atoms. In
these ZSM-5 samples, most of the acid sites are positioned at the
channel intersections. The authors had found that the oligomerization
process over close protons is about 2–10 times higher in turn-over rates
per acid site than over the ZSM-5 zeolites with isolated protons located
at the channel intersection as well [182]. The additional study revealed
that the presence of Na+ in the initial zeolites synthesis mixture results
in a high population of single Al atoms in the final material’s framework
due to the stabilization effect of Na+ on single SiAlO4− species in the
amorphous precursor [183]. On the other hand, the Al pairs get in-
Fig. 12. Schematic representation of the Al sitting within the final MFI-type corporated in the 6MRs due to the impact of the positive charge of
material prepared from the zeolite synthesis mixtures containing TPA, TPA with TPA+ that can be polarized by anions. The polarization ability of anions
Na+, and pentaerythritol with Na+. together with OH– on the N atom charge decreases in the order
OH– > Cl– > PO43– > NO3–: the lower the positive charge on the N
Na+ the number of acid sites in the intersection positions is very low. atom, the lesser population of Al pairs and higher incorporation of
On the other hand, when Na+ is not present in the TPA containing single Al atoms sited in the vicinity of TPA+.
reaction mixture, the acid sites in the obtained ZSM-5 material mostly Two ZSM-5 samples of similar Si/Al ratio (≈ 15) were prepared
reside in large spaces, i.e. in the channel intersections. Likewise, ZSM-5 from dry amorphous aluminosilicate precursors with the assistance of
zeolites synthesized in the DPa, Cha, and HMi systems with Na+ possess TPAOH as OSDA [184]. Silica sol was employed as the Si source, and in
the acid sites predominantly located at the channel intersections [176]. the sample ZSM-5(p) Al source was aluminium butoxide while in the
Accordingly, Pashkova et al. established that the addition of Na+ ions ZSM-5(s) polyaluminium chloride PAX-18 was used. Prior to the hy-
to the initial zeolite synthesis mixture does not affect the location of Al drothermal treatment, both dried aluminosilicate precursors were
at the intersection, but does influence its distribution over single iso- mixed with water, ethanol, NaOH, and NH3 with the addition of 1 wt%
lated Al (increased fraction) and paired Al sites (reduced number) of ZSM-5 seeds. In order to account for the Al position within the zeolite
[177]. framework 27Al 3Q MAS NMR spectra of the studied materials together
Yokoi et al. further investigated the topic by the use of pentaery- with UV/Vis spectra of the samples ion-exchanged with [Co(H2O)6]2+
thritol with Na+ in the ZSM-5 synthesis. The product contained Al were recorded. It was concluded that the majority of Al is facing the
atoms predominantly situated at straight and sinusoidal channels in the channel intersections in both samples, yet the dominant Al distribution
MFI framework (Fig. 12) [178]. This work was further extended by in ZSM-5(p) is as single atoms (83 %) wheres the paired Al atoms are
using a series of straight- and branched-chain alcohols (1,3-propanediol prevalent in the ZSM-5(s) (70 %). In addition, the samples are similar in
(PDO), 1,6-hexanediol (HDO), glycerol (GLY), diethylene glycol (DEG), terms of the quantity of Brønsted and Lewis acid sites, containing
triethylene glycol (TEG), tert-buthanol (TBO), trimethylolethane (TME) mainly Brønsted and a few Lewis type sites. Likewise, these acid sites
and pentaerythritol (PET)) in the ZSM-5 synthesis. The Al atoms in the have nearly equal strength. The authors investigated the ethanol
ZSM-5 prepared with bulky and branched-chain alcohols such as TBO, transformation to hydrocarbons in the presence of the prepared mate-
TME, and PET combined with Na+ were located in narrow straight rials. Based on the FTIR and operando experiments, it was found that the
and/or sinusoidal channels [179]. ethanol adsorption on the protonic sites is faster on isolated Al than on
TPA/Na ZSM-5 material was the least stable in the n-hexane the paired sites. At 250 °C the conversion degree is lower for the paired
cracking. In this reaction, the highest yield of propane was measured Al sites, but both catalysts exhibit high selectivity towards ethene. The
for TME/Na and PET/Na samples. Two tested ZSM-5 materials prepared paired Al atoms stabilize the ethanol molecule by forming an additional
with the bulky OSDAs, TME/Na and PET/Na, were the most stable hydrogen bond, thus promoting the ethanol-ethoxy-mediated dis-
catalysts in the MTO reaction. The deactivation took place as a con- sociative pathway. Besides, the adjacent Brønsted sites facilitate the
sequence of the coke deposition; thus, the improved endurance of TME/ dimerization and hydrogen-transfer reactions. The data suggest that the
Na- and PET/Na-derived catalysts to coking is ascribed to the acid sites regeneration of Brønsted acid sites at higher temperatures takes place
occupying the channel positions, thus posing steric constraints on the via releasing of ethane [184]. Another study reports the synthesis of
formation of the coke precursors [179]. In the following study of the two series of ZSM-5 zeolite materials with silica sol and tetra-
PET/Na system, the Al in the prepared ZSM-5 material was again pri- ethylorthosilicate (TEOS) as the silicon source. Both series of materials
marily located within the 10 MR channels presenting a higher number present similar properties in terms of their acidity, morphology, and
of acid sites than ZSM-5 synthesized with the aid of TPA [180]. textural properties. Nevertheless, they differ with respect to aluminium
Moreover, the Brønsted sites acid are stronger, and Lewis sites weaker location in the framework, as in the silica sol series prevails the Al
in comparison with the material yielded in the TPA system. In n-octene position in the sinusoidal and straight channels, while in the samples
cracking reaction, PET/Na-ZSM-5 was more active catalyst with longer prepared in TEOS systems Al is dominantly sited in the channel inter-
lifetime and lower hydrogen transfer coefficient than the TPA-ZSM-5 sections. Consequently, they exhibit different performance as catalysts
in methanol to olefins reaction. The results suggest the Al in the channel
11
intersections favours the aromatic cycle reaction pathway while the Al materials were tested as catalysts in n-heptane hydroisomerization and
in the channels promotes the alkene cycle in MTO reaction [185]. methanol-to-hydrocarbons reaction. Their performance correlates well
In terms of their performance in a specific application, nanosized with the Brønsted acid site density of the ZSM-5 zeolites. Yet, the na-
materials may exhibit strikingly different behavior than their micron- nolayered ZSM-5 zeolites exhibit similar catalytic performance as the
sized counterparts. Keeping this in mind, researchers have devoted bulk ZSM-5 reference. The higher isomers’ selectivity and the selectivity
special attention to design nanosized zeolites presenting particular to di-branched isomers of the nanolayered ZSM-5 was attributed to the
properties. For instance, nanosized ZSM-5 materials were synthesized in shorter diffusion pathway. In methanol-to-hydrocarbons reaction, the
a system with varying H2O/Al ratio from 200 to 2600. Decreasing the nanolayered materials showed higher propylene to ethylene ratio than
Al content in the synthesis mixture yielded samples with Al distributed the reference ZSM-5 sample. Furthermore, the turnover number was
at the rim of the crystals. In addition, these acid sites were more higher for the nanolayered ZSM-5 zeolites suggesting that all the ex-
abundant and stronger. However, testing these materials as catalysts in isting Brønsted acid sites are accessible [189].
methanol to hydrocarbon (MTH) reaction showed they are less stable
and have lower catalyst capacity than the samples prepared with higher 4.1.2. FER-type materials
Al concentration [186]. In another study, nanosized ZSM-5 materials Ferrierite is a medium-pore zeolite which possesses four crystal-
were prepared at 100, 120, 150, and 170 °C [187]. The materials pre- lographically distinct tetrahedral sites in its structure (Fig. 14). The
sent similar Si/Al ratio (≈ 30), but the particle size, the number of acid sites are distributed over two different channel systems, 10 MR (parallel
sites, and their strength increase with the increase of synthesis tem- to the [001] direction) and 8 MR (parallel to the [010] direction)
perature. Further, in the samples that crystallized at lower temperatures channels. At the intersection of the 8 MR and 10 MR channels, the so-
(100 and 120 °C), deposition of amorphous alumosilicate species within called ferrierite cage is formed. Comprehensive investigations of the Al
the zeolite particles was observed, suggesting that under such synthesis location within the FER framework have shown that it can be directed
conditions, the incorporation of aluminum in the zeolite framework is by utilizing a particular OSDA. Moreover, heteroatoms such as B, Ga,
reduced. Upon testing in MTO reaction, the ZSM-5 material prepared at Ti, and Fe have been successfully incorporated in the FER framework
the lowest temperature (100 °C) showed the most extended catalyst [190–195]. FER-type materials have been obtained in the presence of a
lifetime, highest propene selectivity, and light olefins yield. On the range of OSDAs (tetramethylammonium (TMA), pyridine, pyrrolidine
other hand, on the materials synthesised at higher temperatures (150 (Pyr), choline, piperidine, 2,4-pentandione, etc.) [196]. Besides, very
and 170 °C), the aromatics cycle pathway of the MTO became more often dual-templating concept is applied for FER preparation (tetra-
expressed, resulting in more ethene produced. The high-temperature methylammonium + trimethylamine, tetramethylammonium + 1,3-
samples present more than the double quantity of coke in the spent diaminopropane, pyridine + propylamine, tetramethylammonium +
catalyst than do the samples prepared at 100 and 120 °C. Further, in the 1-benzyl-1-methylpyrrolidinium (BMP), piperidine + cetylmethylpi-
materials obtained at 150 and 170 °C are present alkylated polycyclic peridinium [197–201]). Furthermore, it is possible to prepare ferrierite
aromatic compounds, whereas in the chromatograms of the spent 100 materials in the absence of OSDAs. In this case, a cooperative effect of
°C ZSM-5 were detected partially hydrogenated oxygen-containing Na+ and K+ cations was established [202].
species. The reason for such different behaviour of the ZSM-5 sample An extensive structural study of FER-type zeolite material of Si/Al
prepared at 100 °C is the lower acid site density, lower acid strength, = 16 synthesized using a combination of tetramethylammonium (TMA)
and shorter diffusion path. The larger external surface area of this and pyrrolidine (Pyr) as OSDAs has shown that TMA+ species occupy
sample also contributes to better performance in the MTO reaction the ferrierite cage solely, whereas Pyr is present in both the ferrierite
[187]. cage and the 10MR channels (see Table 3). In the latter case, the ar-
Aggregated nanosized MFI-type crystals with size from 30 to 2000 rangement of Pyr is slightly different in the sample prepared with
nm were prepared using different quantities of sodium bromide by a pyrrolidine exclusively. The results suggest that in the FER sample
two-step heating hydrothermal synthesis. The decrease of NaBr content prepared in the presence of TMA and Pyr, aluminum tends to populate
resulted in lowering the crystal size and higher ratio of weak to strong the T1 site in the 8MR and the cage. As shown in Table 3, in the ma-
acid sites, as well as in the higher number of Brønsted acid sites at the terial prepared solely with Pyr, Al exhibits a preference for the T3 site
external surface as determined by di-tert-butylpyridine titration. located in the ferrierite cage [203]. The authors surmised that the or-
Moreover, the total number of Brønsted acid sites, as well as the ratio of ganic molecules with protons able to form hydrogen bonds with oxygen
Brønsted to Lewis acid sites, is decreasing [188]. Testing of these ma- atoms present a stronger effect on the Al distribution than the qua-
terials as catalysts in methanol to hydrocarbon reaction showed that the ternary ammonium cations. Namely, in the latter system, the organic
samples with moieties shield the positive charge of the N atom, thus disabling the
crystal size in the range 80−200 nm and fewer internal Brønsted cation to establish strongly directed interactions with the Al-containing
acid sites promote the selectivity to propylene as well as extend the species in the zeolite synthesis mixture. Accordingly, Al is not in-
zeolite catalyst lifetime. corporated into a specific position within the zeolite framework. In the
Nanolayered ZSM-5 zeolites of Si/Al = 19–27 were synthesized case of FER-type materials prepared in the presence of fluoride ions
using C22H45–N+(CH3)2–C6H12–N+(CH3)2–R (R = hexyl or propyl) as using 1-benzyl-1-methylpyrrolidinium, Pyr, and TMA, the aluminium
structure-directing agents (Fig. 13) [189]. Upon using the propyl group occupation of T positions depends on the OSDA employed [204].
instead of hexyl, the crystallization was accelerated due to the miti- Using a combination of TMA cations with cyclic amines having
gated occupation of the MFI channel intersections by quaternary am- different dimensions (pyrrolidine and hexamethyleneimine (HMI))
monium moieties. When NaF was added to the reaction system, a na- FER-type zeolites of low Si/Al ratio (< 20) and various Al distributions
nolayered ZSM-5 zeolite of high crystallinity was formed. However, not have been synthesized. When Pyr was used, either in the presence or
all Al atoms were incorporated into the zeolite framework, which af- absence of TMA cations, materials with the majority of the acid sites
fects the Brønsted acidity of the prepared materials – the acid sites within the 8MR channels were produced. On the other hand, HMI, to-
concentration is lower when compared with a ZSM-5 reference syn- gether with TMA, resulted in materials having acid sites predominantly
thesized in the absence of bulky OSDA. The acid site density was found located within the 10MR channels [205]. It was suggested that there are
to be a function of the material’s crystallinity. Still, the Brønsted acid very strong electrostatic interactions between the cyclic amines used as
sites of all the nanolayered ZSM-5 samples were of comparable strength OSDAs and the zeolite framework. The change of the acid site dis-
to that of the reference ZSM-5 zeolite. Further, more Lewis acid sites tribution depends on the physicochemical properties of the amine and
were measured in the nanolayered ZSM-5 zeolites than in the bulk ZSM- its relative position/orientation within the lattice.
5 due to the presence of extra-framework Al species. The prepared Further, the addition of ferrierite seeds to the FER synthesis reaction
12
Fig. 13. TEM images of nanolayered ZSM-5 materials synthesized using C22H45–N+(CH3)2–C6H12–N+(CH3)2–R (R = hexyl or propyl).
Fig. 14. A c-axis view on the FER-type framework in the hypothetical case when Al atoms occupy all T1 (left) and T3 (right) sites.
mixture without the presence of OSDAs yielded material denoted as products [207].
FER@FER having enhanced crystallinity compared to seed crystals. Catizzone et al. synthesised FER-type materials using pyrrolidine
Such material exhibited a lesser amount of defect sites, i.e., extra-fra- (Pyr), ethylenediamine (En), tetrahydrofuran (THF) as well as 1,8-
mework Al species yielding Lewis sites, and an increased amount of diaminooctane (DAO) as OSDAs [195]. Moreover, SLS was used to
Brønsted acid sites assigned to stable T2 sites. The highly crystalline control the crystal size of the FER-type material prepared with Pyr as
FER@FER showed high methyl acetate productivity and selectivity in OSDA. The obtained crystals were different in size, morphology, and
gas-phase carbonylation of dimethyl ether (DME). Besides, its deacti- the agglomeration level. At the same time, the addition of SLS to the
vation rate in this reaction is lower. Tetrahedral Al sites, especially the pyrrolidine mixture resulted in the formation of notably smaller crystals
T2 sites, were found to be the active sites required for the selective with the longest dimension < 500 nm, than in the absence of SLS. The
27
formation of hydrogen-bonded DME intermediates by suppressing a Al MAS NMR data indicate THF produced FER-type materials with all
competitive water absorption generated by the methanol dehydration Al built into zeolite framework. Further, in Pyr, En, and DAO samples,
on the Brønsted acid sites [206]. On the other hand, the addition of 3 wt there is less than 10 % octahedral extra-framework Al. NH3-TPD pro-
% of FER seeds with respect to silica in the pyrrolidine-based synthesis files are nearly identical for the Pyr-FER and SLS-Pyr-FER, demon-
gel resulted in a FER-type material with lower number of Brønsted acid strating that the surfactant molecules alter the crystal morphology ra-
sites and higher number of Lewis acid sites than the non-seeded ther than acidic properties. According to IR spectra of the samples
synthesis gel [207]. When sodium lauryl sulfate (SLS) surfactant was studied with adsorbed deuterated acetonitrile, the En-FER and DAO-
added to the synthesis gel, a ferrierite material with a substantially FER possess the highest concentration of Lewis acid sites (≈ 40 %). In
higher number of Lewis acid sites than in the materials obtained in the THF-FER there is 15 % of Lewis acid sites with respect to total acidity.
seeded and un-seeded systems. Abundant Lewis acid sites in SLS-de- The fraction of strong Lewis acid sites in this series of samples follows
rived FER make it unappropriate as a catalyst for the vapor-phase de- the order DAO-FER > En-FER > Pyr-FER (≈SLS-Pyr-FER) > THF-FER.
hydration of methanol to DME since they promote the formation of by- THF-FER was the least efficient catalyst in methanol to dimethyl ether
13
reaction, which was attributed to the larger size of the crystals. For the
same reason, Pyr-FER is less active at 180 °C than nanosized SLS-Pyr-
FER, but at higher temperatures, the samples DAO-FER, En-FER, Pyr-
FER, and SLS-Pyr-FER display similar performance. In terms of DME
selectivity at 180 °C, the yield is 100 % over THF-FER and DAO-FER. At
higher temperatures, the DME selectivity gradually decreases. THF-FER
sample continuously loses its activity during the reaction at 240 °C with
the most significant quantity of deposited carbonaceous species. The
highest concentration of Brønsted acid sites, as well as the largest size of
the crystals, may cause fast deactivation of the THF-FER material.
Further, the samples Pyr-FER and SLS-Pyr-FER have similar acidic
properties, yet less coke is formed on smaller SLS-Py-FER [195].
4.1.3. CHA
CHA-type zeolite is a small pore material. The CHA framework is a
member of both the D6R-only and ABC-6 zeolite structures families.
Namely, its structure can be represented by stacking planes of non-
connected 6MRs following the AABBCC sequence. Further, the CHA-
type framework can be represented by the assembling of exclusively
D6Rs. Cha cage is a part of the three-dimensional pore system, and the
CHA-type lattice comprises one unique inequivalent T site. The synth-
esis of low-silica alumosilicate CHA-type materials is usually conducted
by employing zeolite Y as both Si and Al source in potassium hydroxide
reaction media [208]. In order to prepare a CHA material having Si/
Al > 5 (SSZ-13), the presence of an OSDA like N-methyl-3-quinucli-
dinol iodide, N,N,N-trimethyl-2-ammoniumexonorborane, choline and
benzyltrimethyl-ammonium hydroxide in a reaction mixture is re-
quired. Still, the N,N,N-trimethyl-1-adamantammonium hydroxide
(TMAdaOH) is the most common OSDA for SSZ-13 synthesis [209]. All
Fig. 15. The fraction of paired Al atoms in a series of SSZ-13 zeolites (Si/Al =
siliceous CHA material has been attained in the fluoride medium [210].
15), plotted versus the ratio Na+/TMAda+ in the initial crystallization mixture
Recently, efforts have been made in reducing chabazite synthesis costs
of the equivalent total concentration of cations. The dashed field represents the
and finding more environment-friendly preparation routes such as by area where a mixture of two phases (CHA and MOR) is formed. Reprinted with
using TEAOH and/or adding CHA seeds to the reaction mixture permission from reference [219]. Copyright (2016) American Chemical Society.
[211,212].Besides well-known silicoaluminophosphate CHA-type
analog SAPO-34, the acidity of CHA-type aluminosilicate zeolites can
function of the Na+ incorporated into the crystalline solids [199]. This
be tuned by the framework incorporation of heteroatoms. Thus B-, Ge-,
work was extended by involving various Al sources (Al(OH)3, AlCl3, Al
Zn-, Sn-, Zr-, In-, Ga- and Ti-containing CHA materials have been pre-
(NO3)3, NaAlO2, Al2O3, Al(O-i-Pr)3) in the synthesis. The SSZ-13 ma-
pared, often with the addition of seed crystals to the preparation mix-
terial prepared with the aluminium isopropoxide contained a double
ture [213–217].
quantity of the paired Al atoms than the material crystallized using Al
Recently, Lusardi et al. prepared a series of SSZ-13 materials with
(OH)3. In addition, the CHA-type material prepared from Al(O-i-Pr)3
varied aluminium content, and hence the materials presented frame-
contained a greater amount of Na+ [113]. The data suggest that the
work Si/Al ratio ranging from 9 to 35 [218]. As the Al amount in-
Na+ is occluded in the extra-framework locations adjacent to the ca-
creased, both the number of Brønsted acid sites and extra-framework Al
tionic charge of TMAda+, consequently directing the formation of
sites increase too. SSZ-13 of Si/Al = 10 together with MOR- and FER-
paired framework Al atoms. In methanol dehydration reaction, the
type materials of similar Si/Al ratio were tested in the reaction of
samples with paired protons accelerate the turnover rates by order of
carbonylation of dimethyl ether (DME) to methylacetate (MA). MOR
magnitude compared to the SSZ-13 samples with isolated protons. It
was found to be the most active in the initial stage of the reaction but
seems that the paired protons stabilize surface methoxy species in-
slowly lost its activity as the carbonaceous deposits formed within the
volved in an alternate dehydration mechanism. Interestingly, in the
12MRs channel. FER-type material was a notably less active catalyst,
case when K+ substitutes Na+ in the otherwise identical reaction
whereas CHA is comparable to MOR selectivity-wise and remains active
conditions, just single 6MR Al atoms are formed in SSZ-13 [220]. This
for a longer time. Further, SSZ-13 materials of lower Al amount yielded
effect was explained by postulating that K+ competes for TMAda+
less MA because the surface coverage of methoxy groups is broader for
occlusion within larger void spaces. DFT calculations indicate that in
materials with more Al; hence the probability for the successful colli-
this case, the number of 8MR paired sites might be greater.
sion with CO is higher. The fact that this relation is not linear is owing
The ability of paired Al sites in the CHA framework that have high
to the highest methylacetate production rates on methoxy groups re-
capacity towards divalent cation to get ion-exchanged with Fe2+ is
siding in the 8MRs. The lowest carbonylation rates are attained for the
convenient for designing catalyst for partial methane oxidation.
methoxy groups in the CHA cage above the 6MR, as predicted by the
Namely, the Fe located in the 6MRs with paired Al in the CHA frame-
DFT calculations [218].
work are the active sites for this reaction. Inspired by this fact, Devos
In order to tune their acidic properties, Di Iorio et al. synthesized
et al. prepared a series of SSZ-13 samples (Si/Al = 30–45) from
CHA-type zeolite materials (Si/Al = 15–30) in hydroxide media in the
amorphous hydrogel precursors and via interzeolite conversion [221].
presence of TMAda+ cations. The samples contained only isolated
The materials prepared via interzeolite conversion possessed more
framework Al sites (see Table 3). The addition of Na+ to the zeolite
paired Al sites and consequently exhibited higher methanol pro-
preparation reaction mixture, at the same time, maintaining the con-
ductivity when Fe-modified SSZ-13 materials were employed as cata-
centration of cations ((Na+ + TMAda+)/Al) and other reaction para-
lysts in partial methane oxidation.
meters, yielded SSZ-13 zeolites of a fixed Si/Al ratio but with paired Al
In 2018 Nishitoba et al. produced CHA framework-type zeolites
sites (Fig. 15). The amount of paired sites was found to be a linear
14
with the assistance of TMAdaOH in a system comprising fumed silica, precursor lies in the higher acid sites density that accelerates coke
aluminum hydroxide, and the FAU-type zeolite with altering propor- formation [224]. Lastly, in the Table 4 is demonstrated the effect of
tions of Al-comprising chemicals – Al(OH)3 and FAU-type zeolite [222]. zeolite acidic properties on their performance as catalysts in MTO and
Besides, 5 wt% of calcined SSZ-13 seed crystals were added to the re- MTH reactions. In MFI-type material lower amount of Brønsted acid
action mixtures. The prepared materials have a similar amount of acid sites favours the formation of propylene, whereas in the case of CHA
sites, yet the distribution of Al atoms is different. When the proportion materials having fewer acid sites ethylene was the main product. In
of the Al source derived from the FAU-type zeolite was increased, the addition, both types of materials deactivate faster if they present a high
fraction of Q4 Si species with two neighboring Al atoms (Si number of acid sites.
(OSi)2(OAl)2) was higher as well. The authors correlate the relative Detailed NMR study of a set of Na-SSZ-13 samples of Si/Al ratio in
population of Q4(2Al) with the hydrothermal stability of the material the range 4–48 prepared with varied Al content in the synthesis gel
since the Al atoms in Q4(2Al) positions would be easier for deal- revealed that in the high silica Na-CHA zeolite, Na+ cations are pre-
umination than the ones in Q4(1Al). A higher fraction of the paired Al ferentially found at 6MR cationic SIIa0 site corresponding to one Al in
sites in the CHA-type materials prepared from the systems with a high the Cha cage. As the Al content rises, Na+ ions are located at 6MR SIIa1
quantity of FAU-type zeolite resulted in the formation of a larger and 8MR SIII’a1 sites suggesting the presence of Al pairs. In low silica
amount of aromatic carbonaceous deposits in the material and thus CHA materials, Na+ cations occupy all possible ion-exchange sites of
shortened the catalyst lifetime in MTO reaction in comparison to the the CHA framework due to many Si(2Al) and Si(3Al) moieties [225]. In
sample prepared with a lower amount of FAU material [222]. Nano- a recent study, SSZ-13 material was obtained by non-classical attach-
sized SSZ-13 zeolites (Si/Al ratio = 9–25) prepared by steam-assisted ment growth of nano building blocks mediated by Pickering emulsion
synthesis method have been employed in MTO reaction as well. The in a biphasic water/toluene medium aided by trimethoxy[3-(phenyla-
method involves the preparation of a clear Al-Si precursor sol, followed mino)propyl]silane. 95 % of Al present in the solid sample was in-
by water evaporation at 90 °C. The powder was charged in the top part corporated into the CHA zeolite framework, and, as observed by NH3-
of Teflon-lined autoclave with inserted Teflon vial containing a certain TPD, it presented acidity comparable to the CHA-type material pre-
amount of water, avoiding direct contact between liquid water and pared from a conventional synthesis mixture. Upon ion-exchange with
dried gel. In contrast to SSZ-13 (Si/Al = 14) zeolite prepared by con- Cu2+, this material outperformed the conventional one as a catalyst in
ventional hydrothermal synthesis from amorphous hydrogel precursor, NOx removal by NH3-SCR under both, low- and high-temperature
the nanosized vapor-phase synthesized CHA-type material (Si/Al = 15) conditions [226].
exhibited 2.6-fold longer catalyst lifetime keeping the 100 % conver-
sion. Likewise, the total selectivity towards ethane and propane is 4.1.4. MOR
higher for the nanosized SSZ-13. This example clearly shows that zeo- MOR-type zeolite framework contains a straight 12 MR channel
lite downsizing notably contributes to overcoming the diffusion lim- intersecting with 8 MR side pockets. There are four unique T positions
itations in catalytic processes [223]. in the MOR-type framework: T1 in the 12 MR channel, T2 and T4 in the
Another approach in developing an efficient CHA-type catalyst for intersection between the 12 MR channel and the 8MR pocket, and T3
MTO is by interzeolite conversion of zeolite L. Different amount of NH4- within the 8MR pocket. It has been found that in mordenite, Al pre-
LTL zeolite was added to the system containing fumed silica, TMAdaOH ferentially resides in T3 and T4 sites (Fig. 16) [227]. Mordenite occurs
and NaOH providing a series of SSZ-13 materials having Si/Al ratio as a mineral and with the Si/Al ratio of 5 is the most siliceous natural
from 25 to 183. When compared with SSZ-13 prepared from the zeolite. MOR-type materials of Si/Al up to 10 can be prepared without
amorphous hydrogel precursor (Si/Al = 31), the LTL-derived materials OSDAs (Table 3) [228], whereas the higher Si content has been reached
have lower peak intensities in the NH3-TPD, and the high-temperature with the assistance of TEA+, n-buthanol, 1-butyl-3-methylimidazolium
desorption peak is shifted towards lower temperatures. Further, the bromide, etc. [229–232]. It should be noted that all-silica MOR-type
27
Al MAS NMR spectrum of the sample having Si/Al = 47 demonstrates material has not been prepared so far. Similar to other zeolite frame-
the presence of only tetrahedral Al. The SSZ-13 materials originating works, the properties of MOR-type materials have been altered by in-
from LTL systems present much longer catalyst lifetime and higher corporation of different heteroatoms (B, Ti, Fe, Zn, Ga, Sn, …) into the
selectivities towards ethane and propane in MTO reaction. Maximal framework [233–238].
catalyst stability and highest ethane and propane yields were achieved Millimeter-sized mordenite (MOR) zeolite spheres (Si/Al = 6–10)
for the SSZ-13 where Si/Al ratio was 96. In this case, the reason for with excellent mechanical strength have been prepared via vapor-as-
more rapid deactivation of the SSZ-13 obtained from amorphous sisted transformation of Na- and Al-doped SiO2 spheres in the presence
of tetraethylammonium hydroxide (TEAOH), tetramethylammonium
Table 4 hydroxide (TMAOH), hexamethylenimine (HMI) and water (Fig. 17)
Impact of MFI- and CHA-type zeolite acidic properties on the MTO and MTH [239]. According to the 1H MAS NMR spectra and NH3-TPD analysis,
reactions. the quantity of Brønsted acid sites in the MOR synthesized from
Property Catalytic performance Reference
TEAOH-containing system is higher than in commercial mordenite with
Si/Al = 6.5 and the similar total amount of acid sites. Moreover, in the
MFI-type materials TEAOH sample, the number of Brønsted acid sites in the 8MR side
Al at channel intersections aromatic cycle [185] pockets is determined to be three times higher than that in the 12MRs
channel Al alkene cycle [185]
(Table 3). As a consequence of the preferential position of acid sites in
improved endurance of catalysts [179]
to coking the 8-MR side pockets, the TEA-MOR material displays superior cata-
Al at the rim of the crystals less stable catalyst of lower [186] lytic activity in the DME carbonylation reaction with a steady DME
capacity conversion of 90 % in comparison to 23 % conversion over the com-
less Brønsted acid sites alkene cycle [187]
mercial MOR sample. Both samples are highly selective towards methyl
lower Brønsted acid site alkene cycle
strength acetate (> 95 %), yet TEA-MOR catalyst slightly outpases the com-
fewer internal Brønsted acid higher selectivity to propylene [188] mercial one [239].
sites extended catalyst lifetime Nanocrystalline mordenite (nanorods and nanosheets) materials of
CHA-type materials Si/Al = 30–56 and possessing up to 60 % of acid sites located on the
higher fraction of paired Al shorter catalyst lifetime [222]
external surface have been prepared with the aid of Gemini-type sur-
higher acid sites density shorter catalyst lifetime [224]
higher propylene yield factants. On the other hand, conventional MOR crystals in the com-
mercial sample have only 12 % of the acid sites at the external surface.
15
Fig. 16. A c-axis view on the MOR framework in the hypothetical case when Al atoms occupy all T3 (left) and T4 (right) sites.
MOR catalysts with enhanced crystallinity and a higher quantity of

strong acid sites in comparison to the reference zeolite obtained
without PEG [243]. The stability and activity of the PEG-MOR-type
materials employed as catalysts for DME carbonylation is greatly en-
hanced with respect to the conventional MOR-type sample. In the
course of the reaction, the selectivity towards methyl acetate was al-
ways higher than 98.5 % for the hierarchical MOR materials. Besides,
markedly lower selectivities towards methanol and hydrocarbons are
achieved over PEG-MOR than over reference MOR, suggesting that the
side-reactions are hindered for the hierarchical catalysts. Clearly, a
more significant amount of strong acid sites and improved mass transfer
efficiency facilitate the DME conversion over the PEG-MOR-type ma-
terials [243].
4.1.5. Zeolite beta (BEA@BEB)

Zeolite Beta possesses a three-dimensional system of intersecting
channels and nine distinct crystallographical T sites. Zeolite Beta is a
disordered material, but this does not cause any blocking of the 3D
Fig. 17. SEM images of MOR spheres synthesized under TMAOH, HMI, and 12MR channel system [4]. The family of zeolite Beta consists of three
H2O vapors. Reprinted with permission from reference [239]. Copyright (2018) polymorphs: polymorph A (BEA), polymorph B (BEB), and polymorph C
American Chemical Society. (BEC). Typical zeolite Beta contains polymorphs A and B in a 60:40
ratio [244]. Polymorph A- and polymorph B-enriched materials have
Still, all of the been synthesized [245,246], wheraes pp\olymorph C has been firstly
studied materials, both nanocrystalline as well as micron-sized prepared as Ge-silicate material [247], and subsequently, a pure silica
MOR, exhibit a similar fraction of strong Brønsted and Lewis acid sites material was obtained [248]. All-silica standard zeolite Beta can be
[240]. Owing to the improved accessibility of active sites, the nanorod prepared in both fluoride and hydroxide media [210,249]. Further,
and nanosheet mordenites show higher catalytic activity in acid- cata- next to Al, a range of other atoms (Ti, Sn, B, Zr, Hf, Zn, etc.) have been
lyzed annulation reaction of 2-naphtol with methylbut-3-en-2-ol than incorporated into zeolite framework in various positions either by in
does the commercial zeolite. Furthermore, over the nanorod MOR-type situ or post-synthesis methods [244,250–257]. TEAOH is a typical
material was achieved the highest yield of dihydronaphthofuranes OSDA for zeolite Beta synthesis [258], though it can be obtained with
[240]. In a similar study, Wang et al. prepared a hierarchical MOR, numerous organic templates [144,244,259].
which had acid sites identical in nature, yet more abundant than the The Al atoms in the as-synthesized zeolite Beta samples of Si/Al
conventional MOR-type material synthesized without utilizing Gemini- ratios 9–215 prepared in fluoride medium with TEA as OSDA were
type surfactant [241]. Both materials are stable and active catalysts for found to reside in two crystallographically distinct positions [260]. The
the dehydration of ethanol. site denoted as Td2 becomes more populated with increasing the fra-
Liu et al. have fabricated hierarchical MOR-type nanosheets by self- mework Si content. However, in the calcined materials of Si/Al = 9–56
assembly of nanocrystals and hexadecyltrimethylammonium bromide octahedral Al species appear. In addition, for the calcined materials, the
(CTAB) combined with polyethylene glycol (PEG) molecules. In com- Td1 site is more populated than Td2. In the case of zeolite Beta sample
parison to material synthesized in the absence of CTAB and PEG, a of Si/Al = 215 the Td2 signal in 27Al 3Q MAS NMR resolved into two
higher amount of both Brønsted and Lewis acid sites is present within components. The observed effect is attributed to TEA+ cations, which
the hierarchical pore system. Accordingly, nanosheet MOR material affect the TeOeT angles and shield the Al and Si atoms, thus changing
exhibits higher activity, xylene selectivity, and longer catalyst lifetime the chemical shifts of some T sites. Noteworthy, the different popula-
in the toluene disproportionation reaction [242]. The PEG has acted as tions of T sites indicate non-random Al distribution within the zeolite
a mesopore generation agent in the formation of a set of hierarchical framework. The results suggest that the octahedral Al sites detected
upon calcination are formed by the conversion of tetrahedrally
16
coordinated Al located at specific sites and with another Al site in close Si/Al ratio 15 and 30 produced samples of approximately equal Si/Al
proximity needed for the hydrolysis of the SieOeAl bond [260]. Zhao ratio, that is 15 and 30, respectively. In each of the pristine Beta zeo-
et al. have prepared high-silica Beta zeolite (Si/Al = 136–340) em- lites, all the Al species are present in tetrahedral coordination. After the
ploying TEAOH as OSDA in the presence of HF. Expectedly, the acid site calcination at 580 °C, in the material of Si/Al = 15, 15–20 % of Al is
density in the obtained materials got lower with the increase of the Si released from the framework. However, in the Beta samples having Si/
content in the framework. The authors varied the HF content (HF/SiO2 Al ratio 30, only about 5 % of Al was released from the framework upon
= 0.35–0.65) in the reaction mixture, keeping the ratio between the calcination. Similarly to the previously described series of Beta zeolite,
other reactants constant [261]. The increase of HF content leads to Beta the samples with higher Al content exhibited a higher quantity of
zeolites having similar NH3-TPD profiles, but a different distribution of Brønsted acid sites. Likewise, these materials show enhanced catalytic
tetrahedral Al species, as shown by the 27Al MAS NMR spectra. A broad activity and selectivity towards desired molecules in the industrially
weak signal in the range −20–0 ppm corresponding to extra-frame- relevant reaction of benzene propylation to cumene. The nanosized
work octahedral Al becomes more pronounced as the quantity of the HF BEA-type materials are active and stable catalysts for the oligomeriza-
added to the synthesis mixture is reduced. Furthermore, the sample tion reaction of 1-pentene, with diesel being the most dominant product
prepared with the lowest HF amount presents a broad resonance at [264].
about 15 ppm, which most probably arises from distorted extra-fra- Sazama et al. prepared Al-rich zeolite Beta materials (Si/Al = 4.5
mework octa- or penta-coordinated Al species, yet in a different en- and 5.1) in an OSDA-free system using seeds. The materials possess a
vironment than the ones around 0 ppm. The 27Al MQ MAS NMR spectra very low fraction of extra-framework octahedral Al. In comparison to
suggest that Al atoms primarily abide T3, T7, T8, and T9 sites in all the commercial zeolite Beta (Si/Al = 11) prepared in an OSDA-con-
samples, but the relative population of these sites varies. In all mate- taining system, the seeded materials present a higher number of acid
rials, the relative occupancy of the T8 and T9 sites by Al is about 90 %. sites yet of similar strength as the commercial material [265]. In the Al-
This study unambiguously showed that the HF content of the synthesis rich zeolite Beta samples, 40%–100% of all Al atoms are found in the
mixtures directly impacts the stability of Al species as well as the Al AleOeSieOeAl sequence while in the Si-rich commercial sample,
distribution within the ultimate crystalline products. The sample of these sequences were not observed. Further, in the Al-rich material, the
medium HF/SiO2 ratio, 0.45, exhibited the longest catalyst lifetime in Al atoms face two different channels, whereas two Al atoms from two
methanol conversion with propene selectivity of 49.7–58.3 % via the different AleOeSieOeAl sequences can be oriented towards the same
dominantly alkane-based mechanism of the reaction. In this study for channel denoting close unpaired Al atoms sited in two different rings.
the first time, were detected phenol compounds in the spent catalyst. Only Al atoms in AleOeSieOeSieOeAl sequences in one ring and a
The authors hypothesize that the phenols get strongly adsorbed on the small relative population of AleOeSieOeAl sequences face the same
acid sites and thus induce the catalyst deactivation. It was concluded channel. It was concluded although the Al- and Si-rich BEA samples
that the cooperative effect of the catalyst acidity and the reaction exhibit significant differences in the distribution of the AleOeSieOeAl
temperature impact the overall MTO reaction. A small quantity of acid sequence, they are similar in terms of the arrangement of Si and Al in
sites facilitates the formation of propene, and high reaction tempera- the zeolite channels and accordingly are similar in binding counter-ion
tures increase the cracking ability of heavier olefins as well as promote species [265]. The same group reported that the Al-rich zeolite beta
the diffusion of the products [261]. In a series of zeolite Beta samples materials with a higher number of Brønsted acid sites are more active in
(Si/Al = 15–230) synthesized in fluoride medium with the quantity of the alkylation of benzene with ethylene. This reaction is not affected by
Brønsted acid sites correlates with the Al content. The tetrahedral T the Lewis sites [266]. Further, a series of hierarchical zeolite Beta was
atoms present three peaks in 27Al MAS-NMR spectra displaying dif- prepared from concentrated amorphous precursors (H2O/Si = 2.5–14)
ferent environment of the framework Al. The highest fraction of extra- using TEAOH as OSDA. As the synthesis time was extended, and the
framework Al with respect to the total Al amount was observed in the crystallinity degree of the materials increased, the total concentration
materials with the Si/Al = 230 due to a lower degree of Al in- of medium and strong Brønsted acid sites got higher. Likewise, the ratio
corporation. When tested as catalysts in aqueous phase cyclohexanol of Brønsted and Lewis acid sites in the more crystalline materials in-
dehydration, samples with a lower number of Brønsted acid sites ex- creased. These materials were found efficient catalysts in 1-octadecanol
hibit longer catalyst lifetime [262]. conversion [267].
Uniform nanosized high-silica Beta zeolites (10–20 nm) obtained by
Martinez-Franco et al. in OH− and F− media using simple alkyl-sub- 4.1.6. Other framework type materials
stituted flexible dicationic OSDAs (1,10-(pentane-1,5-diyl)bis(1-bu- FAU-type zeolites represent the bedrock of oil refining with their
tylpyrrolidin-1-ium) and 1,10-(pentane-1,5-diyl)bis(1-butylazepan-1- acidic properties mostly engineered by post-synthesis treatments.
ium)) present Si/Al ratio ranging from 13 to 31 [263]. Almost 80 % of Namely, FAU-type zeolites of Si/Al ≈ 2.5 can be obtained from con-
the Al species are retained at tetrahedral positions upon the calcination ventional Na2O–SiO2–Al2O3–H2O systems. Higher Si/Al ratios are
in these nano-sized zeolite Beta samples. The materials of Si/Al ratio 15 achieved by dealumination, usually by the steaming process, since the
synthesized both in hydroxide and fluoride media show the highest in situ methods are not very efficient. Hence, a large part of the in situ
number of Brønsted acid sites. In accordance with the lower Al content, work is devoted to developing organic-free methods of preparing high-
the zeolite Beta materials having the Si/Al ratio 30 exhibit lower silica FAU-type materials. Recently Ferdov et al. obtained a series of
Brønsted acidity. Nevertheless, these sites are stronger than the ones in zeolite Y materials of Si/Al > 2.5 from the OSDA-free system with
the samples of Si/Al = 15, as determined by pyridine desorption at 350 higher framework stability than the reference industrial zeolite Y [268].
°C. The studied materials have been tested as catalysts in the cumene These materials were less prone to generate extra-framework Al species
synthesis via alkylation of benzene with propylene. The highest cumene upon calcination than the commercial zeolite of similar Al content. On
yield as compared to the commercial nano-sized Beta zeolite, as well as the other hand, the commercial zeolite Y maintained a higher crystal-
reduced catalyst deactivation with time on stream, has been achieved linity degree. Nevertheless, both types of materials exhibit comparable
for the samples of Si/Al = 15 due to its higher Brønsted acidity [263]. activity towards cracking of 1,3,5-triisopropylbenzene. Venkatesan
The same research group prepared a set of nano-sized zeolite Beta with et al. have prepared mesoporous zeolite Y using seeded intial gel and
the assistance of N-butyl-n-methylhexamethyleneiminium hydroxide, amphiphilic organosilane (3-(trimethoxysilyl)propyl octadecyldi-
N-butyl-N,N-dimethylcyclohexylammonium hydroxide and N-butyl- methylammonium chloride) [269]. The resultant material exhibits a
N,N-dimethylcycloheptylammonium hydroxide in hydroxide medium higher number of strong external acid sites when compared to the
[264]. The Si/Al ratio of the crystalline product was controlled by material prepared from a system where zeolite crystals were added as
variation of the composition of the initial reaction mixture – the gels of seeds instead of the seeded gel. Consequently, mesoporous zeolite Y
17
showed high catalytic activity towards decalin cracking owing to the

high accessibility of acid sites located on the external zeolite crystal
surfaces. In addition, the selectivity to light hydrocarbons was almost
four-fold greater than of heavy hydrocarbons being 79 % and 20 %,
respectively.
MEL-type zeolite belongs to the pentasil family of high silica zeo-
lites, which possesses two intersecting 10MR channel systems. In con-
trast with the MFI-type zeolite, which also has two intersecting 10MR
channel systems, the MEL contains only straight channels.
Tetrabuthylammonium cation is the typical OSDA for the synthesis of
MEL-type material, and the aluminium containing materials are de-
noted as ZSM-11 while the all-silica counterpart as silicalite-2 [270]. A
thorough study of ZSM-11 synthesized in a Na+/TBA+ system, as
presented in Table 3, revealed that Al preferentially occupies sites in the
straight 10MR channels of the MEL framework. In the case of ZSM-5
obtained from Na+/TPA+ system, the fraction of Al located at the MFI
channel intersections was higher. This difference in acid site location is Fig. 18. RTH zeolite framework with labels of crystallographically non-
reflected in substantially different performance and mechanisms in the equivalent T sites.
MTO reaction for the two zeolite materials. The intersection acid sites
promote the aromatic cycle, whereas the alkene cycle is preferred for uniformly distributed on all T sites. Further, there are weak and strong
the acid sites in the straight channels. Consequently, the accumulation Brønsted acid sites associated with the framework Al species in the PY-
of coke species in ZSM-11 is faster and results in its short catalytic RTH, while PMP-RTH and MP-RTH have just one type of the weak
lifetime [271]. Wang et al. further extended this work by investigating Brønsted acid sites. The order as a function of the strong acid sites is PY-
the impact of the addition of varied quantities of Na+ and Li+ cations RTH > PMP-RTH ≈ MP-RTH. Noteworthy, the weak acid sites in PMP-
to the ZSM-11 preparation mixture with a higher concentration of and MP-RTH samples gave longer lifetime and higher propene se-
TBAOH than in the previous study [272]. The prepared materials pre- lectivity in the MTO reaction than the strong one in PY-RTH.
sent bulk Si/Al ≈ 35. Although their acid sites were of similar strength, SSZ-39 is a small pore AEI-type material. Ranson et al. synthesized a
the data suggest that the presence of Na+ in the reaction mixture does series of SSZ-39 samples via interzeolite conversion of FAU-type zeolite
not have a considerable impact on the Brønsted sites, whereas Li+ re- from identical synthesis gels with only different amounts of the trans
duces their number. 27Al MAS NMR demonstrated that the ZSM-11 isomer of N,N-dimethyl-3,5-dimethylpiperidnium hydroxide which
material prepared in an alkali-free system has slightly higher occupancy served as the OSDA [274]. The materials present similar Si/Al ratio
of Al in the channel intersection positions (54.7 %) than in the straight 8.6–10. Yet, according to TEM-EDS analysis in the sample made with 28
channels. Herein, with the addition of Na+ and/or Li+, Al showed a wt% trans-OSDA, the intergrowths of single crystals have different Si/
higher preference for the intersection sites. However, it is necessary to Al values within different single crystals that form the intergrowth
note that in the sample obtained from TBA/Li reaction mixture, 51.2 % particle. Therefore, there is aluminium zoning in intergrown particles of
of Al exists in the Al2O3 form. Moreover, the relative population of SSZ-39 prepared with 28 wt% trans-OSDA. Different Al distribution is
framework Al is getting lower as the quantity of Li+ in the TBA/Na/Li reflected in different copper uptake during performing ion-exchange
mixtures increases. Further, in the TBAOH and TBA/Na MEL-type under the same conditions. Namely, pure cis isomer yields material
zeolites was measured a high fraction of paired Al sites (82 %). The with Cu/Al = 0.25 (2.4 wt% Cu) whereas the 28 wt% trans isomer
contribution of paired Al sites becomes lower in the Li+-containing results in Cu-SSZ-39 of Cu/Al = 0.33 (3.0 wt% Cu). When tested in
systems (67–48). Such action of Li+ was attributed to strong interac- selective catalytic reduction of nitrogen oxides as catalysts, the Cu-SSZ-
tions of the alkali cation with the Al species. Testing the ZSM-11 ma- 39 possessing more Cu was more active in the whole temperatures
terials with Al dominantly located at the channel intersection as a range 150–550 °C. With the purpose of being able to compare the
catalyst in the MTO reaction revealed that the aromatic cycle is pro- catalytic efficiency of the materials, the sample from cis-OSDA system
moted, and more ethene and aromatics are formed. On the other hand, was additionally ion-exchanged until reaching the same Cu content as
in the sample with an approximately similar fraction of Al in the with the trans-OSDA. In this case, the activity of the catalyst made with
straight and intersection channels was observed a more noticeable pure cis-OSDA is higher above 350 °C. At elevated flow rate, the Cu-
contribution of alkene cycle MTO pathway. As the amount of the extra- SSZ-39 from the 28 wt% trans-OSDA system is more active at 150 and
framework Al is increasing, and there are fewer Brønsted acid sites, the 200 °C, while the cis-OSDA shows more than 10 % higher conversion at
catalyst lifetime of ZSM-11 materials is shorter. Thus, it is possible to higher temperatures. Further, it was found that the Cu-SSZ-39 zeolites
adjust the selectivity and catalyst stability in the MTO reaction by al- synthesized with a different fraction of trans-OSDA display different
tering the Al position at different zeolite MEL-type framework sites activity. The authors speculate this behavior arises due to the differ-
[272]. ences in Al distribution within the studied samples [274].
The framework of RTH-type small pore zeolites is built of rth cages A medium pore MTT-type material known as ZSM-23 is synthesized
with 8MR openings. There are four crystallographically non-equivalent with isopropylamine (IPA) and pyrrolidine (PY) as structure-directing
sites. The structure features two channels of non-distorted 8MR pores agents. These two templates were employed either alone or in ratio
and distorted 8MRs, which run along with the a- and c-axis, respec- IPA/PY = 3 and varying the Al content of the reaction mixture. The
tively. As shown in Table 3, Liu et al. have synthesized RTH-type zeolite usage of the two OSDAs did not affect the total acid site number when
by using 1,2,2,6,6-pentamethylpiperidine (PMP), N-methylpiperidine compared with the materials prepared with a single template yet did
(MP) or pyridine (PY) with the addition of ethylenediamine [273]. alter their distribution. Upon Pt precipitation on the studied samples,
Moreover, in the scope of the same investigation, the RTH-type zeolite they were evaluated for their efficiency in n-hexadecane hydro-
has been prepared without using any OSDA by employing seeds and isomerization. The samples possessing more weak Brønsted acid sites
sodium cations. The obtained results indicate that the use of bulky facilitated the hydroisomerization reaction. Moreover, the highest se-
OSDAs such as PMP and MP leads to the preferential incorporation of Al lectivity of iso-hexadecan was reached over the material with most of
species at T1, T2 and/or T3 sites (Fig. 18). Brønsted acid sites [275].
On the other hand, in the OSDAs-free synthesis, Al species are
18
STW-type zeolite, denoted as Al-HPM-1, exhibits chiral framework aluminium halides showed that the AlCl3 and AlBr3 generate both oc-
with helical pores. The material was synthesized by a two-step proce- tahedral and tetrahedral Al species. The incorporation of solely tetra-
dure, referred by the authors as an in situ seeds generation synthesis hedral Al in ZSM-5 was achieved by hydrothermal treatment using an
method [276]. In the study, the all-silica precursor was firstly prepared (NH4)3AlF6 solution of pH 10.5 [278].
and treated at 175 °C. After three days, Al(OH)3 has been added to the Upon treatment of ultrastable zeolite Y (Si/Al = 6.3) with the 0.05
reaction mixtures in order to achieve the Si/Al = 15, 25, and 35. The mol dm−3 solution of Al(NO3)3 FAU-type materials of Si/Al = 5.1 (12 h
hydrothermal treatment of the synthesis mixture obtained in this way of treatment) and Si/Al = 4.7 (24 h of treatment) were obtained.
was then continued at 175 °C for 1 day. 29Si and 27Al MAS NMR spectra Framework Si(0Al) sites have been substituted by Al ions, keeping the
indicate that the Al occupies both octahedral and tetrahedral positions crystallinity and micropore volume preserved. The number of Brønsted
in the prepared STW materials. Increasing the Si/Al ratio in the reaction acid sites and strong Lewis acid sites was higher in aluminated samples,
mixture resulted inhigher amount of Al located in tetrahedral frame- whereas the quantity of weak Lewis acid sites decreased two times,
work positions. All samples were active as catalysts in the reaction of suggesting lowering the concentration of extra-framework Al species
ethanol conversion into ethylene and diethylether, which was con- [279]. The two FAU-type materials were modified by ruthenium and
ducted to evaluate the acidity of the synthesized STW materials. It was tested as catalysts in benzene hydrogenation. Aluminated USY zeolite
observed that the extra-framework Al inhibited ethanol conversion and exhibited a higher catalytic activity than the initial zeolite as the re-
diethylether was the preferred product [276]. The presented results action rate increased by 5.5 times. Indeed, the enhanced quantity of
indicate that all of the species present in the zeolite synthesis system Brønsted acid sites increases the active site concentration.
can exhibit an impact on the crystallization course and hence influence The insertion of Al into the zeolite Beta framework was performed
the Al incorporation within the zeolite framework and consequently, by using NaAlO2 solutions. Si/Al was lowered as a consequence of Al
their catalytic performance. incorporation into structural vacancies and substituting framework Si
atoms. The process was facilitated by increased NaAlO2 concentration
and the temperature of treatment [280]. Further, two dealuminated
4.2. Post-synthesis aluminium incorporation zeolite Beta materials realuminated by NaAlO2 showed different ten-
dencies towards Al re-insertion in the framework. The material deal-
The in situ control of aluminium content and location in the zeolite uminated via calcination was realuminated by treatment in mild con-
framework is often challenging. Therefore, numerous studies, em- ditions, and the zeolite acidity was restored to the level of the initial
ploying different methods, have been devoted to the post-synthesis material. On the contrary, the sample dealuminated by acid leaching in
alumination of zeolites. Besides the possibility to introduce Al where HCl could be realuminated only in the presence of TEAOH at 150 °C for
the in situ method failed, the post-synthesis aluminantion is cost-effec- 5 days. The framework stability of the realuminated material was not
tive and provides the opportunities for achieving different Al location. improved with respect to dealuminated samples. In addition, this pro-
The level of Al insertion and the position it is going to occupy within the cess generated additional acid sites, mostly weaker than in the parent
zeolite lattice is related to the zeolite framework type, energetics of the sample [281]. Similarly, purely siliceous zeolite Beta was treated with
particular site and its environment as well as to the nature of the aluminium isopropoxide in dry hexane under a nitrogen atmosphere,
leaving T atom. Some materials have been attained only in all-silica and Al has been introduced into the zeolite framework. However, only a
form or in the presence of T atoms other than Al. Moreover, very often, part of tetrahedral Al atoms present in the aluminated samples is re-
such materials can be synthesized only within a limited range of Si/T lated to the Brønsted acid sites [282]. The same group also treated
ratio, where T is a heteroatom, or in the presence of specific OSDAs. dealuminated zeolite Beta with aluminium isopropoxide. They obtained
These heteroatoms, particularly Ge and B, were found to be more tetrahedral aluminium at framework position along with highly dis-
readily substituted with Al than the framework Si. B and Ge are easily torted extra-framework tetrahedral Al, which was attributed to an
hydrolyzed, which favors there substitution with Al. The following amorphous silica-alumina phase. Consequently, the concentration of
section presents an overview of the approaches applied to incorporate Brønsted acid sites has increased in the realuminated sample, yet it is
Al into zeolite materials via post-synthesis methods, including vapor associated with approximately 10 % of the total Al incorporated into
phase treatment by Al halides, solution mediated isomorphous sub- the sample [283].
stitution as well as by layered atomic deposition. Further, the Al co- Silicalite-2 (MEL-type) was stirred for 30 min at 60 °C in a solution
ordination, acidity of the materials, and the benefits attained by the containing sodium hydroxide, tetrabuthylammonium hydroxide, and
treatment are discussed. aluminium nitrate, the final SiO2/Al2O3 of the reaction mixtures was
Octahedrally and tetrahedrally coordinated Al atoms were in- 100 and 400. The obtained samples presented more Lewis than
troduced into the silicalite-1 sample (Si/Al > 400), which was exposed Brønsted acid sites revealing the formation of both framework and
to AlCl3 vapour at 400 °C. Pyridine adsorption indicates that the ma- extra-framework Al species in the course of the alumination treatment
terial possesses both Brønsted and Lewis sites [277]. Another study [284]. In MTH reaction, the aluminated MEL-type zeolites showed
devoted to the alumination of high-silica MFI-type material with
Fig. 19. Principle stages of the ALD process.

Reproduced with permission from [286].
19
tetrahedral. The remained 19 % of Al is assigned to distorted tetra-

hedral and pentacoordinated Al. Although a small quantity of the Al has
been incorporated into the framework, the material exhibited certain
Brønsted acidity. In addition, the annealing of the structure resulted in
the elimination of silanol groups, and thus the pore size widened from
7.2 to 7.9 Å. When modified with Pt nanoparticles, the ALD-COK-14
exhibits remarkable catalytic activity in n-decane hydroconversion in
comparison to totally inactive all-silica -COK-14. The marked catalytic
Fig. 20. Schematic representation of Ge substitution for Al in the BEC-type performance of ALD-material can be solely assigned to the Brønsted
framework. acid sites in spite of their low concentration [288]. Wet ball-milling in
Reproduced from [292] by permission of The Royal Society of Chemistry. the presence of aluminium isopropoxide was recently found as an al-
ternative route to stabilize OKO-type material by introducing Al to the
structure. In this case, octahedral Al is the prevailing (77 %) specie,
enhanced activity and catalyst lifetime than the Al-MEL-type materials
whereas 14 % of the Al is incorporated into tetrahedral positions. Once
prepared via the conventional zeolite synthesis route.
again, Brønsted acid sites were generated in the aluminated sample,
Martens et al. have introduced Al into ultra-stable zeolite Y, zeotile-
which is the basis for improved catalytic activity in n-decane hydro-
4 (ordered mesoporous silica material) and silicalite-1 by atomic
isomerization and hydrocracking with respect to ALD-COK-14. In n-
layered deposition (ALD) of Al(CH3)3 (Fig. 19) [285]. ALD is a tech-
decane hydroisomerization reaction remarkably high selectivity of
nique of thin-film deposition in two cycles where the substrate is ex-
skeletal isomers (72 %) was reached, uncommon for large pore zeolites
posed to metal compound vapour and subsequently to water vapour at
[289].
200 °C and 0.2 Pa base pressure. The authors pinpoint that the ad-
The alumination of non-calcined germanium-rich zeolite was used
vantages of ALD from a practical point of view in comparison to other
to stabilize the zeolite framework [290]. Micron-sized crystals of BEC-
methods are the automation and the rapidness of the treatment. The
type material with Si/Ge = 2.5 were subjected to a series of post-
materials obtained by this method comprised significant quantities of
synthesis treatments with polyaluminium hydroxide chloride solution
Al, yet there was a substantial fraction of extra-framework Al species. In
at 80 °C followed by the extraction of extra-framework Al with hy-
ALD-treated USY the number of Lewis acid sites remained unchanged,
drochloric acid (Fig. 20). The described procedure was repeated twice.
while the total number of Brønsted acid sites got enhanced. Considering
Germanium was partially substituted for aluminium, and only the
the high amount of EFAl in modified USY, the increase of the con-
peripheral part of the crystals was aluminated. The process included
centration of Brønsted sites has been attributed to bridging hydroxyls
partial OSDA extraction and incorporation of Al into Ge tetrahedral
bonded to distorted Al tetrahedra connected to the framework of
sites. The partial OSDA extraction is essential for the efficiency of the
oxygen atoms. In decane hydroconversion, the ALD-USY was active at
isomorphous substitution since the remaining molecules stabilize the
lower temperatures while the selectivity and product yields remained
structure. In order to induce alumination within the whole volume of
similar to the parent sample. Likewise, ALD-zeotile-4 material pre-
the crystals, nano-sized BEC-type material of Si/Ge 3.6 were employed
sented an increase in the number of acid sites and enhanced catalytic
and subjected to identical post-synthesis treatments as the micron-sized
activity in the n-decane hydroconversion reaction with respect to the
ones [291]. The chemical composition of the resulting material was as
non-modified sample. On the contrary, there was a small Al uptake and
follows: Si/Al = 30.8, Si/Ge = 6.7. Again the Al was incorporated into
low catalytic activity of ALD-silicalite-1, suggesting that the pore
the tetrahedral zeolite framework sites replacing the easily hydrolyzed
openings of the MFI framework are not large enough for transport of Al
Ge. The material preserved its crystallinity upon calcination at 600 °C
(CH3)3 [285].
and being exposed to 67 % humidity for a month, which demonstrated
Further, the ALD has been employed to deposit either Si either Al on
the significant enhancement of its hydrothermal stability [291].
the pillared MWW (PMWW or MCM-36) and pillared MFI (PMFI) zeo-
Germanosilicate ITH zeolite materials having Si/Ge = 2.5, 4.4, and
lites. The treatment reduced mesopore volume and preserved micro-
5.8 have been subjected to post-synthesis alumination with an aqueous
pores. In Si-ALD materials, Al exhibited a similar environment as in the
solution of Al(NO3)3 [293]. Upon alumination, the samples of Si/Ge =
initial materials, while in Al-ALD samples, additional Al coordination
2.5 and 4.4 presented strong Brønsted and Lewis acid sites as well as
was generated. The introduction of Si caused the reduction of the total
additional porosity, which was attributed to the extraction of Ge from
acidity and the number of external acid sites in both pillared materials.
D4Rs regularly arranged in the parent ITH materials. On the other
In MWW, the total acidity is higher after treatment with Al, yet the
hand, additional pores were not formed during the treatment of the
external acidity gets lower. In contrast, in pillared MFI material, both
zeolite possessing Si/Ge = 5.8. The authors found that the quantity of
total and external acidity got enhanced upon Al-ALD. The obtained
Al inserted into the ITH framework becomes higher as the Si/Ge ratio of
materials were tested in ethanol dehydration, alkylation of benzyl al-
the initial material is decreasing. This effect is related to a higher
cohol in mesitylene, and direct methane aromatization reactions. The
fraction of Ge–O(Si) bonds prone to hydrolysis, which generates defects
set of experiments showed that the intrinsic catalytic behavior of
that are subsequently condensed with Al. Moreover, the increase of the
Brønsted acid sites in PMWW and PMFI was not altered significantly by
pore size due to the Ge–O(Si) bonds hydrolysis facilitates the avail-
the ALD treatment. However, a certain selectivity of external acid sites
ability of the formed vacancies for Al incorporation. Furthermore, rising
in the alkylation reaction of benzyl alcohol with mesitylene was es-
the alumination temperature from 80 to 175 °C leads to the formation
tablished [287].
of 1.5–2-fold higher number of Brønsted acid sites and a lower quantity
Using the same technique, the group from Leuven introduced Al by
of framework Al accessible to pyridine and 2,6-ditert-butylpyridine
ALD into all-silica large pore OKO-type material denoted as -COK-14
probe molecules. Aluminated ITH zeolites exhibited catalytic activity in
[288]. The hyphen denotes an interrupted structure which is stable at
the reaction of tetrahydropyranylation of alcohols while the parent
room temperature under standard humidity conditions. The fully con-
materials containing a small concentration of Lewis sites were almost
nected OKO framework can be attained upon heating the all-silica
completely inactive. What’s more, solely aimed tetrahydropyranyl
-COK-14 material at a minimal temperature of 300 °C and remains
ethers were detected as the products in the studied reaction over the Al-
stable in the absence of moisture (COK-14). On the other hand, the
ITH materials. Since the lower activity was measured when the size of
ALD-COK-14 material was found to preserve the structure upon storage
the substrate alcohol molecule grew larger, the authors point out that,
of 6 months under ambient conditions. 60 % of Al introduced into the
in order to evaluate the catalytic activity of the studied zeolites, is
modified -COK-14 has octahedral coordination and only 21 %
necessary to take into consideration the total concentration of the
20
accessible acid sites [293]. ring zeolite Al-SSZ-56 implies similar transition state selectivities in
The UTL-type framework can be represented as dense 2D layers these materials, which potentially comes from the increased fraction of
connected by D4R. In germanosilicate materials possessing this frame- the Al sites at the intersections of 10- and 12MRs [298]. Zones at al.
work, Ge preferentially occupies the positions in D4Rs [294]. The further extended this work by performing a comprehensive investiga-
tendency of germanium for hydrolysis has been the basis of the ADOR tion of a series of borosilicate zeolite materials (SSZ-33, SSZ-57, SSZ-70,
(assembly-disassembly-organization-reassembly) method of zeolite SSZ-56, SSZ-82, SSZ-24, MEL, Beta) of various framework types pos-
synthesis employing UTL-type materials as starting materials. A series sessing intersecting channels of 10- and 12-membered ring channels
of materials (IPC materials) comprising the same 2D layers yet bridged treated with Al(NO3)3 solution [299]. It was found that the first step of
by different linking units has been prepared in this way. Al-IPC (IPC-2, Al insertion into a nest “vacancy” is the boron hydrolysis away from the
IPC-4, IPC-6, IPC-7) materials have been prepared by the treatment of lattice. The process of boron leaving is faster than Al incorporation.
calcined UTL and Al-UTL materials with the solution of Al(NO3)3, in NMR analysis shows that the Al is introduced in tetrahedral sites where
certain cases in the presence of acetic acid. All Al-IPC materials pre- the boron was located. Besides, different degree of alumination for the
sented similar and significantly higher amounts of Brønsted and Lewis studied materials was connected to the higher B occupancy of 4MR
acid sites than the Al-UTL material. Besides, 27Al NMR indicates there is positions. Likewise, more boron in the initial zeolite enables achieving
a certain amount of extra-framework Al entities in the studied samples. higher final Al content since, in this case, a more significant number of
Still, these materials exhibited notably different acid sites distribution B atoms is located in T sites where isomorphous substitution is viable
due to the differences in the channel systems of respective frameworks. [299].
Consequently, their performance in the tetrahydropyranylation of
bulky 1-decanol changed as a function of the concentration of “ex-
4.3. Al zoning
ternal” acid sites. It was found that as the concentration of “external”
acid sites becomes higher, the activity of Al-IPC materials in the cata-
Aluminium zoning, i.e., the non-uniform distribution of Al atoms
lyzed reaction is enhanced [294]. In addition, Al was incorporated in
throughout the zeolite crystal, was reported by many researchers [300].
Ge-containing IPC-2, OKO-type material. The approach involves the
For instance, the spatial distribution of aluminum over ZSM-5 crystals
preparation of the layered zeolite precursor by acid hydrolysis of Ge-
was studied using electron microprobing on large polished crystals
UTL material and subsequent hydrothermal treatment of the layered
[301]. In the crystals prepared from the reaction mixture where TPABr
material with aluminium butoxide in nitric acid solution at 175 °C. The
plays the role of the OSDA, Al was concentrated in the crystal rim no
presence of both types of acid sites, i.e. Brønsted and Lewis, indicates
matter the initial Al source chemical used. However, the distribution
that Al was only partially introduced into the framework and there are
profile was less inhomogeneous in the systems where a source chemical
EFAl species [295].
possessing organic functional groups bonded to Al was used. In con-
Germanium containing AFI-type zeolite material of Si/Ge = 8.1 was
trast, in the case of 1,6-hexanediol and OSDA-free synthesis mixtures,
subjected to de-germanation with HCl prior to the alumination with the
crystals with homogeneous aluminium profiles were prepared, while
solution of Al(NO3)3 at 80 °C. The Al introduction did not affect the
the addition of KNO3 to the 1,6-hexanediol system leads to an in-
crystalline structure of the parent materials, yet the material which was
homogeneous Al profile. The authors postulate the difference in the Al
firstly de-germanated showed enhanced Al uptake, increased pore-vo-
spatial distribution arises from the interactions between the cations and
lume, as well as the higher concentration and strength of both Brønsted
(alumino)silicate species. Namely, inorganic cations preferably interact
and Lewis acid sites in comparison to the solely aluminated material.
with aluminosilicate species, and thus in the 1,6-hexanediol or in-
The benefits of the de-germanation step preceding Al treatment are
organic systems, the Al is built into the crystals from the early stage of
attributed to the creation of hydroxyl nests by removal of germaniun
the reaction since Na+ induces the structure formation. Accordingly, in
atoms from the framework, which are more prone to Al incorporation.
the presence of inorganic cations, TPA+ primarily interacts with the
In alkylation of toluene with isopropyl alcohol, the AFI-type material
silicate species resulting in the Si-rich core MFI-type material with Al
modified by two steps procedure exhibited relatively high toluene
incorporated in the later stage of the crystal growth.
conversion and selectivity to valuable p-cymene than the catalysts
EDX mapping of ZSM-5 crystals (bulk Si/Al = 34) displayed in
usually used for this reaction such as zeolites Beta and MTW [296].
Fig. 21 obtained from a reaction mixture of sodium hydroxide, sodium
As-prepared boron-containing zeolite Beta treated with 1 mol dm−3
solution of Al(NO3)3 at 170 °C was almost entirely aluminated in seven
days. NMR data show a decrease of the peak intensity at -11 ppm in 11B
MAS NMR spectrum simultaneously with the increase of the peak cor-
responding to tetrahedral Al in 27Al MAS NMR spectrum indicating the
B removal from the BEA framework for Al. It was concluded this iso-
morphous substitution is a thermally activated process comprising three
steps: 1) aluminium insertion in the defect sites near the crystal surface;
2) slow substitution of B by Al in the bulk of the crystals; 3) faster B
exchange for Al due to the formation of mesopores in the crystals [297].
B-SSZ-57 (*SFV-type material) contains mostly intersecting inter-
mediate pore channels (10MRs) and a minor area of large pores
(12MRs). Boron was selectively substituted in the SSZ-57 framework
with aluminium in the large pore region upon treating with the solution
of aluminium nitrate. Accordingly, strong Brønsted acid sites were
created exclusively in the large pore areas of the zeolite. On the other
hand, the Al insertion into B-ZSM-11 with similar 10MRs lattice fea-
tures was not successful [298]. The alumination of the 12MRs regions
in SSZ-57 was substantiated by the constraint index test of n-hexane
and 3-methylpentane cracking, as well as the isomerization and dis-
proportionation of 1,3-diethylbenzene. Furthermore, the fact that in Fig. 21. (a) Scanning electron micrograph of the ZSM-5 crystal and EDX maps
hydroisomerization of n-hexane the Pd-modified aluminated SSZ-57 corresponding to (b) aluminum, (c) silicon, and (d) oxygen. Reprinted with
presents similar product selectivities as does the Pd-modified 10-/12- permission from reference [38]. Copyright (2010) American Chemical Society.
21
acid strength and hydrothermal stability than the aluminium countr-

parts. Other elements such as Ti, Sn, Ge, Zr, Hf, Mo, Nb, W and Ta
induce Lewis acid character of the zeolite framework sites that they
occupy. In general these materials present higher hydrothermal stabi-
lity and hydrophobicity than the respective Al-counterparts. Moreover,
the heteroatoms present in the zeolite framework alongside Al impact
the overall acidity of the material and might display a cooperative ef-
fect on its final preformace. Further in text are demonstrated examples
how the heteroatoms, both in the presence and absence of framework
Al contribute in designing zeolites of novel acidic properties thus ex-
panding the extent of (potential) zeolite applications.
4.4.1. Boron-containing zeolites

Boron is rather easy to get incorporated into zeolite framework sites,
and thus, there are many examples where it was employed for the en-
gineering of zeolite acidity. Quantum chemical calculations reveal that
the energy difference between the most and least stable Al sitting in the
MFI framework is lower than 9 kcal/mol [303]. Contrarily, boron un-
doubtedly exhibits thermodynamic preference to be located at the T6
position at the channels’ intersection, followed by T10 in the sinusoidal
10MR channel [304]. It seems that boron is more stable at T sites with
shorter SieSi distances, in agreement with the smaller dimensions of
the BO4 tetrahedra in comparison to AlO4. The preferred boron occu-
pation of T6 and T10 sites is retained in mixed Al-B-ZSM-5 models in
which two Al and two B atoms are placed at the same T position, di-
Fig. 22. X-rays diffraction intensity maps and time-of-flight secondary ion mass recting the location of Al into the 10MR channels of the MFI lattice.
spectrometry sputter-depth profiling analysis of a single ZSM-5 crystal inside This premise was confirmed experimentally. A series of B-ZSM-5, Al-
orientation demonstrating the Al zoning. (a) Crystal lattice parameter a plotted ZSM-5 and Al-B-ZSM-5 samples having different compositions were
against the short crystal coordinate (20 μm). (b) Estimated Si/Al ratio within prepared from synthesis gels of varied Al and B content [304]. The
the zeolite ZSM-5 crystal as a function of increasing sputter depth. (c) 3D re- boron species extracted from the framework during calcination have
presentation of the depth profiles of Si+ and Al+ secondary ions versus sputter been washed with the NH4NO3 solution. In the cases when Si/(Al +
time.
B) < 24 there is competitive incorporation of Al and B at the available
positions. All Al present in the synthesis gel is incorpotated into the
zeolite framework, while just a fraction of the B is inserted in the MFI
aluminate, silica sol, and tetrapropylammonium bromide revealed the structure. Nevertheless, the Co2+-exchange experiments show the
preferential location of Al in the rim of the crystals [38]. Furthermore, sample of Si/Al = 46 and Si/B = 82 presented a higher quantity of
crystallographical mapping displayed in Fig. 22 confirmed differences paired Al sites compared to the corresponding Al-ZSM-5 sample having
in the aluminium concentration within the studied single ZSM-5 crystal Si/Al = 44 (Table 5). Most probably, the Al atoms get incorporated in
[39]. Similar zoning of Al has been also observed in ZSM-5 crystals the closer framework positions because of the effect of boron already
having different size taken at various stages of synthesis. The authors presents within the framework. Besides, the amount of paired Al sites in
concluded that the presence of majority of catalytically active sites at the straight 10MR channels is higher in the B-containing sample. Ac-
the shell of the ZSM-5 crystals arises from the Al deposition during the cordingly, the result of the 1-hexene cracking test reaction gives a
cooling of the synthesis mixture. Recently Li et al. reported that the higher ratio of mono- to bimolecular cracking for the Al-B-ZSM-5 cat-
level of Al zoning within the crystals becomes higher with the ZSM-5 alyst denoting a more significant relative population of Al active sites
synthesis advancement. Owing to structural rearrangement in the al- located within the 10MR channels, i.e., boron favours channels inter-
kaline reaction medium, the Al migrates towards the rim of the crystals. section positions when competing with Al. In methanol to propene
Besides, it was found that the alumosilicate species of high Al content process, this Al-B-ZSM-5 sample showed higher propene selectivity,
are deposited on the growing MFI crystals in the late stage of the re- lower aromatics, and alkanes selectivity and longer catalyst lifetime
action [302]. than the materials prepared without the assistance of boron [304].
On the contrary, homogeneous distribution of Al has been reported In the case of MFI synthesis systems where TPA and Si/Al ratio were
for coffin-shaped large ZSM-5 crystals having a Si/Al ratio of 17 syn-
thesized from Ludox AS-40, tetrapropylammonium bromide, alumi- Table 5
nium sulphate, and ammonia [44]. The statistical Results of Co2+-exchange experiments on different ZSM-5 samples synthesized
analysis of atom probe tomography data had shown that Al atoms with and without boron added to the crystallization media. Reprinted (adapted)
are uniformly distributed in the ZSM-5 crystals with the most probable with permission from reference [304]. Copyright (2018) American Chemical
Al–Al neighbour distance of 18 ± 6 Å, an average Al density of 0.025 Society.
atoms nm−3. Hence, it can be concluded that the synthesis conditions Sample Compositiona Co-exchange experiment
markedly affect the Al distribution within the zeolite crystal.
Si/Al Si/B Alisolb Alpairc Alαd Alβd Alγd
4.4. Controlling the zeolite acidity by incorporating heteroatoms in the Z5-50 44 – 45 % 55 % 32 % 65 % 3%

Z5-50-B1 46 82 30% 70 % 45 % 55 % <1 %
zeolite framework
a
Measured by ICP-AES.
The incorporation of heteroatoms into zeolite frameworks re- b
Calculated according to equation n(Alisol)=n(Altotal)-n(Alpair).
presents another avenue in tuning their acidity. The framework T3+ c
n(Alpair)= n(Co2+).
atoms as B, In, Fe, Ga, provide Brønsted acidity, yet with much lower d
Measured by deconvolution of UV–vis spectra of dehydrated ZSM-5.
22
kept constant (≈ 50) and B content varied, 20–40 % of Al sites were

paired, independently on the boron quantity added [305]. On the other
hand, in analogous experiments where a mixture of tetra-
propylammonium cations and ethylenediamine (EDA) is used as OSDA,
the obtained B-Al-MFI zeolites contain less than 5 % of Al in paired
configurations, irrespectively of the Si/B ratio. Herein, in the systems
with solely TPA+, one TPA+ moiety gets confined per one channel
intersection of the MFI framework while in the crystals formed with
EDA/TPA+ = 15 and n(Si) > n(TPA+) there is one TPA+ per two MFI
channel intersections. EDA is located within the voids not occupied by
TPA+, and as the B content increases, the EDA-B complexes build two B
atoms per EDA molecule in the MFI framework. First-order rate con-
stants of methanol dehydration to dimethylether over B-Al-MFI indicate
acid sites are confined within smaller voids. Given this, the Al dis-
tribution within the zeolite framework is directed by the widespread
impact of the organic molecules over the boron atoms present within
the synthesis mixture [305].
The boron-containing zeolite Beta materials were prepared in the
presence of seeds (Si/B = 4–38; Si/Al = 170–90). The addition of boric
acid in the reaction mixture affected the morphology and the size of the
crystals compared to the seed crystals. When compared to the Al-BEA
sample, the addition of B exhibited two different sites. Namely, boron Fig. 23. 27Al MQMAS NMR spectra of [Al,B]−CON zeolite materials prepared
assumes both tetrahedral and trigonal coordination in the BEA@BAB by direct synthesis under (a, b) static (Si/Al = 106 and 196) and (c) tumbling
framework. Trigonal B coordination is related to the weak Brønsted conditions (Si/Al = 134) and (d) the material prepared by post-synthesis
acid sites, while the tetrahedral coordination offered Lewis acid sites. treatment (Si/Al = 87).
Lowering the boron content in the synthesis gel led to a reduced amount Reprinted with permission from reference [308]. Copyright (2015) American
Chemical Society.
of boron of trigonal coordination while the amount of B in tetrahedral
coordination remained the same. The B-samples possessed fewer
Brønsted acid sites, more Lewis acid sites, and an increased fraction of high propene selectivity, low ethene selectivity, and a very long cata-
weak acid sites than the Al-BEA material. The catalyst with the highest lytic life compared to Beta and ZSM-5 zeolite in methanol to olefins
Si/B ratio of 6 was the most active and stable in the methanol to olefins (MTO) reaction. Further, it was surmised that in the sample with Si/Al
reaction. It reached the highest propylene selectivity of 60 %, together ratio of 87 prepared by post-synthesis alumination, aluminium occu-
with the highest propylene/ethylene ratio of 7 [306]. pied the 12MR positions as it showed higher heavy compounds se-
Al- and B-containing AEI-type zeolite materials have been synthe- lectivities and the lower propene selectivity [308]. This conclusion is in
sized from commercial FAU zeolite by using tetraethylphosphonium line with the report of Zones et al. on the SSZ-57 treatment with Al
hydroxide (TEPOH) as OSDA. Solid-state NMR and FT-IR confirmed the [299].
incorporation of B into the lattice. The samples having Si/Al = 13 and
Si/B = 260 displayed a lower quantity of Brønsted acid sites derived
from framework Al species compared to the boron-free AEI sample of 4.4.2. Germanium-containing zeolites
Si/Al = 11. Yet, the strength of Al acid sites is not affected by the The positions of Brønsted acid sites in Al-ITQ-21 of a range of (Si +
presence of boron in the framework. Accordingly, in B,Al-AEI material, Ge)/Al ratios have been evaluated by comparing them with Al-free ITQ-
there are Brønsted acid sites related to framework B species, which are 21 [309]. The materials were prepared using N(16)-methylsparteinium
weaker than Al-derived acid sites [307]. B,Al-AEI zeolite sample has cations as OSDA with varying amounts of added aluminium isoprop-
improved catalytic lifetime in the ethene conversion reaction with re- oxide. Germanosilicate ITQ-21 has no Brønsted acid sites, while in Al-
spect to B-free material due to the decreased amount of the strong acid ITQ-21, the Brønsted sites are generated due to the isomorphic sub-
sites. Besides, it exhibits high selectivity to butenes. Suppressing the stitution of Si by Al. The quantity of Brønsted acid sites is nearly pro-
successive reactions of butenes such as their cracking represents an- portional to the Al concentration in Al-ITQ-21 material. Almost all of
other benefit brought about by the introduction of B in the zeolite the Al atoms occupied T positions in the Al-ITQ-21 for the samples
framework, thus lowering the acid site density. Another study reports having (Si + Ge)/Al higher than 25. There are three distinct T positions
the preparation of the CON framework-type zeolite materials (Si/B = in the ITQ-21 structure. Germanium has a preference for the T1 site,
22–37; Si/Al = 87–196) by post-synthesis and the direct-synthesis while the Al atoms mainly occupied T1 positions at high (Si + Ge)/Al
methods [308]. The post-synthesis method involves the deboronation of and then began to populate T2 positions when (Si + Ge)/Al became
B-CON sample and subsequent alumination. In the direct synthesis lower than 44. Moreover, an increase of the Al amount in Al-ITQ-21
method, B-BEA@BAB seeds were added to the reaction mixture com- induced the generation of two different kinds of acidic protons, i.e.,
prising boric acid, aluminum sulfate, sodium hydroxide, fumed silica, Brønsted acid sites. The acidic protons are preferentially generated on
and N,N,N-trimethyl-(−)-cis-myrtanylammonium hydroxide O1 by occupying T1 positions with Al when the Al concentration of Al-
(TMMAOH). There is a substantial difference between the in situ and ITQ-21 is low and are successively generated on O3 by occupying T2
post-synthesis- aluminated CON-type samples in terms of the environ- positions with Al when the Al concentration increases. It was reported
ment of Al species. Moreover, as indicated by the 27Al MQMAS NMR that n-heptane conversion over investigated Al-ITQ-21 samples pro-
spectra in Fig. 23, there is a marked difference in the Al distribution ceeds by parallel isomerization and cracking reactions. As the Al
among the samples prepared in situ under the static and tumbling amount in the materials increased, the selectivity for cracking was
conditions. Besides, the sample prepared by the post-synthesis method lower while the isomerisation selectivity rose. The catalytic activities
has a higher quantity of Lewis acid sites as well as a slightly higher for both isomerization and cracking of n-heptane for acidic protons
amount of defect sites than the directly prepared CON-type material. bonded to O3 atoms in Al-ITQ- 21 were higher than those for acidic
Consequently, CON-type aluminosilicate zeolites prepared directly protons at O1 atoms [309].
under the tumbling conditions (Si/B = 26; Si/Al = 134) exhibited a
23
Fig. 24. Examples of Sn sites in Sn-BEA zeolite: (A) tetrahedral closed Sn site and (B) a partially hydroxylated open Sn site according to the definition in [316].
4.4.3. Tin-containing zeolites ethylbenzene oxidation it showed almost two times higher turnover
Tin-containing zeolite materials were included in the present review number than did TS-1 [330]. This research group also successfully
to demonstrate the possibilities offered by the Lewis acidity in zeolites. obtained Sn-Beta zeolite. Yet, Al was present both in the reaction
The presence of Sn in the framework of crystalline microporous solids mixture and in the end products. These Sn-Beta materials were found to
generates Lewis acidity since the σ∗ orbitals of the SneO cluster can be functioning catalysts in the acetylation of 1,3,5-trimethylbenzene
accept the electron density of the substrate and thus enable the onset of (1,3,5-TMB) with acetyl chloride and in the m-cresol and 1,3,5-TMB
the catalytic process. Sn-containing zeolites have shown to be ex- oxidation with H2O2 where their activity depended on the amount of Al
ceptionally active and selective Lewis-acid catalysts. They are arguably in the sample [331]. A giant leap in the field occurred with the work of
one of the best water-resistant heterogeneous catalysts for liquid-phase Corma et al. where was reported direct preparation of highly crystalline
catalysis. Sn-containing zeolites are employed in reactions of oxyge- Al-free as well as defect-free Sn-Beta zeolite of Si/Sn ratio 125 in the
nated reactants, which are of particular importance in fine chemistry fluoride-containing system using dealuminated nanosized zeolite Beta
and biomass valorization processes (e.g. Baeyer-Villiger (BV) oxidation, seeds [310]. 119Sn MAS NMR indicated the presence of tetrahedrally
Meerwein-Ponndorf-Verley (MPV) reaction, Diels-Alder reaction, aldol coordinated Sn, suggesting that Sn is built into the zeolite framework.
condensation, ring-opening of epoxides [310–315]), whereas the most The material showed a remarkable selectivity in BV oxidation of di-
important chemicals that can be produced using Sn-zeolites are glucose hydrocarvone, a molecule containing ketone group along with a double
isomers and epimers, 5-(hydroxymethyl)furfural (5-HMF), lactates, le- bond, which is prone to react with an oxidizing agent forming a range
vulinates, ε-caprolactones, nopol, catechol, γ-valerolactone, etc. of products. Sn-Beta yielded the target lactone circumventing the
Similar to the other heteroatoms-containing zeolitic materials, var- double bond oxidation. This work paved the way for a plethora of
ious types of active sites may be generated when Sn is introduced into studies both in terms of incorporating Sn into various zeolite lattices
zeolite framework. Closed sites correspond to Sn incorporated into the and exploring the catalytic activity of Sn-zeolites in numerous reac-
framework as a fully coordinated distorted tetrahedron (Sn(SiO)4). In tions. A selection of these studies is presented in the following section.
contrast, open sites refer to partially hydrolyzed tin located within the in situ insertion of Sn into the zeolite framework connotes the pre-
zeolite framework ((SiO)3SnOH, Fig. 24) [316]. It was found that the sence of the Sn species in the starting reaction mixture before zeolite
interconversion between open and closed Sn sites can take place and material is formed. A rather long synthesis period of Sn-zeolites, as well
might have an impact on the catalyst’s reactivity [317]. In the reaction as the usage of fluorides in many systems, represent the most significant
of glucose isomerization to fructose, glucose epimerization to mannose, impediments to their large-scale production. For instance, the synthesis
BV oxidation as well as in MPV reduction, the open Sn sites were in the work of Corma takes 20 days at 140 °C in a tumbling oven [332].
proposed as the active sites [312,316,318] while in ethanol dehydra- The data suggest that the zeolite crystallization kinetics is retarded
tion to diethylether the closed sites seem to be the most relevant for the when Sn is present in the initial synthesis mixture [333]. An extensive
reaction [319]. It should be noted that generally, under ambient con- study of Sn-Beta crystallization in the fluoride medium found that it is a
ditions, Sn sites possess distorted octahedral coordination since they are function of the type and quantity of tin source added to the initial re-
hydrated with two water molecules [320]. In addition, extra-framework action mixture [334]. Increasing the tin loading required a longer
SnO2 moieties can be deposited on the material or within the zeolite period to obtain a material of high crystallinity, e.g., at Si/Sn = 100
pores. There is an interesting example of glucose isomerization where with SnCl4·5H2O it took 60 days to reach fully crystalline material.
extra-framework SnO2 clusters located within the zeolite Beta channels Further, zeolite Sn-Beta crystals grew larger as the Sn amount
act as catalytically active sites, whereas bulk SnO2 displays any activity
[320,321].
The first attempt to introduce Sn into a zeolite framework concerns
the addition of SnCl4 to the silicalite-1 synthesis mixture as early as in
1976 [322]. Later on, both in situ and post-synthesis approaches have
been attempted to introduce tin efficiently in a zeolite [323–328]. Still,
not until the work of Mal et al. was confirmed the embedding of Sn in
the zeolite framework [329]. In the latter study, SnCl4 was directly
added to TEOS, water, and TPAOH were subsequently admixed. The
unit cell volumes of the prepared materials increased with the tin
content in the sample. Further, the TeOeT lattice vibrations wave- Fig. 25. Sn distribution based on SEM wavelength dispersive spectrometry
numbers are shifted towards lower values in the samples of higher Sn analysis of the cross-sections of Sn-Beta zeolites with Si/Sn ratios of (a) 400, (b)
content. The obtained Sn-MFI material was a comparably active cata- 200, and (c) 100.
lyst to TS-1 in the phenol hydroxylation reaction, whereas for the Reproduced from Ref. [334] with permission from The Royal Society of
Chemistry.
24
increased, whereas the pyramidal faces shrank, and the pinacoidal ones
became the dominant crystal feature. No matter the Si/Sn ratio, all of
the crystals analyzed by SEM wavelength dispersive spectrometry ex-
hibit Sn zoning with Sn located in the rim of the crystals, as displayed in
Fig. 25. In the reaction of conversion of dihydroxyacetone to methyl
lactate the Sn-Beta of Si/Sn = 150 exhibited the highest activity for the
samples, which are prepared for a rather short time, yet show high
crystallinity [334]. Clearly, the addition of Sn to the zeolite synthesis
mixture substantially alters the crystallization process. Thus various
resourceful approaches were scrutinized in order to achieve the Sn
anchoring to zeolite structure and control of the end product properties
at the same time trying to reduce the preparation period.
Nearly identical reaction mixture as in Corma’s work yielded
Sn‐Beta zeolite material of Si/Sn = 96 (140 °C, 40 days, static condi-
tions) [321]. When added to a 10 wt% glucose water solution, the Sn-
Beta produced a mixture containing glucose (46 wt%), fructose (31 wt
%), and mannose (9 wt%). The same reactivity was observed after three
repeated cycles, as well as in the case of 45 wt% glucose solution.
Noteworthy, the material was active at pH = 2. Under the same con-
ditions, any isomerisation activity was found neither for bulk SnO2 nor
SnCl4·5H2O suggesting that in the studied process, the active species are
the Sn sites integrated within the zeolite framework [321].
A relatively short synthesis time of Sn-containing zeolite Beta (Si/Sn Fig. 26. FT-IR spectra in the hydroxyl stretching vibration region for (a) parent
= 63) was achieved by the interzeolite conversion of ITQ-1 (all-silica zeolite H-Beta and its derivatives: (b) zeolite Beta calcined at 823 K for 30 min;
(c) calcined zeolite Beta treated with HNO3; and (d) Sn-Beta (Si/Sn = 83)
MWW-type zeolite) in the presence of dealuminated zeolite Beta seeds,
prepared from the calcined and HNO3 treated zeolite Beta.
TEAOH and NH4F [335]. Here solely isolated tetrahedral Sn was ob-
served by XPS and UV/Vis spectroscopy. The high catalytic activity of
the material in the Baeyer-Villiger oxidation of 2-adamantanone with
H2O2 was attributed to rather high Sn framework content and small six-coordinated tin species or small SnO2 clusters beside the framework
crystal size. The hydrothermal treatment of the NaOH-TPAOH-SiO2 Sn atoms. In the toluene alkylation with tert-butyl alcohol reaction, the
system with an added solution of SnCl4 and EDTA with citrate buffer p-tert-butyltoluene selectivity is higher for Sn-Al-MOR catalysts than
represents another efficient approach for the in situ insertion of Sn in that for Al-MOR of Si/Al = 9. Moreover, MOR catalyst having Si/Sn =
the zeolite framework [336]. Al was added to some of the reaction 182 retained its catalytic activity upon five consecutive cycles [339].
mixtures, and thus Sn-MFI materials of Si/Sn ranging from 122 to 69 Sn-CHA was prepared using TEOS, SnCl4·5H2O, and TMADAOH in
and Sn-Al-MFI materials having Si/Sn ≈ 90 and Si/Al in the range the presence of H2O2. The ethanol released from TEOS and the excess
240–80 were prepared. Based on the XPS and UV/Vis data, the authors water in the solution were evaporated until H2O/SiO2 = 3. The almost
conclude that in the studied series of the samples, Sn occupies only dry powder was dispersed in water and again dehydrated until reaching
tetrahedral positions within the zeolite framework. IR spectra of pyr- the H2O/SiO2 ratio of 3, mixed with HF, and heated at 150 °C (48 h,
idine adsorbed on the materials reveal the presence of Lewis sites in the rotation). If the dehydration steps are omitted, any crystalline material
Sn-MFI materials and both the Brønsted and Lewis acid sites in Sn-Al- is formed up to 10 days of hydrothermal treatment [340]. 119Sn NMR
MFI samples, as corroborated by 31P NMR spectra of adsorbed TMPO data (Fig. 26) combined with DFT models suggest that the closed Sn
probe molecule. Both types of materials are comparably active catalysts sites in dehydrated material become hydrated hydrolysed open sites
in the conversion of 1,3-dihydroxylacetone to methyl lactate, the BV upon the exposure to a water-containing environment. Thus prepared
oxidation of cyclopentanone, and the aldol condensation reaction be- Sn-CHA displays significant catalytic activity in the reactions of MPV
tween furfural and acetone which indicate that Brønsted acid sites are reductions of propionaldehyde, Oppenauer oxidation of ethanol, and
beneficial in these reactions. Still, there is an optimal Al amount, which glucose isomerization. Still, Sn-Beta is a more active catalyst, especially
is advantageous for achieving desired product selectivity. in the isomerization of glucose, where the turnover rates are four orders
Sn introduced by in situ synthesis into a series of porous materials of magnitude higher than on Sn-CHA. The observed performance of Sn-
(SBA-15, Beta, and MFI-type) was evaluated for its catalytic activity in CHA is attributed to the distinctive transport limitations in these ma-
the epichlorohydrin epoxide ring-opening. Sn-Beta by far exceeded Sn- terials.
SBA while Sn-MFI performed slightly inferiorly. Besides, the Sn-Beta As already mentioned, the properties of Sn-containing zeolites are
zeolite performed similarly after three cycles [315]. Worth reporting, susceptible to the Sn source and the mode it is added to the reaction
the Zr- and Hf-containing Beta zeolites exhibit certain activity in the mixture. Some of the proposed synthetic routes concern where the
studied reaction, but 6 and 7 times less than does Sn-Beta. The in situ bonds SieOeSn exist prior to the hydrothermal treatment as achieved
preparation of nanosized Sn-zeolites was the extension of this work in by milling or preparing xerogels [323,341]. Further, one should bear in
terms of the substrate size. Namely, nanosized Sn-MFI (Si/Sn = 200) mind that Na in the zeolite MFI synthesis mixture may limit the
and Sn-Beta (Si/Sn = 170) exceeded the catalytic activity of corre- quantity of Sn built into the framework and that at pH below 12, so-
sponding Sn-zeolite materials with larger crystals in the reactions of dium stannate impurity gets formed on the surface of the crystals [342].
1,2-epoxyhexane with methanol and 1,2-epoxyoctane with ethanol, Indeed, numerous parameters affect Sn and Si behavior under hydro-
respectively [337,338]. thermal conditions, and thus it is necessary to continue pursuing the
A series of Sn-Al-MOR samples with Si/Sn in the range ∞–143 and goal to produce (new) materials of improved properties/performance.
Si/Al = 12–9 was prepared in the presence of 1-butyl-3-methylimida- An alternative avenue to Sn-containing zeolite catalysts is the post-
zolium bromide. UV/Vis spectra indicated the insertion of Sn in the synthesis tin incorporation. Different Sn compounds in solid, solution,
zeolite framework, although the Si/Sn ratio as low as 455 was obtained or vapor form were explored to introduce Sn in zeolite structures. The
for the initial system with the lowest Sn quantity. The MOR materials post-synthesis treatment can be executed with conventional laboratory
originating from the systems with higher initial Sn content presented equipment and usually requires shorter treatment time with respect to
25
the in situ synthesis. The degree of introduced Sn, as well as its location, by nitric acid resulted in 90 % of Al removed and substantial reduction
are related to zeolite framework type, presence of defect sites, and the of material’s crystallinity [347]. Two post-synthesis routes were un-
tin source, i.e., susceptibility/availability of Sn atoms to react with the dertaken in order to introduce Sn into zeolite framework: 1) refluxing
zeolite. In the following section are going to be addressed different with SnCl4 in isopropanol and 2) adding trimethylamine to the SnCl4
methods developed to conduct post-synthesis stannation of zeolites, the solution in acetone and dichloromethane. The obtained materials
types of generated Sn sites as well as the catalytic efficiency of the comprised 1–2.2 wt% of tin. The features in the UV/Vis spectra of the
prepared materials. samples prepared in isopropanol show the presence of Sn with co-
A series of nanosized dealuminated commercial zeolite Beta samples ordination number higher than four implying there are extra-frame-
were exposed to SnCl4 vapors at 200–600 °C. The samples treated at work Sn species together with SnO2 domains. On the other hand, the
400 and 500 °C present the lowest Si/Sn ratio of 35 and 36, respec- UV/Vis spectra of the trimethylamine-derived zeolite suggest a low
tively. Herein, Sn occupies tetrahedral framework positions according abundance of extra-framework Sn species. Besides Lewis acid sites,
to the 119Sn MAS NMR results. Further, the IR spectrum of the adsorbed which should originate from Sn, a noteworthy quantity of Brønsted acid
pyridine indicates the presence of Lewis acid sites solely. The decreased sited was observed and ascribed to Al, which remained after the deal-
intensity of the silanol nests band at 3500 cm−1 in the IR spectrum of umination. Such samples were poor catalysts with poor selectivity in
the Sn-Beta samples together with the decrease of the Q3 resonance at methyl lactate synthesis from glucose solutions in methanol. Namely, a
-103 ppm in the corresponding 29Si MAS NMR spectra supports the variety of products was formed due to several reactions pathways
conclusion that the mechanism of the Sn incorporation occurs through through which the glucose undergoes because both Brønsted and Lewis
the reaction with SiOH groups in the hydroxyl nests, thus healing the acid sites take part in the processes. However, the trimethylamine-de-
framework defects [343]. The nanosized Sn-Beta obtained herein out- rived materials that were ion-exchanged with the alkali cations ex-
performs the conventional Sn-Beta prepared in fluoride medium in the hibited switched products’ selectivities with methyl lactate being the
Baeyer-Villiger oxidation of 2-adamantanone. The same research group main product and thus suggesting the retro-aldol reaction pathways
applied the modification procedure by SnCl4 vapors on the zeolite Beta become dominant. The Na+ and K+ have double-action – suppressing
prepared via a seeded synthesis route in the caustic medium [344]. The of the Brønsted sites and enhancing the catalytic activity of Sn species
Sn was found to be exclusively in tetrahedral positions, and the me- in retro-aldol reaction through the interaction with the Sn sites [347].
chanism of Sn incorporation was attributed to the healing of silanol The promotion effect of Na+ and K+ on the epimerization and retro-
nests defect sites as supported by the IR spectra analysis shown in aldol reactions was observed on Sn-Beta zeolites as well [312,348].
Fig. 26. The material outpassed Sn-Beta obtained by the fluoride-as- In order to obtain Sn-MWW zeolite material, as-prepared B-MWW
sisted method in the BV oxidation of 2-adamantanone. zeolite was deboronated with nitric acid and subsequently treated with
Noteworthy, the post-synthesis obtained Sn-Beta showed slightly SnCl4 and hexamethyleneimine [349]. Samples with Si/Sn ratio of 52
higher catalytic activity than the in situ synthesized F-Sn-Beta in the and 54 were obtained. XRD and UV/Vis data confirmed that Sn occu-
conversion of dihydroxyacetone to ethyl lactate. At the same time, bulk pies the zeolite framework sites. When assessed as catalysts in the
SnO2 acted with lower conversion and yielded a small quantity of ethyl conversion of dihydroxyacetone into lactic acid, Sn-MWW zeolites were
lactate [344]. more efficient than Ti- and B-MWW counterparts. Further, in the con-
Commercial TEA-Beta zeolite was dealuminated with HNO3 to reach version of glucose, fructose, and sucrose, the Sn-MWW zeolites yield the
Si/Al > 1000 [345]. This material was subsequently treated with SnCl4 highest amount of desired product methyl lactate, comparable to Sn-
solution, and thus Sn-Beta materials having 0.5 and 2 wt.% of tin were Beta performance reported in the literature [350].
prepared. The interaction of Sn and silanol groups of the zeolite defect Lari et al. investigated a series of materials: Sn-MFI materials syn-
sites is evidenced by the 29Si CP MAS NMR spectra of the materials. The thesized in OH medium, Sn-MFI and Sn-Beta synthesized with the as-
tin-containing materials displayed a reduced intensity of Q3 species sistance of fluoride ions and Sn-Beta, Sn-MFI, Sn-FAU as well as Sn-
compared to the dealuminated samples. The IR spectra of the Sn-con- MOR prepared by post-synthesis modification with SnSO4 in basic so-
taining zeolites showed a decreased intensity of silanol bands corro- lutions [351]. Generally, the post-synthesis treatment with Sn notably
borating the interaction of Sn with the silanol nests. According to the IR reduced the crystallinity of all samples with respect to parent zeolites.
analysis of the samples with adsorbed probe molecules, additional In each of the studied materials, there are Lewis acid sites present and
Lewis acid sites are generated upon the Sn treatment. The Meerwein- the UV/Vis spectra provided information on the respective Sn co-
Ponndorf-Verley reduction of cyclohexanone takes place on both cata- ordination – the coordination number 6 is dominant in the MFI pre-
lysts. A higher conversion was achieved on the sample having a larger pared in the OH medium, while in the F-containing medium and by a
amount of Sn. Likewise, in the case of the reduction of 4-methox- post-synthesis system more tetrahedral Sn is formed. In Sn-FAU and Sn-
ybenzaldehyde with 2-butanol to 4-methoxybenzylalcohol followed by MOR was observed that Sn mostly resides in tetrahedral positions.
its etherification, the 2 wt% Sn-Beta material shows higher conversion Based on their catalytic performance, in the isomerization of dihy-
degree. However, the catalysts deactivate when the MPV process is droxyacetone in water and methanol and in that of xylose in water, the
followed by etherification, arguably due to the water adsorption on authors concluded that Sn incorporated into zeolite framework during
Lewis acid sites. Considering that the turnover number per Sn atom is hydrothermal synthesis is generating materials with higher hydro-
higher for the material with less Sn, the authors conclude that the active phobicity and improved catalytic activity [351]. The investigation by
sites in all studied reactions are isolated tetrahedral Sn atoms in- van der Graaff et al. confirmed the findings that the zeolite materials
corporated into the zeolite framework [345]. with Sn introduced by post-synthesis modification are more prone to
Hammond et al. obtained materials comprising 5 and 10 wt% of Sn deactivation, tin leaching, and structural degradation than the Sn-zeo-
by grinding dealuminated zeolite Beta with tin(II) acetate, followed by lites obtained by in situ routes [352].
calcination at 550 °C [346]. The IR band of silanol nests in these
samples diminished, whereas the UV/Vis spectra provide evidence of 5. Summary and outlook
the presence of tetrahedral Sn. Employed as catalysts in BV oxidation of
cyclohexanone with H2O2 into ε-caprolactone, the samples present high Acid sites in zeolites are related to Al and heteroatoms present
selectivity. On the other hand, SnO2 deposited on dealuminated zeolite within the material, and their nature and strength are a function of the
Beta as well as pristine zeolite Beta treated with Sn(II) acetate were number, coordination, and framework position of these atoms.
utterly inactive. These results confirm that isolated, tetrahedral Sn built Depending on the structure type, aluminium atoms have shown a pre-
into the zeolite framework is the active site herein [346]. ference for certain T positions within the framework. Furthermore, in
Subjecting the commercial zeolite Y (Si/Al = 6) to dealumination some zeolite crystals has been observed a gradient of Al concentration
26
throughout the volume of the crystal. A range of experimental techni- well as on the ones that have the potential to be used for commercial
ques (NMR, IR, XPS, EDX, ICP, …) is available to examine zeolite acid purposes, most often because of their pores’ dimensions. Intensive
sites providing information on the local environment of Al atoms, studies have been conducted on MFI-, MOR-, BEA-, FER-, CHA- and
connectivity between Si and Al, the nature and position of hydroxyl FAU-type materials, and in these frameworks, the Al quantity, location,
groups together with their spatial proximity and interactions. and acid sites strength can be controlled to a great extent. There are
Monitoring the interactions with probe molecules (CO, NH3, CH3CN, three main reasons these materials to be in the focus of academic and
pyridine, 2,6-lutidine, 2,4,6-collidine, trimethylphosphine oxide, etc.) applied researchers: 1) important industrial processes are based on
enables the assessment of the acid sites’ nature and strength as well them, and any improvement may have significant practical con-
their location with respect to zeolite channel system and within 6- sequences; 2) they proved the ability to undergo modifications (Si/Al
membered rings, and consequently the accessibility to molecules of ratio, particle size, …) and thus to be adapted to different applications;
various sizes. In addition, the theoretical calculations are frequently and 3) their preparation and post-synthesis modification is optimized. A
employed either to predict the acidic properties of a particular material number of zeolites offer promises for practical applications, however,
or to complement and clarify the experimental findings. the preparation conditions limit their uses. For instance, CON-, *SFV-,
In general, there are two principally different approaches for in- RTH-, STW-, OKO-type materials, etc., are mostly prepared in the pre-
troducing and controlling the Al sites within the zeolite materials – in sence of a specific OSDA in a relatively narrow range of chemical
situ and post-synthesis methods. in situ route includes the incorporation compositions of the synthesis mixture. For this reason, the degree of
of Al into the growing zeolite skeleton. The critical factors determining acid site control in these materials is rather low and is limited to pre-
the level of Al incorporation and distribution in a particular framework paring and modifying a few representative materials. Hence, the ability
are the composition of the synthesis systems and the structure-directing to synthesize less common zeolite framework types materials of broader
agent(s) employed. On the other hand, the post-synthesis concept in- chemical composition range is going to allow for engineering of their
volves the incorporation of Al in the already formed zeolite framework acidity as well.
by treatment in gas or liquid phase with a very reactive Al compound. This overview presents a comprehensive picture of the analysis and
Aluminium incorporated in this way is preferentially embedded in the control of active sites in aluminum-containing zeolites. The presented
framework vacancies or replaces T atoms of lower stability. Both fra- findings indicate that further studies need to be conducted in order to
mework and extra-framework Al species are usually generated by the achieve complete control over tailoring the acidic properties of any
post-synthesis modification of zeolite materials with Al. The Al can be zeolite material. This goal can be accomplished by preparing new
incorporated in the defect sites during the crystallization of (alumino) zeolite materials with unknown framework topologies and acidic
silicate zeolites. Alternatively, Al can substitute isomorphous T sites properties different from the now available zeolites. A good example in
that remain vacant upon the hydrolysis of heteroatoms (most common this respect is MWW-type zeolite [353]. Modifying the acidic properties
are B and Ge). Sometimes multi-step procedures such as several cycles of well-known zeolites by in situ and/or post-snthesis methods is also an
of alumination followed by hydrochloric acid treatment or partial T avenue that proved efficiency and will continue to be explored. Fur-
atom removal prior to the alumination are beneficial for preparing thermore, engineering the acidity of zeolites can be realized by the
materials with Al in the framework tetrahedral positions. Besides, the incorporation of heteroatoms into zeolite framework. In the present
Al incorporation in some materials can be more efficient in the case review, this concept is illustrated by highlighting the example of Sn-
when the treatment temperature is increased, or the OSDA is not zeolites that bear Lewis acidity and have particularly disclosed new
completely eliminated. opportunities in biomass valorization as well as in the production of
The preparation of zeolite materials of tailored acidic properties by certain groups of commodities. In addition, there are multiple-step re-
performing one-step synthesis (in situ control of acid sites) has many actions where both Brønsted and Lewis sites are the operating features
advantages: it is an integrated process, the reproducibility degree is that represent another direction for developing zeolite-based processes
usually higher since there are fewer steps to be undertaken, low energy aiming to enhance the prospects to attain sustainable solutions in the
consumption, less waste produced and the material’s production costs energy transition period.
are low. As already mentioned, the post-synthesis zeolite modification This survey is expected to provide guidelines for the preparation of
by Al is not as selective for building Al into the tetrahedral positions as zeolite materials by design in terms of their acidity (number, strength,
in the case of in situ methods. Moreover, this approach requires several and position) and consequently developing more efficient acid zeolite
steps, more waste remediation, as well as higher energy and solvent catalysts in already existing as well as in the new processes.
consumption. However, these two axes of zeolite materials preparation
are complementary, not exclusive. Namely, the post-synthesis treat- Declaration of Competing Interest
ment by Al allowed the preparation of a number of materials possessing
properties that could not have been obtained by the in situ procedure The authors report no declarations of interest.
and vice versa. Thus, it is necessary to continue research in both di-
rections in order to be able to meet the demand on zeolite production to Acknowledgments
deliver materials of desired size and morphology, with a controlled
fraction of structural defects in terms of silanols and/or extraframework This work has been supported in part by Croatian Science
species and with Al or other heteroatoms incorporated in any T position Foundation under the project UIP-2019-04-4977 and the CARNOT-ESP
in any quantity. project 3DNANOZET 5281. V.V. acknowledges the support from the
Designing zeolite materials in terms of their acid site distribution Industrial Chair ANR-TOTAL “Nanoclean Energy”.
can be achieved at several levels of acid sites position: the occupation of
crystallographically non-equivalent sites, the paired sites arrangement, References
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Analysis and Control of Acid Sites in Zeolites

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Applied Catalysis A, General 606 (2020) 117795

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Applied Catalysis A, General

Analysis and control of acid sites in zeolites T

ARTICLE INFO ABSTRACT

1. Introduction range from heterogeneous catalysis, ion and molecular separations to

Fig. 1. Schematic representation of zeolite

Another framework-related effect is that the strength of each proton

Fig. 3. Depiction of the most common distributions of Al atoms in zeolite 6MRs.

well as some promising new framework types. In addition, altering the

3.2. Experimental methods for zeolites’ acidity evaluation

Since Al is related to the acid sites in zeolites, information on its

3.3. Zeolites’ acidity assessment by probe molecules

The very definition of the acids involves the exchange of H+ or

Fig. 9. UV/Vis spectra after pyridine adsorption on hypothetical solid acids

is a powerful technique for zeolite acidity evaluation. Table 2

4. In situ control of acid sites in zeolites

The two avenues of incorporating Al into zeolite framework posi-

1 SiO2:0.01Al2O3:0.5 TPAOH:8.3 H2O Al(NO3)3‡ 40 wt% SiO2† MFI intersections 53 [176]

[180]. In another set of experiments, ZSM-5 materials have been syn-

MOR catalysts with enhanced crystallinity and a higher quantity of

4.1.5. Zeolite beta (BEA@BEB)

showed high catalytic activity towards decalin cracking owing to the

Fig. 19. Principle stages of the ALD process.

tetrahedral. The remained 19 % of Al is assigned to distorted tetra-

acid strength and hydrothermal stability than the aluminium countr-

4.4.1. Boron-containing zeolites

4.4. Controlling the zeolite acidity by incorporating heteroatoms in the Z5-50 44 – 45 % 55 % 32 % 65 % 3%

kept constant (≈ 50) and B content varied, 20–40 % of Al sites were

[4] http://www.iza-online.org (Accessed 27 January 2020). https://doi.org/10.1080/01614940.2012.632662.

10.1016/0144-2449(83)90169-0. [195] E. Catizzone, M. Magliori, S. van Daele, T. Mineva, V. Valtchev, G. Giordano,

123–129, https://doi.org/10.1016/j.apcata.2018.08.024. 10.1039/A607038H.

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