Chemical Science: Edge Article
Chemical Science: Edge Article
Chemical Science: Edge Article
Science
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Lewis acidic aluminum in zeolites, particularly acidity that is inherent to the framework, is an indeterminate
concept. A fraction of framework aluminum changes geometry to octahedral coordination in the proton
form of zeolite mordenite. Such octahedrally coordinated aluminum is the precursor of a Lewis acid site
and its formation is accompanied by a loss in Brønsted acidity. Herein, we show that such Lewis acid
sites have a preferred location in the pore structure of mordenite. A greater proportion of these Lewis
acid sites resides in the side-pockets than in the main channel. By reverting the octahedrally coordinated
aluminum back to a tetrahedral geometry, the corresponding Brønsted acid sites are restored with
a concomitant loss in the ability to form Lewis acid sites. Thereby, reversible octahedral–tetrahedral
aluminum coordination provides a means to indirectly switch between Lewis and Brønsted acidity. This
Received 6th November 2020
Accepted 25th January 2021
phenomenon is unique to Lewis acidity that is inherent to the framework, thereby distinguishing it from
Lewis acidity originating from extra-framework species. Furthermore, the transformation of framework
DOI: 10.1039/d0sc06130a
aluminum into octahedral coordination is decoupled from the generation of distorted tetrahedrally
rsc.li/chemical-science coordinated aluminum, where the latter gives rise to the IR band at 3660 cm1 in the OH stretching region.
a
Institute for Chemical and Bioengineering, Department of Chemistry and Applied
Biosciences, ETH Zurich, 8093 Zurich, Switzerland. E-mail: jeroen.vanbokhoven@
chem.ethz.ch
b
Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, Villigen,
5232, Switzerland
† Electronic supplementary information (ESI) available. See DOI: Fig. 1 Sketch of (a) Brønsted acid site and (b) three-coordinated Lewis
10.1039/d0sc06130a acid site in a zeolite.
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experimentally evident from the existence of an optimal Lewis knowledge gaps, our objective is to arrive at a better under-
to Brønsted acid ratio to achieve the highest yield of the standing of the Lewis acidic property of framework-associated
product.20,21 Likewise, in glycerol dehydration over zeolites, aluminum and of zeolites in general. We demonstrate how
Brønsted acid sites are involved in activating the substrate, but evolution in aluminum coordination with varying conditions
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the selectivity to acrolein or acetaldehyde is dictated by the inuences both Lewis and Brønsted acidity in the zeolite, with
Lewis acid content in the zeolite.22 Consequently, under- the two kind of acid sites being partially interchangeable.
standing the skew of these two different types of acid sites is Furthermore, we highlight the role of the side-pockets in mor-
paramount for the catalytic applications of zeolites. However, denite in this phenomenon. Current knowledge on the gener-
despite zeolites being used commercially on a large scale and ation of Lewis acid sites, irrespective of which kind of
extensive research being carried out over a number of decades aluminum species shows Lewis acidic property, is that they are
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now, the origin of Lewis acidity in these materials remains formed with a loss in Brønsted acidity.24,26,49 Overall, we report
a nebulous concept.15,23–30 Several proposals for Lewis acidic a novel conceptual advance on the possibility to toggle between
aluminum species exist, which include framework Lewis and Brønsted acidity, founded on the basis of aluminum
aluminum,26,27,31 extra-framework aluminum (EFAl),25,32–34 and species that exhibit reversible octahedral–tetrahedral coordi-
framework-associated aluminum.15,30 In a recently published nation. The Lewis acid sites generated from such aluminum
perspective, we discussed this classication in detail and illus- species are preferentially located in the side-pockets as opposed
trated that the multiple proposals point towards a plurality of to the main channel of mordenite.
Lewis acid sites and mechanisms that generate these species.35
The uncertainty in demarcating the origin of Lewis acidic Results and discussion
aluminum in zeolites hampers the analysis of Lewis–Brønsted 27
acid synergy in catalytic applications.36,37 Aluminum structure from Al MAS NMR
The most extensively characterized mechanism for Lewis Fig. 2 illustrates that the coordination of aluminum in zeolite
acidity in zeolites is of that formed aer dealumination via MOR is a function of the charge-compensating cation and
steaming.38 This route entails the hydrolysis of framework Si–O– treatment conditions, in line with what is typically observed for
Al bonds, translating in the removal of aluminum from the zeolites.46,47,50 The details of sample nomenclature and treat-
framework.32,34,39–42 In comparison to this mechanism, the ment procedure are provided in Table 1. Since the aluminum
proposal of Lewis acidity that is inherent to the zeolite frame- structure is sensitive to many factors, such as water content and
work is less rigorously examined, but has received greater temperature,48,51 the structure determined by a conventional
27
attention of late.26,35,43,44 NMR experiments performed at high Al MAS NMR experiment is the structure that prevails aer
elds have enabled the characterization of a second framework
Al(IV) site,45 and the elucidation of the acidic nature of tri-
coordinated framework aluminum in dehydrated ZSM-5.43 The
precursor to Lewis acid sites in this mechanism – unlike for the
Lewis acid sites generated from EFAl – is tetrahedral framework
aluminum.
Framework-associated aluminum refers to species that can
undergo reversible changes in coordination from octahedral to
tetrahedral.46 Through a combination of 27Al MAS NMR and
FTIR spectroscopy, we demonstrated that framework-associated
aluminum can be assigned Lewis acidic property in zeolite
mordenite.30 It adopts an octahedral coordination in the proton
form of the zeolite aer calcination in static air and exposure of
the sample to moisture under ambient conditions.15,30,46,47 Such
an aluminum species is associated with Lewis acidity upon
dehydration.30,48 The octahedrally coordinated framework-
associated species can be reverted into a normal framework
tetrahedral coordination, and should therefore, not be
described as simply extra-framework. While the Lewis acidic
character of framework-associated aluminum was evidenced,
the nature of these species, its evolution as a function of
conditions, and its location in the pore system of zeolite mor-
denite remain unaddressed. Also, the potential role of distorted
tetrahedral and penta-coordinated aluminum in generating
Fig. 2 27Al MAS NMR spectra of zeolite MOR under ambient condi-
Lewis acidity was not evaluated. As per current knowledge, the
tions of NH4–MOR, H–MOR-450, H–MOR-550, MOR-450-NH4 and
extent to which the generation of these latter species are MOR-550-NH4. The broad shoulder at the high field side of the peak
coupled to the generation of framework-associated octahedrally corresponding to tetrahedrally coordinated framework aluminum in
coordinated aluminum is unknown. By targeting these H–MOR-550 is highlighted by the black arrow mark.
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Table 1 Sample name and treatment procedure. A more detailed description of synthesis procedures is provided in the experimental section in
the ESI
NH4–MOR Commercial mordenite zeolite in the ammonium form, Zeolyst CBV21A, Si/Al ¼ 11
H–MOR-450 NH4–MOR calcined at 450 C in static air & subsequent exposure to ambient conditions
H–MOR-550 NH4–MOR calcined at 550 C in static air & subsequent exposure to ambient conditions
MOR-450-NH4 H–MOR-450 aer ammonium ion-exchange using aqueous solution of NH4NO3
MOR-550-NH4 H–MOR-550 aer ammonium ion-exchange using aqueous solution of NH4NO3
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hydration at room temperature.52 The 27Al MAS NMR spectrum geometry on back-exchanging the zeolite to its ammonium
of NH4–MOR contains one resonance at around 56 ppm, char- form.30 This phenomenon of reversible octahedral–tetrahedral
acteristic of tetrahedral framework aluminum. Upon calcining aluminum coordination was rst observed for zeolite BEA,46 and
NH4–MOR in static air at 450 C and subsequent exposure to later conrmed40 and generalized for other zeolites.15,31,48,50,53
ambient conditions (H–MOR-450), a fraction of aluminum Likewise, we observe that the octahedrally coordinated species
adopts an octahedral geometry, evidenced by the sharp reso- in both, H–MOR-450 and H–MOR-550, can be forced back into
nance at 0 ppm. There is an additional change in the spectrum a tetrahedral environment on ammonium-exchange (Fig. 2).
of the sample calcined at a higher temperature of 550 C The sharpness of the feature at 0 ppm implies that the electric
(H–MOR-550). Besides the presence of octahedrally coordinated eld gradient surrounding this aluminum atom is small and
aluminum, the tetrahedral feature at 56 ppm has a broad therefore suggests a high symmetry.
shoulder stretching to lower chemical shis. This broadening is The conversion of tetrahedrally coordinated framework
not present in the spectrum of NH4–MOR and is barely aluminum to an octahedral coordination is driven by the
discernible in that of H–MOR-450. Octahedrally coordinated adsorption of water through hydrolysis reactions.50,54,55 The
aluminum represents 11% of the total aluminum content original proposal for the octahedral framework-associated
in H–MOR-550 and 10% of the total aluminum content in species was that the aluminum is connected to the framework
H–MOR-450. via four oxygen atoms with a water molecule and a hydronium
Octahedrally coordinated aluminum in mordenite, which is ion being the two other coordinations.46 However, theoretical
characterized by a narrow resonance at 0 ppm by 27Al MAS work shows that hydrolysis of Si–O and Al–O bonds readily
NMR, can be forced back into the typical framework tetrahedral occur and a fourfold coordination to the framework is
Fig. 3 27Al MQMAS NMR spectra measured under ambient conditions for NH4–MOR, H–MOR-450, H–MOR-550, MOR-450-NH4 and
MOR-550-NH4. The F1 projection shows a purely isotropic dimension and the F2 projection depicts the corresponding 27Al MAS NMR spectrum,
which is acquired in a separate experiment.
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unlikely.42 Despite the lack of certainty about the exact struc- suggesting that the Al(IV)b species is not a precursor to the Al(VI)
ture, enough experimental evidence has emerged to suggest sites.
that such octahedrally coordinated aluminum cannot be trivi- Fig. 3 shows that the 27Al MQMAS NMR spectrum of
ally dismissed as EFAl.46–48 MOR-450-NH4 is very similar to that of NH4–MOR, but the same
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The 27Al MQMAS NMR spectrum of NH4–MOR shows observation does not hold for MOR-550-NH4. In the spectrum of
a single feature assigned to tetrahedral framework aluminum the latter, the resonance of the Al(VI) species disappears and that
(Fig. 3). The spectrum of H–MOR-550 shows two types of of Al(IV)a reappears but that of Al(IV)b species continues to be
tetrahedrally coordinated aluminum species, one type of octa- present. The population of distorted tetrahedral Al(IV)b sites is
hedrally coordinated species and no penta-coordinated an important point of difference between the spectra of
aluminum. The 27Al MQMAS spectrum demonstrates that the MOR-550-NH4 and NH4–MOR. Since the Al(IV)b sites are only
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two types of tetrahedral species have different anisotropy. formed at a calcination temperature of 550 C, these aluminum
Tetrahedrally coordinated framework aluminum denoted as species most likely represent irreversible thermal damage
Al(IV)a hugs onto the F1 ¼ F2 diagonal pointing to a very low inicted on the zeolite framework, preventing their trans-
anisotropic quadrupolar interaction. In contrast, the signicant formation back into a framework T-site, unlike the framework-
quadrupolar interaction for the Al(IV)b sites is evidenced by the associated octahedrally coordinated aluminum.
broad contours parallel to the F2 dimension. The absence of The phenomenon of reversible tetrahedral–octahedral
penta-coordinated aluminum is in line with the ndings from aluminum coordination in zeolite mordenite can be realized
Chen et al., who have previously detected ve-coordinated independent of the Si/Al ratio. To illustrate this, we calcined
aluminum in mordenite only upon calcination at tempera- three ammonium–mordenite samples of different Si/Al ratio at
tures in excess of 650 C.56 The fraction of Al(IV)b is a function of 550 C to obtain the corresponding proton forms (Table S1†).
calcination temperature. Such species is barely detectable in the The percentage of octahedrally coordinated aluminum
spectrum of H–MOR-450. However, this sample does contain decreases from 13% for zeolite MOR with a Si/Al ratio of 8.8 to
a substantial amount of octahedrally coordinated aluminum, 10% for a sample of a higher Si/Al ratio of 19.7. In comparison,
up to 19% of aluminum adopts an octahedral coordination in
Fig. 4 FTIR spectra of (a) adsorbed pyridine over activated NH4–MOR, H–MOR-450, H–MOR-550, MOR-450-NH4 and MOR-550-NH4; (b)
samples activated under vacuum at 450 C for 4 h (solid line) and after pyridine adsorption–desorption at 150 C (dashed line) in the OH
stretching region. The names of the samples refer to the form of the zeolite prior to heat treatment in the IR setup.
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the proton form of zeolite BEA with a Si/Al ratio of 9.57 When the framework upon converting to the ammonium form (vide
protonic zeolites are exchanged back into the ammonium form, supra). Consequently, the conversion of the Lewis acid-forming
we observe a quantitative transformation of octahedrally coor- framework-associated aluminum to a typical tetrahedral
dinated aluminum into tetrahedral coordination (Table S1†). framework species results in increased Brønsted acidity upon in
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high temperature evacuation and pyridine adsorption–desorp- desorption. The most prominent absorption in the evacuated
tion. The names of the samples in the gure refer to the form of samples is that at 3610 cm1, which is attributed to bridging
the zeolite prior to heat treatment in the IR setup; high hydroxyl groups (Brønsted acid sites). The feature at 3745 cm1
temperature activation of the samples under vacuum before is the signature for silanols. FTIR spectra of H–MOR-550 and
pyridine adsorption–desorption converts all the zeolites to the MOR-550-NH4 (Fig. 4b) show a shoulder at around 3660 cm1,
proton form. The absorption features at 1455 and 1620 cm1 in which is attributed to the presence of Al–OH species.58 This
Fig. 4a are assigned to pyridine bound to Lewis acid sites, while feature is barely visible in the spectra of NH4–MOR, H–MOR-450
those at 1545 and 1635 cm1 correspond to protonated pyri- and MOR-450-NH4. The peak area associated with Brønsted
dine. Activation of NH4–MOR under vacuum results in a minor acid sites decreases in the order NH4–MOR z MOR-450-NH4 >
population of Lewis acid sites. In a previous study, we estab- H–MOR-450 > MOR-550-NH4 > H–MOR-550 (Table 2). The total
lished that framework-associated aluminum in proton- Brønsted acidity measured aer high temperature in situ acti-
exchanged zeolites adopts an octahedral coordination under vation of MOR-450-NH4 is highly comparable to that of in situ
ambient conditions and is the precursor for Lewis acid sites.30 activated NH4–MOR. However, in the case of MOR-550-NH4, the
Upon activation, both H–MOR-450 and H–MOR-550 have total Brønsted acidity, while being appreciably higher than in
a lower concentration of Brønsted acid sites (BAS, 1545 cm1) H–MOR-550, is still inferior to that of NH4–MOR. Therefore, the
than NH4–MOR. Likewise, the spectrum of H–MOR-450 exhibits extent to which Brønsted acid sites are restored depends on the
a larger peak associated with Brønsted acidity (1545 cm1) and temperature at which the proton form is calcined. A nearly
a smaller feature corresponding to Lewis acidity (LAS, complete retrieval of Brønsted acidity is possible with the
1455 cm1) than that of H–MOR-550. Therefore, the generation zeolite calcined at 450 C, but not with samples calcined at
of Lewis acid sites is accompanied by a loss of Brønsted acid higher temperatures. The presence of irreversibly formed Al–
sites. In other words, some of the framework aluminum that OH groups in MOR-550-NH4 results in the total Brønsted acidity
generate Brønsted acidity convert into framework-associated being inferior to that of NH4–MOR (Table 2).
octahedrally coordinated species, which aer dehydration Aer adsorption of pyridine at 150 C followed by desorption
show Lewis acidity. Fig. 4a and Table 2 show that MOR-450-NH4 at the same temperature, the spectrum of activated NH4–MOR
and MOR-550-NH4 have lower Lewis acid and higher Brønsted shows a feature centered at approximately 3587 cm1 in the OH-
acid concentrations aer in situ activation than the corre- stretching region (Fig. 4b). This corresponds to the fraction of
sponding proton forms, H–MOR-450 and H–MOR-550. This Brønsted acid sites that are not probed by pyridine. The side-
observation is consistent with the 27Al NMR results discussed pockets in mordenite present accessibility limitations for
earlier, where aluminum in octahedral coordination in the sterically bulky molecules. While pyridine can access Brønsted
proton form of mordenite was shown to reinsert into the acid sites in the main channel in a pristine mordenite sample, it
cannot probe bridging OH groups located in the side-
pockets.59–61 The above-mentioned OH-stretch frequency at
Table 2 Analysis of total Brønsted (BAS) and Lewis acidity (LAS) in the 3587 cm1 is representative of such inaccessible Brønsted acid
different mordenite samples
sites. This feature continues to be present in the spectrum of
LAS peak area LAS peak area H–MOR-450, but is barely observed in the spectrum of
BAS peak as assessed using as assessed using H–MOR-550 (Fig. 4b). The disappearance of this feature
Sample areaa [a.u.] pyridineb [a.u.] carbon monoxidec [a.u.] suggests that only a small number of bridging hydroxyl groups
remain in the side-pockets of the H–MOR-550 sample and that
NH4–MOR 52 3.9 1.2
nearly all bridging hydroxyl groups can be accessed by pyridine.
H–MOR-450 41 4.1 1.6
H–MOR-550 26 6.5 1.8 Using carbon monoxide as a probe molecule enables the
MOR-450-NH4 49 3.5 1.2 distinction of Lewis acid sites in terms of their coordination
MOR-550-NH4 37 3.6 1.1 number. Assuming the assignment of IR signatures from pub-
a
Computed by integration of the peak at 3609 cm1 in the activated lished literature, the interaction of carbon monoxide with three-
sample. b Computed by integration of the peak at 1455 cm1 in the and ve-coordinated Lewis acidic aluminum result in FTIR
pyridine-adsorbed sample. c Computed by integration of the peaks at absorption bands at 2224 cm1 and 2198 cm1 respectively.62–64
2224 cm1 and 2198 cm1 in the CO-adsorbed sample. The relative
error for all numbers listed in the table is 5%. Three-coordinated Lewis acid sites are typically found in mor-
denite zeolites of both high and low aluminum content, but
4098 | Chem. Sci., 2021, 12, 4094–4103 © 2021 The Author(s). Published by the Royal Society of Chemistry
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H–MOR-450 remain inaccessible to pyridine, nearly all increasing Si/Al ratio.30 The negligible amount of octahedrally
Brønsted acid sites can be probed in H–MOR-550 (dashed lines, coordinated aluminum in the proton form of Si-rich zeolites
Fig. 4b). Previous studies on zeolite mordenite of a comparable suggests that isolated aluminum atoms do not undergo this
Si/Al ratio suggested that pyridine can access a part of Brønsted phenomenon, and instead, two or more aluminum atoms in
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acid sites in the side-pockets in the proton form calcined at close proximity might be needed for the generation of octahe-
550 C, which is not the case with the parent ammonium dral framework-associated species. Based on the FTIR results
form.59,60,65 Based on these ndings, it appears that Lewis acid presented herein, the side-pockets in mordenite can be envi-
sites originating from framework-associated aluminum tend to sioned to provide a more favorable environment in terms of
be localized more in the side pockets than in the main channel proximal aluminum location for the generation and stabiliza-
of mordenite. This would explain why the Lewis acidity tion of octahedral framework-associated aluminum. In this
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measured with pyridine in H–MOR-450, wherein pyridine has context, it is worth noting that the relatively stronger acidity of
considerable accessibility limitations in the side-pockets, is Brønsted acid sites in the side-pockets compared to those in the
much lower than the acidity measured in H–MOR-550, wherein main channel of mordenite is assigned to the stronger
these restrictions are more relaxed. And notably, the use of connement effect imposed by the zeolite framework.68
carbon monoxide reveals a smaller difference in Lewis acid
content between these two samples.
The Al–OH groups, which are present in H–MOR-550 and Al–OH groups and its relation to distorted tetrahedrally
characterized by the IR band at 3660 cm1, do not engage in coordinated aluminum
a Lewis acidic interaction with pyridine. The corresponding The FTIR spectroscopic signature at around 3660 cm1 for Al–
back-exchanged sample, MOR-550-NH4, continues to have OH groups correlates with the signature for distorted tetrahe-
appreciable amounts of Al–OH moieties (Fig. 4b), but shows drally coordinated aluminum on the 27Al MQMAS NMR. Fig. 4b
Lewis acidity that is comparable to activated NH4–MOR and shows that Al–OH species is virtually non-existent in the spectra
MOR-450-NH4 (Table 2), neither of which show signatures for of NH4–MOR and H–MOR-450, but present in substantial
Al–OH. The Al–OH groups are also not Brønsted acidic, since amounts in the spectrum of H–MOR-550. Stacking this against
the signature for these species in the OH stretching region the corresponding 27Al MQMAS NMR spectra (Fig. 3) reveals
remains largely unperturbed aer pyridine adsorption (dashed that Al–OH groups are linked to the distorted tetrahedral sites
lines, Fig. 4b). The low Lewis acid content in MOR-550-NH4, as (Al(IV)b). The same interpretation can also be drawn from the
detected by pyridine, is unlikely to be caused by accessibility back-exchanged ammonium samples. MOR-450-NH4 has
limitations as most of the Brønsted acid sites in this sample can a negligible population of distorted tetrahedral sites, as evi-
be accessed by pyridine (dashed line, Fig. 4b). Consequently, denced by 27Al MQMAS NMR (Fig. 3) and correspondingly, no
the low Lewis acid content of MOR-550-NH4 is truly reective of pronounced feature for Al–OH groups in the FTIR spectrum
the transformation of Lewis acid-forming framework-associated (Fig. 4b). MOR-550-NH4 has a far more substantial number of
aluminum to tetrahedral framework aluminum, which is not distorted tetrahedral sites on the 27Al MQMAS NMR and
Lewis acidic. This observation is further validated by measure- correspondingly, a distinct feature for Al–OH groups in the FTIR
ments of Lewis acidity using carbon monoxide (Table 2). spectrum. Consequently, the generation of the Al–OH species
While the concept of certain aluminum species exhibiting upon calcination at high temperatures corresponds to
reversible tetrahedral-octahedral coordination has been re- a different aluminum species than the framework-associated
ported in the past, we show that Lewis acid sites originating aluminum that changes coordination. H–MOR-450 is exem-
from framework-associated aluminum has preferential site plar of this hypothesis as it has appreciable amounts of octa-
occupancy in zeolites; in the case of mordenite, the side-pockets hedrally coordinated aluminum but barely any distorted
are more favored to host these sites than the main channel. This tetrahedral aluminum on the 27Al MQMAS NMR (Fig. 3) or
insight can have far-reaching implications for the rational signature for Al–OH groups in the FTIR spectrum (Fig. 4b).
synthesis of Lewis acid sites in zeolites by virtue of controlling Therefore, octahedrally coordinated aluminum in morden-
aluminum distribution.66 Furthermore, such information on ite, Al(VI), which is characterized by the narrow 27Al signal at
site specicity can aid in the engineering of improved catalysts, around 0 ppm under hydrated conditions - and which shows
as realized in the case of Brønsted acid-catalyzed carbonyla- Lewis acidic behavior aer dehydration – is able to revert into
tion.67 While the distribution of Brønsted acid sites can be a framework site. However, distorted tetrahedrally coordinated
assessed using 1H DQMAS NMR of acetonitrile-d3 adsorbed over aluminum, Al(IV)b, which has one or more OH coordinations
mordenite, catalytic activity in the carbonylation of dimethyl and is generated by calcination at a higher temperature,
ether correlates with the number of acidic protons in the side- behaves differently and does not change coordination upon
pockets.68,69 Analogous to these ndings on the specicity of ammonium exchange. While substantial amounts of octahe-
Brønsted acid sites in carbonylation reactions, knowledge on drally coordinated aluminum is present under ambient condi-
the site specicity of Lewis acid sites in zeolites will enhance the tions in H–MOR-450 (Fig. 2), the accessibility limitations for
understanding of their role(s) in catalytic applications. pyridine in this sample is comparable to that in NH4–MOR
As is generally observed with different zeolite types, the (Fig. 4b). Based on this observation and on the FTIR line shapes
amount of octahedrally coordinated framework-associated of H–MOR-550 and MOR-550-NH4 aer pyridine adsorption
aluminum in the proton form of mordenite decreases with (Fig. 4b), it appears that it is the distorted tetrahedral sites, and
4100 | Chem. Sci., 2021, 12, 4094–4103 © 2021 The Author(s). Published by the Royal Society of Chemistry
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species are listed in a table as part of Scheme S1.† We further form converts octahedrally coordinated aluminum back into
indicate the nature of each species, as likely being/originating a framework tetrahedral coordination, with the bridging
from framework, extra-framework or framework-associated hydroxyl groups being formed upon ammonia removal. The
aluminum. Calcining the ammonium form of mordenite at degree of retrieval of Brønsted acidity is a function of the
450 C in static air and subsequent exposure of the sample to calcination temperature. Higher calcination temperature yields
ambient conditions yields the proton form of the zeolite a distorted tetrahedrally coordinated aluminum species that is
(H_MOR_wet in Scheme S1†) with aluminum in two different irreversibly formed and is characterized by a high anisotropy of
geometries: tetrahedral framework aluminum (Al(IV)a) and chemical shi. This species contributes to the IR feature at
octahedrally coordinated framework-associated aluminum 3660 cm1 in the OH-stretching region, assigned to Al–OH
(Al(VI)). The zeolite is devoid of penta-coordinated and dis- moieties. The presence of these Al–OH species modies pyri-
torted tetrahedral aluminum moieties. Evacuating H_MOR_- dine accessibility to the acid sites in the side-pockets of mor-
wet at elevated temperature converts the octahedrally denite. The attribute of framework-associated aluminum to
coordinated aluminum species into primarily three- undergo reversible transformation in coordination from tetra-
coordinated and some ve-coordinated Lewis acidic species hedral to octahedral enables the possibility to switch between
(H_MOR_activated in Scheme S1†) that are preferentially Brønsted and Lewis acidity. Aluminum in the side-pockets in
localized in the side-pockets of mordenite.30 Upon ammonium mordenite are more prone to show such behavior. Therefore,
exchange of the H_MOR_wet sample, the coordination envi- Lewis acid sites formed from framework-associated aluminum
ronment of aluminum in the zeolite reverts to being exclusively are found to have a preferential site occupancy in the pore
tetrahedral (H_MOR_NH4 in Scheme S1†), as present in the structure of mordenite. These observations are fundamentally
parent NH4_MOR. While such a change in aluminum coordi- different to the largely researched Lewis acidic extra-framework
nation from octahedral to tetrahedral has been observed with aluminum and could enable a paradigm shi in the rational
several zeolite topologies, an elaborate mechanism on how design of Lewis acid sites in zeolites.
ammonium ion-exchange, or equivalently ammonia treatment,
facilitates this transformation is yet to be deduced and should
be a key research direction to be explored in the future.47,55 Conflicts of interest
Evacuating H_MOR_NH4 under vacuum at high temperature
shows greater Brønsted acidity that in the preceding proton There are no conicts of interest to declare.
form. This is because the conversion of octahedrally coordi-
nated aluminum to a tetrahedral geometry on ammonium
exchange restores the typical tetrahedrally coordinated frame- References
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