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On the location of Lewis acidic aluminum in zeolite


mordenite and the role of framework-associated
Open Access Article. Published on 26 January 2021. Downloaded on 10/13/2021 8:16:46 AM.

Cite this: Chem. Sci., 2021, 12, 4094

All publication charges for this article


aluminum in mediating the switch between
have been paid for by the Royal Society
of Chemistry
Brønsted and Lewis acidity†
a b *ab
Manoj Ravi, Vitaly L. Sushkevich and Jeroen A. van Bokhoven

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.

adsorbed probe molecules.12,13 Not only can Lewis acid sites be


Introduction distinguished easily from Brønsted acid ones, but ner
Zeolites are extensively used as catalyst and support materials nuances, such as acid site strength and accessibility can also be
for a wide array of industrially applied reactions.1,2 The presence assessed. For instance, evacuating adsorbed pyridine at
of tetrahedrally coordinated aluminum in a zeolite framework different temperatures provides information on the strength of
necessitates a charge-compensating cation to yield a neutral adsorption, which to some extent relates to acid site
material. When this cation is a proton, it results in a Brønsted strength.14–16 Likewise, using probe molecules of different sizes
acid site (Fig. 1a),3 which is at the origin of industrial applica- sheds light on the accessibility of the sites.17
tion of zeolites as solid acid catalysts, replacing homogeneous Alongside Lewis acidic aluminum species in zeolites,
mineral acids in various processes.4 Protonic zeolites are Brønsted acid sites engage in a cooperative fashion to catalyze
extensively used for several reactions, in particular, cracking, multi-step ‘domino’ reactions.18 Examples of such reactions in
alkylation, and isomerization.5–7 Apart from Brønsted acid sites, biomass valorization chemistry include the conversion of
certain aluminum species in zeolites possess Lewis acidic glucose to 5-hydroxymethylfurfural (HMF) and of C3-sugars to
character. Lewis acidic aluminum (Fig. 1b) plays a pivotal role lactic acid esters.19–21 These conversions feature consecutive
not only in traditional cracking reactions, but also in salient reaction steps that take place over different active sites and
biomass valorization reactions,8,9 which include the conversion consequently, require a precise balancing of the number of
of trioses to alkyl lactates,10 and cellulose to glucose.11 Lewis and Brønsted acid sites in the zeolite. This is
Conventionally, one of the o-used techniques to study the
above-mentioned acid sites in zeolites is FTIR spectroscopy of

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.

4094 | Chem. Sci., 2021, 12, 4094–4103 © 2021 The Author(s). Published by the Royal Society of Chemistry
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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 inuences 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
Open Access Article. Published on 26 January 2021. Downloaded on 10/13/2021 8:16:46 AM.

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 classication 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 aer 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 aer
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 aer 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

Sample name Treatment procedure


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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 aer ammonium ion-exchange using aqueous solution of NH4NO3
MOR-550-NH4 H–MOR-550 aer ammonium ion-exchange using aqueous solution of NH4NO3
Open Access Article. Published on 26 January 2021. Downloaded on 10/13/2021 8:16:46 AM.

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 conrmed40 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 shis. 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 inicted on the zeolite framework, preventing their trans-
anisotropic quadrupolar interaction. In contrast, the signicant 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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situ activation of the back-exchanged samples. The greater


intensity of the peak corresponding to pyridinium ion in the
Relationship between aluminum coordination and Brønsted–
FTIR spectra of the activated back ammonium-exchanged
Lewis acidity
samples duly reects this.
Fig. 4a depicts the FTIR spectra of NH4–MOR, H–MOR-450, Fig. 4b illustrates the FTIR spectra of the same samples in
H–MOR-550, MOR-450-NH4 and MOR-550-NH4 aer in situ the OH stretching region, before and aer pyridine adsorption–
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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 aer 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 aer dehydration Aer 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 aer 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

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Scheme 1 Reversible tetrahedral–octahedral coordination exhibited


by framework-associated aluminum and its impact on Brønsted and
Lewis acidity.

Therefore, the property of reversible tetrahedral–octahedral


coordination exhibited by framework-associated aluminum
facilitates the indirect switching between Brønsted and Lewis
acidity (Scheme 1). While the switch in acidity was experimen-
tally observed herein with mordenite, we believe that this can be
extended to zeolite topologies that allow the formation of
Fig. 5 FTIR spectra of adsorbed carbon monoxide over activated
octahedrally coordinated framework-associated aluminum,
parent ammonium form NH4–MOR, H–MOR-450, H–MOR-550, which have been observed in a range of different zeolites,
MOR-450-NH4 and MOR-550-NH4. The names of the samples refer including BEA46 and zeolite Y.50
to the form of the zeolite prior to heat treatment in the IR setup.

Location of framework-associated aluminum in the pore


ve-coordinated aluminum species are detected in appreciable system of mordenite
amounts only in samples of low Si/Al ratio.30 Fig. 5 reveals that The Lewis acid content detected with pyridine as the probe
a major portion of Lewis acid sites aer activation of each molecule in H–MOR-450 is only marginally higher than that in
sample is three-coordinated. Calcining NH4–MOR in situ under activated NH4–MOR (Table 2). However, there is a large differ-
vacuum results in an almost ideal proton form with a low ence in the Lewis acid site concentration between H–MOR-450
contribution of Lewis acid sites. While this sample is largely and H–MOR-550. From 27Al MAS NMR, we know that the frac-
devoid of ve-coordinated Lewis acid sites, such sites are tion of Al(VI) in these acidic zeolites are not substantially
present in non-negligible amounts in the other samples. different (vide supra). Therefore, the large difference in the
The ndings presented in this section constitute an impor- intensity of the peak at 1455 cm1 for these two zeolites (Fig. 4a,
tant conceptual advance in the relationship between aluminum Table 2) might not reect such a quantitative difference in acid
coordination and Brønsted–Lewis acidity in zeolites (Scheme 1). site density, but instead could be caused by differences in
Framework aluminum adopts a tetrahedral geometry in the accessibility of the Lewis acid sites for pyridine. Being a much
ammonium form of the zeolite. In situ activation of such sample smaller molecule, carbon monoxide can probe all acid sites in
yields Brønsted acid sites through ammonia removal. On the mordenite, including the ones located deep in the side-pockets.
other hand, when NH4–MOR is calcined in static air and From Fig. 5 and Table 2, we infer that the Lewis acid site
exposed to ambient conditions, a fraction of the aluminum concentration detected with carbon monoxide in H–MOR-450
described as being associated to the framework adopts octa- and H–MOR-550 differ minimally, while being higher than
hedral geometry. Upon high-temperature activation, this that observed in in situ activated NH4–MOR. This suggests that
aluminum species has Lewis acidic character. When the acidic the much lower Lewis acid content, as measured with pyridine
form of the zeolite is back-exchanged into the ammonium form, in H–MOR-450 compared to H–MOR-550, is due to differences
the framework-associated aluminum reverts to a tetrahedral in acid site accessibility for pyridine. Fig. 4b corroborates this
geometry. In situ activation of such a back-exchanged sample hypothesis from the context of Brønsted acid site accessibility.
shows low Lewis and high Brønsted acid concentration. While a substantial portion of bridging hydroxyl groups in

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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 connement 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 aer 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 reective 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 specicity 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 aer 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 specicity 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 specicity 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 aer pyridine adsorption
aluminum in the proton form of mordenite decreases with (Fig. 4b), it appears that it is the distorted tetrahedral sites, and

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not the octahedrally coordinated species, that modify accessi- Conclusions


bility for pyridine to acid sites in the side-pockets.
Proton forms of zeolite mordenite, obtained by the calcination
of the parent ammonium form in wet static air, possess
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Evolution of aluminum structure with conditions in framework-associated octahedrally coordinated aluminum


mordenite under ambient conditions. Aer high temperature activation of
Scheme S1† summarizes the key ndings from this study and such sample, the framework-associated aluminum shows Lewis
presents the evolution of aluminum structure in zeolite mor- acidic property. The changes in aluminum coordination and
denite as a function of conditions. The NMR and FTIR spec- conversion of Brønsted into Lewis acidity are partially revers-
troscopic signatures used for the assignment of different ible. Exchanging the proton form back into the ammonium
Open Access Article. Published on 26 January 2021. Downloaded on 10/13/2021 8:16:46 AM.

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 modies 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 conicts 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
work aluminum, which yield bridging hydroxyl groups upon
ammonia removal. The evolution of aluminum structure on 1 C. Marcilly, J. Catal., 2003, 216, 47–62.
calcining the ammonium form of the zeolite at a higher 2 G. Sartori and R. Maggi, Chem. Rev., 2006, 106, 1077–1104.
temperature of 550  C in static air is largely similar to the 3 W. O. Haag, R. M. Lago and P. B. Weisz, Nature, 1984, 309,
evolution observed with the sample calcined at a lower 589.
temperature of 450  C but for one important difference. The 4 W. F. Hölderich and H. Van Bekkum, in Studies in Surface
treatment at the higher temperature generates distorted tetra- Science and Catalysis, Elsevier, 1991, vol. 58, pp. 631–726.
hedral aluminum sites (H_MOR_highT_wet in Scheme S1†), 5 E. T. C. Vogt and B. M. Weckhuysen, Chem. Soc. Rev., 2015,
which result in anisotropic broadening in the 27Al MAS NMR 44, 7342–7370.
spectrum of this proton form. In the FTIR spectrum, the Al–OH 6 K. M. Minachev, V. I. Garanin, V. V. Kharlamov, T. A. Isakova
species are characterized by an absorption at 3660 cm1 in the and E. E. Senderov, Russ. Chem. Bull., 1969, 18, 1611–1615.
OH stretching region and they do not interact with pyridine. 7 I. E. Maxwell, Catal. Today, 1987, 1, 385–413.
While ammonium ion-exchange renders it possible to convert 8 E. Taarning, C. M. Osmundsen, X. Yang, B. Voss,
all octahedrally coordinated framework-associated aluminum S. I. Andersen and C. H. Christensen, Energy Environ. Sci.,
into tetrahedral coordination, the distorted tetrahedral 2011, 4, 793–804.
aluminum sites do not revert to the pristine tetrahedral 9 H. Y. Luo, J. D. Lewis and Y. Román-Leshkov, Annu. Rev.
framework coordination (H_MOR_highT_NH4 in Scheme S1†). Chem. Biomol. Eng., 2016, 7, 663–692.

© 2021 The Author(s). Published by the Royal Society of Chemistry Chem. Sci., 2021, 12, 4094–4103 | 4101
View Article Online

Chemical Science Edge Article

10 P. P. Pescarmona, K. P. F. Janssen, C. Delaet, C. Stroobants, 37 S. Li, A. Zheng, Y. Su, H. Fang, W. Shen, Z. Yu, L. Chen and
K. Houthoofd, A. Philippaerts, C. De Jonghe, J. S. Paul, F. Deng, Phys. Chem. Chem. Phys., 2010, 12, 3895–3903.
P. A. Jacobs and B. F. Sels, Green Chem., 2010, 12, 1083–1089. 38 R. A. Beyerlein, C. Choi-Feng, J. B. Hall, B. J. Huggins and
11 P. Lanzafame, D. M. Temi, S. Perathoner, A. N. Spadaro and G. J. Ray, Top. Catal., 1997, 4, 27–42.
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

G. Centi, Catal. Today, 2012, 179, 178–184. 39 V. L. Zholobenko, L. M. Kustov, V. B. Kazansky, E. Loeffler,
12 M. Maache, A. Janin, J. C. Lavalley, J. F. Joly and E. Benazzi, U. Lohser, C. Peuker and G. Oehlmann, Zeolites, 1990, 10,
Zeolites, 1993, 13, 419–426. 304–306.
13 C. A. Emeis, J. Catal., 1993, 141, 347–354. 40 J. A. van Bokhoven, D. C. Koningsberger, P. Kunkeler, H. Van
14 S. M. Maier, A. Jentys and J. A. Lercher, J. Phys. Chem. C, Bekkum and A. P. M. Kentgens, J. Am. Chem. Soc., 2000, 122,
2011, 115, 8005–8013. 12842–12847.
Open Access Article. Published on 26 January 2021. Downloaded on 10/13/2021 8:16:46 AM.

15 B. Gil, S. I. Zones, S.-J. Hwang, M. Bejblová and J. Čejka, J. 41 G. Catana, D. Baetens, T. Mommaerts, R. A. Schoonheydt
Phys. Chem. C, 2008, 112, 2997–3007. and B. M. Weckhuysen, J. Phys. Chem. B, 2001, 105, 4904–
16 M. Boronat and A. Corma, ACS Catal., 2019, 9, 1539–1548. 4911.
17 N. S. Nesterenko, F. Thibault-Starzyk, V. Montouillout, 42 Z. Yu, A. Zheng, Q. Wang, L. Chen, J. Xu, J. P. Amoureux and
V. V. Yuschenko, C. Fernandez, J. P. Gilson, F. Fajula and F. Deng, Angew. Chem., Int. Ed., 2010, 49, 8657–8661.
I. I. Ivanova, Microporous Mesoporous Mater., 2004, 71, 157– 43 S. Xin, Q. Wang, J. Xu, Y. Chu, P. Wang, N. Feng, G. Qi,
166. J. Trébosc, O. Lafon and W. Fan, Chem. Sci., 2019, 10,
18 L. Bui, H. Luo, W. R. Gunther and Y. Román-Leshkov, Angew. 10159–10169.
Chem., Int. Ed., 2013, 52, 8022–8025. 44 T. T. Le, A. Chawla and J. D. Rimer, J. Catal., 2020, 391, 56–
19 P. Y. Dapsens, C. Mondelli and J. Pérez-Ramı́rez, Chem. Soc. 68.
Rev., 2015, 44, 7025–7043. 45 K. Chen, S. Horstmeier, V. T. Nguyen, B. Wang,
20 T. D. Swi, H. Nguyen, Z. Erdman, J. S. Kruger, V. Nikolakis S. P. Crossley, T. Pham, Z. Gan, I. Hung and J. L. White, J.
and D. G. Vlachos, J. Catal., 2016, 333, 149–161. Am. Chem. Soc., 2020, 142, 7514–7523.
21 V. V. Ordomsky, V. L. Sushkevich, J. C. Schouten, J. Van Der 46 E. Bourgeat-Lami, P. Massiani, F. Di Renzo, P. Espiau,
Schaaf and T. A. Nijhuis, J. Catal., 2013, 300, 37–46. F. Fajula and T. Des Courières, Appl. Catal., 1991, 72, 139–
22 S. Suganuma, T. Hisazumi, K. Taruya, E. Tsuji and 152.
N. Katada, ChemistrySelect, 2017, 2, 5524–5531. 47 A. Omegna, J. A. van Bokhoven and R. Prins, J. Phys. Chem. B,
23 M. A. Bañares, J. H. Cardoso, G. J. Hutchings, J. M. C. Bueno 2003, 107, 8854–8860.
and J. L. G. Fierro, Catal. Lett., 1998, 56, 149–153. 48 J. A. van Bokhoven, A. M. J. Van der Eerden and
24 B. Wichterlová, Z. Tvarůžková, Z. Sobalık and P. Sarv, D. C. Koningsberger, J. Am. Chem. Soc., 2003, 125, 7435–
Microporous Mesoporous Mater., 1998, 24, 223–233. 7442.
25 X. Pu, N.-w. Liu and L. Shi, Microporous Mesoporous Mater., 49 D. Ma, F. Deng, R. Fu, X. Han and X. Bao, J. Phys. Chem. B,
2015, 201, 17–23. 2001, 105, 1770–1779.
26 J. Brus, L. Kobera, W. Schoeerger, M. Urbanová, P. Klein, 50 B. H. Wouters, T. H. Chen and P. J. Grobet, J. Am. Chem. Soc.,
P. Sazama, E. Tabor, S. Sklenak, A. V. Fishchuk and 1998, 120, 11419–11425.
J. Dědeček, Angew. Chem., Int. Ed., 2015, 54, 541–545. 51 J. A. van Bokhoven, Phys. Scr., 2005, 2005, 76–79.
27 T. K. Phung and G. Busca, Appl. Catal., A, 2015, 504, 151–157. 52 Z. Zhao, S. Xu, M. Y. Hu, X. Bao, C. H. F. Peden and J. Hu, J.
28 G. Busca, Microporous Mesoporous Mater., 2017, 254, 3–16. Phys. Chem. C, 2014, 119, 1410–1417.
29 X. Yi, K. Liu, W. Chen, J. Li, S. Xu, C. Li, Y. Xiao, H. Liu, 53 P. J. Kunkeler, B. J. Zuurdeeg, J. C. Van der Waal, J. A. van
X. Guo and S.-B. Liu, J. Am. Chem. Soc., 2018, 140, 10764– Bokhoven, D. C. Koningsberger and H. Van Bekkum, J.
10774. Catal., 1998, 180, 234–244.
30 M. Ravi, V. L. Sushkevich and J. A. van Bokhoven, J. Phys. 54 L. C. De Ménorval, W. Buckermann, F. Figueras and
Chem. C, 2019, 123, 15139–15144. F. Fajula, J. Phys. Chem., 1996, 100, 465–467.
31 G. L. Woolery, G. H. Kuehl, H. C. Timken, A. W. Chester and 55 I. J. Drake, Y. Zhang, M. K. Gilles, C. N. Teris Liu,
J. C. Vartuli, Zeolites, 1997, 19, 288–296. P. Nachimuthu, R. C. C. Perera, H. Wakita and A. T. Bell, J.
32 P. A. Jacobs and H. K. Beyer, J. Phys. Chem., 1979, 83, 1174– Phys. Chem. B, 2006, 110, 11665–11676.
1177. 56 T. H. Chen, B. H. Wouters and P. J. Grobet, Eur. J. Inorg.
33 U. Lohse, E. Löffler, M. Hunger, J. Stöckner and V. Patzelova, Chem., 2000, 2000, 281–285.
Zeolites, 1987, 7, 11–13. 57 A. Abraham, S.-H. Lee, C.-H. Shin, S. B. Hong, R. Prins and
34 X. Yi, K. Liu, W. Chen, J. Li, S. Xu, C. Li, Y. Xiao, H. Liu, J. A. van Bokhoven, Phys. Chem. Chem. Phys., 2004, 6,
X. Guo, S.-B. Liu and A. Zheng, J. Am. Chem. Soc., 2018, 3031–3036.
140, 10764–10774. 58 I. Kiricsi, C. Flego, G. Pazzuconi, W. O. Parker Jr, R. Millini,
35 M. Ravi, V. L. Sushkevich and J. A. van Bokhoven, Nat. C. Perego and G. Bellussi, J. Phys. Chem., 1994, 98, 4627–
Mater., 2020, 19, 1047–1056. 4634.
36 Z. Yu, S. Li, Q. Wang, A. Zheng, X. Jun, L. Chen and F. Deng, 59 J. Datka, B. Gil and A. Kubacka, Zeolites, 1997, 18, 245–249.
J. Phys. Chem. C, 2011, 115, 22320–22327.

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View Article Online

Edge Article Chemical Science

60 F. Moreau, P. Ayrault, N. S. Gnep, S. Lacombe, E. Merlen and 65 S. Grundner, M. A. C. Markovits, G. Li, M. Tromp,
M. Guisnet, Microporous Mesoporous Mater., 2002, 51, 211– E. A. Pidko, E. J. M. Hensen, A. Jentys, M. Sanchez-Sanchez
221. and J. A. Lercher, Nat. Commun., 2015, 6, 7546.
61 X. Li, R. Prins and J. A. van Bokhoven, J. Catal., 2009, 262, 66 J. Dědeček, E. Tabor and S. Sklenak, ChemSusChem, 2019, 12,
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

257–265. 556–576.
62 L. M. Kustov, V. B. Kazanskii, S. Beran, L. Kubelkova and 67 A. Bhan, A. D. Allian, G. J. Sunley, D. J. Law and E. Iglesia, J.
P. Jiru, J. Phys. Chem., 1987, 91, 5247–5251. Am. Chem. Soc., 2007, 129, 4919–4924.
63 S. Bordiga, E. E. Platero, C. O. Areán, C. Lamberti and 68 X. Yi, Y. Xiao, G. Li, Z. Liu, W. Chen, S.-B. Liu and A. Zheng,
A. Zecchina, J. Catal., 1992, 137, 179–185. Chem. Mater., 2020, 32, 1332–1342.
64 F. Wakabayashi, J. N. Kondo, K. Domen and C. Hirose, J. 69 Z. Liu, X. Yi, G. Wang, X. Tang, G. Li, L. Huang and A. Zheng,
Open Access Article. Published on 26 January 2021. Downloaded on 10/13/2021 8:16:46 AM.

Phys. Chem., 1995, 99, 10573–10580. J. Catal., 2019, 369, 335–344.

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