Perspective

https://doi.org/10.1038/s41563-020-0751-3

Towards a better understanding of Lewis acidic

aluminium in zeolites
Manoj Ravi   1, Vitaly L. Sushkevich2 and Jeroen A. van Bokhoven   1,2 ✉

Zeolites are a class of materials that are of great relevance for industrial catalysis. Several fundamental questions relating to
the structure and role of the Lewis acid sites in these materials remain unanswered. Proposals for the origin of such species can
broadly be classified into three categories, which have distinct structures: extra-framework, framework-associated and frame-
work aluminium. In this Perspective, we review each of these proposals and proceed to analyse their suitability to understand
experimental results. Contrary to traditional belief, the number of Lewis acid sites does not always correlate to extra-framework
aluminium content. As a result, we highlight that the terms ‘extra-framework’ and ‘framework-associated’ aluminium should
be used with caution. We propose how the usage of different characterization techniques can enable the closure of knowledge
gaps concerning the strength, multiplicity, localization and structure of catalytically active Lewis acid sites in zeolites.

Z
eolites constitute a class of heterogeneous catalysts for acid-,
base- and metal-catalysed reactions in several small- to
large-scale industrial applications. Their catalytic versatility is
due to the coexistence of aluminium and silicon in the framework1.
In a zeolite, framework aluminium is tetrahedrally coordinated with
four –O–Si linkages in accordance with Löwenstein’s rule, which
prohibits the presence of Al–O–Al motifs (Fig. 1)2. The presence
of aluminium in a framework position introduces a negative
charge to the framework that must be charge balanced by an
extra-framework cationic species. If the cation is a proton, this
results in formation of a hydroxyl group bridging aluminium and
silicon, forming a catalytically active Brønsted acid site3 (Fig. 1).
Consequently, zeolites have become the backbone of catalytic pro-
cesses in the petrochemical industry4, with application to some
prominent reactions, including fluid catalytic cracking (FCC)5,
methanol to olefins6, methanol to gasoline7 and hydroisomerization
of hydrocarbons8.
The possibility of hosting diverse active site motifs in zeolites,
which can be tuned for a particular application, means that the
industrial use of zeolites is unrivalled by other catalytic materi-
als. They can be used for the production of value-added chemicals
from oil derivatives, but also have the potential to be catalysts for a
biomass-based economy9. The active sites in biomass valorization
reactions involve both Brønsted and Lewis acidity; however, the
role of these sites is not well understood as of yet. Such coopera-
tive catalysis featuring both types of acidity often entails a multistep
conversion of biomolecules to valuable compounds. For example,
two such important cascade reactions are the conversion of glucose
to 5-hydroxymethylfurfural (HMF)10 and of C3 sugars to lactic acid
esters11. The former reaction comprises two steps, namely, isomeri-
zation of glucose to fructose, catalysed by Lewis acid sites, and dehy-
dration of fructose to HMF, catalysed by Brønsted acid sites. In this
regard, aluminium zeolites represent bifunctional catalysts as they
possess both Lewis and Brønsted acidity, showing high activity and
selectivity to HMF12. Elsewhere, Lewis acid sites are paramount in
modulating product selectivity in the dehydration of glycerol. Using
materials with a greater number of Lewis acid sites results in a lower
selectivity to acrolein and a higher selectivity to acetaldehyde13.
Hence, zeolites play a vital role in several catalytic applications in
biomass valorization chemistry.
Lewis acid sites in zeolites can be generated by introducing
heteroatoms, such as titanium, tin or zirconium, into the frame-
work (Fig. 1). Such acid sites are exploited to catalyse aldol con-
densation14 and propylene epoxidation15. Synthesis of tin- and
zirconium-doped Lewis acidic zeolites is often complicated16,17, as
obtaining isolated acid sites is not trivial and metal incorporation
has been proved only for a limited number of zeolite topologies18,19.
In contrast, Lewis acidic aluminium in zeolites can be formed with-
out tedious synthesis procedures and is not restricted to specific
zeolite topologies. However, unlike Brønsted acidity, the concept
of Lewis acidic aluminium in zeolites is still a grey area. While the
structure of the Brønsted acid site, described as the bridging OH
group in the Si–(OH)–Al unit (Fig. 1)3, is well defined, the same
cannot be said of Lewis acidic aluminium in zeolites. Evaluating
the structure and strength of Lewis acidic aluminium remains an
area of active research and discussion20–23. One of the reasons for
this uncertainty is the plurality of potential Lewis acid sites, aris-
ing from the structural versatility of aluminium that results in
many aluminium species. Aluminium with Lewis acidic character
may be generated through post-synthesis methods, such as steam-
ing, calcination at high temperature, and acid or base leaching24–27.
These treatments generally result in the hydrolysis of framework
Si–O–Al bonds, removing aluminium from the framework and
generating ‘extra-framework aluminium’ (EFAl) species with Lewis
acidity28. Moreover, Lewis acidic aluminium can also be a property
inherent to the zeolite framework20,21,23. Multiple proposals on the
structure and generation of Lewis acid sites have been advanced,
which can broadly be classified as originating from framework20,29,
framework-associated23,30 and extra-framework aluminium31,32.
Thus, Lewis acid sites in a zeolite are not necessarily defined by a
single structure, and the total Lewis acidity has contributions from
multiple species.
Numerous publications have discussed the concept of Lewis acid
sites in zeolites33–35. A number of different proposals on the origins
of Lewis acidity have been posited, but the suitability of each in
matching experimental data collected from many studies has not

Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland. 2Laboratory for Catalysis
1

and Sustainable Chemistry, Paul Scherrer Institute, Villigen, Switzerland. ✉e-mail: jeroen.vanbokhoven@chem.ethz.ch

Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials 1047

Perspective
Oil Biomass
FCC Glucose to fructose
Isomerization Fructose to HMF
Alkylation Glycerol to acrolein
Zeolites
? restores some of the Brønsted acid sites32,43. Increasing the severity
M = Sn, Zr, Ti
Framework aluminium Aluminium Lewis Framework metal
Brønsted acid sites acid sites Lewis acid sites
Fig. 1 | Zeolites, from acid sites to catalytic applications. A sketch showing
the structures of Brønsted and Lewis acid sites in zeolites and their relevant
applications in oil- and biomass-based processes.
been assessed. Through evaluation of published data and analysis of
the different mechanisms that generate Lewis acidic species, a better
understanding of Lewis acid sites in zeolites can be attained. From
a materials perspective, this would provide greater control over the
generation of Lewis acidic aluminium, paving a way towards the
currently elusive design of such sites in zeolites. From a process
perspective, this leaves a tangible impact on catalytic applications
based on Lewis acidic aluminium and Brønsted–Lewis acid synergy.
Finally, we proceed to identify knowledge gaps in the field and dis-
cuss how these may be addressed in the future. Even though there is
room for development, we believe that the tools necessary to attain
a comprehensive understanding are available, and through a con-
certed effort, breakthroughs are a real possibility.
Assessing the proposals for Lewis acidic aluminium in
zeolites
Herein, we review the different proposals for Lewis acidity in
zeolites, starting with Lewis acid sites originating from EFAl, and
progressing to those originating from framework-associated and
framework aluminium.
Lewis acidity of EFAl. The term ‘extra-framework aluminium’ is, by
convention, reserved to describe aluminium species that are ‘entirely’
dislodged from the zeolite framework. EFAl exists in several oxide
and hydroxide forms, such as Al(OH)2+, Al(OH)2+, AlOOH, Al2O3,
Al(OH)3 or multinuclear clusters (Box 1)27,36–38. In the ensuing discus-
sion, we refer to such species as ‘extra-framework’, while those that are
‘partially’ dislodged from the framework will be referred to as ‘frame-
work associated’ (vide infra). In addition, amorphous aluminosilicate
can also constitute extra-framework species, although their experi-
mental observation requires severe steaming/thermal treatment39.
One of the foremost publications to attribute EFAl debris to Lewis
acidic property is the work of Jacobs and Beyer, wherein Lewis acid
sites were shown to consist of Al–O species leached from the frame-
work of zeolite Y31. As performed in this study, Fourier transform
infrared (FTIR) spectroscopy of adsorbed bases is a familiar character-
ization technique to study acid sites in zeolites. The pre-treatment of
the sample before the adsorption of the base, which entails the heating
of the zeolite under vacuum at high temperatures, changes the struc-
ture of aluminium species. Thus, the structural information retrieved
by FTIR spectroscopy corresponds to that prevailing under activated,
dehydrated conditions and not at ambient conditions (Box 1).
Generation of EFAl and its experimental characterization.
Aluminium species external to the lattice are usually generated by
1048 Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
NAture MAterIALS
steaming, wherein water cleaves Si–O–Al linkages at high tempera-
ture to force aluminium into interstitial space27,40–42. There is a pre-
disposition to associate such EFAl with Lewis acidic property. While
this standpoint is not per se incorrect, there are caveats that need
to be considered. One of the first reports that characterized HY
zeolites dealuminated by steaming explicitly states that only a small
proportion of EFAl has acidic character43. Steaming leads to the
loss of Brønsted acid sites through irreversible framework dealu-
mination and reversible poisoning by cationic EFAl. In the case of
the latter, acid leaching of the steamed sample extracts EFAl and
of acid treatment increases the number of restored Brønsted acid
sites while simultaneously reducing the total number of Lewis acid
sites44. Therefore, EFAl does not refer to a single aluminium species
with Lewis acid character, but instead refers to a family of species
that are external to the zeolite lattice and have varying degrees of
acidity (Box 1).
In the case of dealuminated zeolite Y, Al(OH)3 and AlOH2+
have been identified as the extra-framework species38. 27Al
double-quantum magic angle spinning (MAS) NMR experiments
reveal tetrahedral framework aluminium, octahedral Al(OH)3 and
penta-coordinated extra-framework Al(OH)2+ and that they are all
in close proximity to one another (structures A, B and C, respectively,
in Fig. 2)27. 31P solid-state NMR of trimethylphosphine-adsorbed
zeolite Y and density functional theory calculations suggest
that the strongest Lewis acid sites in dealuminated zeolites are
three-coordinated EFAl (structure D in Fig. 2)45. Periodic density
functional theory calculations reveal a thermodynamic preference
for the formation of multinuclear [Al3O4H3]4+ extra-framework
clusters inside the sodalite cage in faujasite (FAU); however, this
remains to be experimentally confirmed46,47.
Our analysis of published data establishes that there is no cor-
relation between the amount of EFAl and the number of Lewis acid
sites in zeolites (Box 1). Therefore, it becomes apparent that trivially
associating EFAl with Lewis acid property is a fallacious argument.
While certain EFAl species undeniably possess Lewis acid character,
the underlying heterogeneity of EFAl debris must not be overlooked.
The classification of aluminium as ‘framework’ or ‘extra-framework’
is commonly done on the basis of 27Al MAS NMR spectra acquired
on wet non-dehydrated samples. In contrast, Lewis acidity is typi-
cally assessed after dehydrating the zeolite, which often affects
the intrinsic structure of the aluminium sites (Box 1). The term
‘extra-framework aluminium’ constitutes a range of aluminium spe-
cies with largely varying acidic properties. Its structure and acidic
properties are influenced by several factors that include the Si/Al
ratio of the zeolite and the method used for dealumination (Box 2).
Lewis acidity of framework-associated aluminium. As opposed
to EFAl, the term ‘framework associated’ refers to species that
are not entirely dislodged from the zeolite framework (Fig. 2).
Framework-associated aluminium adopts a tetrahedral or an
octahedral geometry as a function of conditions and can undergo
reversible transformation from one coordination to the other
(structures A, E, F and G in Fig. 2)48–51. On being charge balanced
by cations such as sodium, potassium and ammonium, this alumin-
ium species assumes a tetrahedral coordination (27Al chemical shift
around 60 ppm) in the hydrated form of the zeolite, and an octa-
hedral environment (27Al chemical shift around 0 ppm) on being
charge balanced by protons23,30,48–50. The property of this species to
fit back into a tetrahedral framework coordination after being at
least partially dislodged from the framework suggests that it has a
memory of its native position, thereby intuitively justifying the epi-
thet ‘framework-associated’ aluminium. Specific T-sites are more
prone to exhibit this phenomenon than others41 and the amount of
framework-associated aluminium depends on the zeolite structure
and Si/Al ratio23,52.
NAture MAterIALS
Box 1 | Correlating EFAl to Lewis acidic property
In the graph below, we collate data from published literature for
the correlation between the number of Lewis acid sites and the
amount of EFAl in different zeolites26,28,85,89,90. Interestingly, a cor-
relation between the two quantities, one that is often assumed
to exist, does not hold for most cases. While some species of the
extra-framework phase are Lewis acidic, not all are. Therefore,
a zeolite with more EFAl content does not necessarily possess a
greater number of Lewis acidic species. Consider as an example,
the experiments with dealuminated HY91. The zeolite steamed at
973 K has a framework Si/Al ratio of 15 and a bulk ratio of 2.4. The
presence of Lewis acidic species in the sample is evidenced by an
infrared band at 1,455 cm–1 on being probed by pyridine. Treating
the zeolite in 1.5 M HCl results in the framework Si/Al ratio re-
maining unchanged, but the bulk Si/Al ratio increases to 6.7. Thus,
a substantial amount of EFAl is leached out by acid treatment, but
the framework composition remains unaffected. However, this
sample with lower EFAl content shows a more intense infrared
feature for Lewis-bound pyridine91. Besides eliminating cationic
species located in the supercages91, the acid treatment modulates
the number of Lewis acid sites by manipulating EFAl species gen-
erated during steaming, or inducing framework-based Lewis acid-
ity (vide infra), or a combination of both. However, dealuminat-
ing USY using citric acid instead of steaming, generates EFAl that
linearly correlates to the number of sites that show Lewis acidic
property (green points)89. The opposite trend is observed while
steaming H-BEA at 753 K (orange points)85. Herein, the popula-
tion of octahedral EFAl barely increases upon steaming, with the
more pronounced changes occurring to tetrahedral EFAl. Of the
Measurements of Al coordination
• Three-coordinated
• Tetrahedral (Td)
• Penta-Coordinated
• Octahedral (Oh)
Techniques
• 27Al MAS NMR
• AI K-edge XAS
• XPS (Al KLL peak)
Typical experimental conditions
• In hydrated state
for 27Al MAS NMR
Framework-associated aluminium
Linking acidity and coordination to structure
Number of Lewis acid sites (a.u.)
Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
Perspective
two tetrahedral EFAl species characterized by chemical shifts of
44 and 63 ppm in 27Al MAS NMR, the fraction of aluminium spe-
cies associated with the former resonance falls substantially on
steaming85. These results suggest that besides displacing alumini-
um from the framework, steaming transforms the nature of EFAl,
thereby influencing its acidity. This serves as another example to
illustrate the pitfall of assuming all of EFAl as Lewis acidic.
An important proviso that applies while correlating a particular
aluminium species to Lewis acidic property comes from the
characterization method used to probe Lewis acid sites. The
plurality of acid sites and their varying strengths are reflected
differently in different techniques. Consider as an example, the
study of Lewis acidity by a rather exotic method like electron
paramagnetic resonance spectroscopy of adsorbed nitric oxide.
This technique only probes sites that are strong enough to quench
the orbital magnetic moment of nitric oxide. The number of such
strong Lewis acid sites increases initially with the amount of EFAl,
and then tapers off with further increase in EFAl (grey points)28.
This trend does not hold when probing the same samples by
FTIR spectroscopy of adsorbed carbon monoxide28. Hence, the
sensitivity to a particular Lewis acid species is fundamentally
different from one technique to another.
The figure shows the structural models for different aluminium
species: framework2,3, extra-framework27,36–38 and framework-
associated aluminium (inspired from refs. 27,50). Experimental
techniques and typical conditions during measurement of
aluminium structure and acidity are listed in blue text boxes. The
curation of data for the number of Lewis acid sites as a function
Structural models Measurements of Al acidity
Framework aluminium • Lewis acid sites
• Brønsted acid sites
Techniques
• FTIR of adsorbed probe
Extra-framework aluminium molecules
• Structure-sensitive
reactions
Typical experimental conditions
• After dehydration in
vacuum or dry gas
Amount of EFAI (a.u.)
1049
Perspective NAture MAterIALS

Box 1 | Correlating EFAl to Lewis acidic property (continued)

of EFAl for different zeolite topologies with the colour codes The amount of Lewis acid sites and EFAl are reported in different
and corresponding references is as follows: blue26, grey28, units in these studies: either on a relative or absolute quantitative
green89, orange85 and purple90. Scatter points from different basis. Hence, the plot is presented with both axes being labelled as
studies are offset for clarity and thus cannot be directly compared. arbitrary units.

Extra-framework aluminium D

Extra-framework LAS

High temperature, vacuum

B C M N

EFAI: octahedral EFAI: penta-coordinated EFAI: tetrahedral Other neutral and cationic EFAI

High Very high Very high Steaming,

temperature temperature temperature acid leaching
H2O, RT H2O, RT H2O, RT Calcination

Framework Al
J A L K
High High
temperature, temperature,
Base, vacuum vacuum vacuum

Framework AI expanding coordination Framework AI with BAS Framework LAS Distorted framework AI

Framework-associated Al H2O, RT H2O, RT

E F

High
temperature,
vacuum

Framework-associated AI: octahedral NH4+ NH3 Framework-associated AI: octahedral

exchange adsorption
H2O, RT G H2O, RT

High temperature, vacuum

>383 K –H2O

Framework AI

I H

High temperature, vacuum

Framework-associated AI: tetrahedral Framework-associated LAS

Fig. 2 | A summary of the current understanding of Lewis acidic aluminium in zeolites. Pathways showing the changes in aluminium structure with
changing conditions and classification of Lewis acidic aluminium as originating from extra-framework27,36–38,89, framework-associated23,27,30,50 and framework
aluminium20,30,34,63. All structures in the figure except for structure K have been reported in FAU. Structure K has been reported in chabazite20. Many
transformations sketched above have been observed in zeolites beyond FAU as well. For the specific zeolite types, refer to the references cited above. LAS,
Lewis acid site; RT, room temperature.

We demonstrated with experiments on zeolite mordenite (MOR) the zeolite, is associated with Lewis acidic character when exam-
that framework-associated aluminium, which adopts an octahe- ined after high-temperature dehydration (structure H in Fig. 2)23.
dral coordination under ambient conditions in the proton form of A linear correlation between the number of Lewis acid sites and

1050 Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials

NAture MAterIALS
Box 2 | Factors regulating the Lewis acidity of EFAl
EFAl in zeolites can be generated by different methods, such as
high-temperature calcination, steaming, acid treatment or other
post-synthesis approaches. The so-formed EFAl comprises a num-
ber of different aluminium species, all of which are completely dis-
lodged from the framework. However, not all of these species are
Lewis acidic. By curating examples from published literature, we
illustrate three factors that regulate the Lewis acidic property of
EFAl. The qualitative dependence of the amount of EFAl on these
factors is shown in the graphs in the figure.
Si/Al ratio. The Si/Al ratio influences the properties of the
aluminium species displaced from the framework upon steaming.
For instance, steaming of a low-aluminium H-ZSM-5 (Si/Al = 45)
results in EFAl with weak acidity and no strong Lewis acid sites92.
In contrast, steaming of H-ZSM-5 with greater aluminium content
(Si/Al = 18) generates Lewis acid sites that are strong enough to
polarize paraffin molecules40. These sites are responsible for the
dehydrogenation step in the cracking of alkanes93. In more recently
discovered mesoporous aluminosilicates, such as AlTUD-1, there
are several different types of EFAl and Lewis acid sites. While
the extra-framework species include penta- and octahedrally
coordinated aluminium, FTIR spectroscopy of adsorbed pyridine
does not always reveal the multiplicity in Lewis acid sites94.
For AlTUD-1 with a Si/Al ratio of 25, the infrared feature for
Lewis-bound pyridine is sharp, while for samples with a Si/Al ratio
in the range of 50 to 75, the feature is much broader and manifests
in the form of two partially overlapping peaks94.
Method used for dealumination and post-synthesis treatment.
EFAl generated by steaming cannot be removed even after
multiple ammonium-exchange treatments24, but dealumination
performed with silicon tetrachloride results in aluminium species
that can be removed by ammonium exchange95. Dealuminating
zeolite BEA by steaming yields a single kind of Lewis acid site
characterized by an infrared feature at 1,456 cm–1 upon interaction
with pyridine, but dealumination using hydrochloric acid or
ammonium hexafluorosilicate yields a second kind of Lewis acid
site, which shows an additional infrared feature at 1,446 cm–1
(ref. 26). Similarly, two kinds of Lewis acid site bound to pyridine
the amount of framework-associated octahedral aluminium was
attained with two probe molecules of contrasting size and strength:
carbon monoxide and pyridine. The amount of octahedral alumin-
ium, and consequently, the number of Lewis acid sites, decreases
with increasing Si/Al ratio of the zeolite. The aluminium content
also influences the plurality of Lewis acid sites23. The Lewis acid
character of three-coordinate aluminium sites in protonic zeolites
may be masked when the local topology permits such aluminium
to expand its coordination through an extra bond to the framework
oxygen atom53. While edingtonite is illustrative of a zeolite topol-
ogy that allows masking to occur rather easily, other zeolites such as
beta (BEA), Zeolite Socony Mobil–5 (MFI) and MOR, do not offer a
favourable environment for under-coordinated aluminium to bind
with the aluminosilicate-framework oxygen atom53.
Zeolite SSZ-33, which possesses octahedral framework-associated
species, shows a prominent infrared signature for Lewis acid
sites when probed by pyridine30. On average, there is more than
one Lewis acid site per unit cell of SSZ-33. This corroborates the
assignment of framework-associated aluminium to Lewis acidity.
Also, the evolution of the structure of framework-associated alu-
minium can be monitored through changes in Brønsted acidity. The
infrared spectrum of NH4–Y after heat treatment and ammonia
Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
Perspective
are observed in Al-SBA-3 synthesized via a post-synthesis
modification of Si-SBA-3 using sodium aluminate. Analysis of the
strengths of these sites is realized by evacuating pyridine at different
temperatures96. Samples produced via a post-synthetic alumination
procedure of TUD-1 with a higher amount of EFAl does not result
in a greater number of Lewis acid sites97. While incorporating
more aluminium through post-synthesis modification results in
more five- and six-coordinated EFAl in TUD-1, the total number
of Lewis acid sites decreases97. Therefore, the post-synthesis
modification of TUD-1 using aluminium isopropoxide generates
non-Lewis acidic EFAl at high aluminium loadings. Modulating
the steaming temperature influences the extent to which neutral
or cationic aluminium species are produced43,98, with the
probability of generating extra-framework species with a high
cationic charge decreasing with the severity of the steaming
treatment62. This apart, the structure of extra-framework species
evolves during acid leaching. Aluminium species characterized
by a signal at about 30 ppm in the 27Al MAS NMR spectrum is
the most vulnerable to acid treatment. While the population of
this species diminishes strongly, the peak shape and intensity
of the feature centred at a chemical shift of around 0 ppm also
change markedly44.
Nature of co-cation. High-temperature treatment of ammonium
and proton forms of zeolites with subsequent exposure to ambient
conditions generally results in a substantial fraction of aluminium
species adopting an octahedral coordination48. However, such
octahedrally coordinated EFAl is usually not observed with zeolites
having sodium or potassium as the charge-compensating cation30,99.
Steaming
Si/Al ratio temperature Co-cation
EFAI
EFAI
EFAI
Si/Al Temperature Na+, Cs+ NH4+, H+
removal shows absorption bands centred at 3,640 cm–1 and 3,545
cm–1, assigned to bridging hydroxyl groups in the super cages and
sodalite cages, respectively54. This sample has all of its aluminium
in a framework tetrahedral coordination (boxed structure A in
Fig. 2). Calcination to the proton form and subsequent exposure
to ambient conditions transforms a fraction of aluminium into the
octahedral coordination (structures E and F in Fig. 2). On evacua-
tion of such HY under vacuum, the infrared features attributed to
Brønsted acidity diminish strongly54. Therefore, the generation of
Lewis acidic framework-associated aluminium is concomitant with
the degeneration of Brønsted acid sites, implying a conversion of
Brønsted to Lewis acid sites.
Distinguishing framework-associated aluminium from EFAl. The
concept of octahedral aluminium insertion into a framework
coordination was first illustrated with zeolite BEA48 and has been
extended to many different zeolites since then23,30,50. Distinguishing
framework-associated aluminium from EFAl, with both of them
being able to adopt an octahedral coordination, can be challeng-
ing. Herein, we highlight specific examples where such a rigorous
distinction has been illustrated. As a first example, consider the
evolution of aluminium structure in SSZ-33 studied by 27Al MAS
1051
Perspective
NMR30. Calcining the zeolite to the proton form results in a sub-
stantial number of octahedral sites under ambient conditions30,
with the appearance of a sharp and a broad feature in the range of
0 to −20 ppm. Converting this sample into the ammonium form
virtually eliminates all octahedral species30. The enhanced inten-
sity of the peak associated with tetrahedral aluminium suggests
that most of the octahedral sites were transformed into framework
aluminium. On calcining this sample and subsequently exposing it
to ambient conditions, the sharp octahedral feature at 0 ppm reap-
pears30. Thus, this sharp feature represents aluminium species that
undergoes reversible tetrahedral–octahedral coordination, which is
the inherent feature of framework-associated aluminium. Likewise,
it has been demonstrated that octahedral aluminium species char-
acterized by a sharp resonance at 0 ppm in zeolite BEA represents
flexible lattice aluminium that can be forced back to a tetrahedral
environment49. Therefore, the fundamental criteria to distinguish
framework-associated aluminium from extra-framework species
must be based on reversible octahedral–tetrahedral coordination,
where the restored tetrahedral structure is comparable to that of
pristine tetrahedral framework aluminium. While such reversibil-
ity in coordination has been mostly demonstrated through NMR,
X-ray photoelectron spectroscopy has independently corroborated
this phenomenon55. Tetrahedral, octahedral and three-coordinated
aluminium have been identified in zeolite BEA using X-ray pho-
toelectron spectroscopy56,57. Furthermore, in situ X-ray absorption
spectroscopy (XAS) reveals that octahedral framework-associated
aluminium changes into a tetrahedral geometry on heating the zeo-
lite to temperatures above 383 K (structure I in Fig. 2)50,58.
High-temperature calcination of zeolite Y yields framework-
associated aluminium, which is three-coordinated to the framework
and coordinated to three water molecules (structure F in Fig. 2)59,60.
The adsorption of ammonia can convert this octahedral species to
a tetrahedral geometry (structure G in Fig. 2)27. However, increas-
ing the severity of the thermal treatment results in the formation of
octahedral extra-framework Al(OH)3 species (equations (1)–(3)),
whose coordination cannot be reversed by ammonia adsorption61.
Likewise, reversible aluminium coordination changes can also be
realized in steamed zeolites. The use of a higher pressure of water
vapour during steaming degrades more than 75% of the bridging
hydroxyl groups, but ammonia treatment restores a substantial frac-
tion of these acid sites62. While steaming is traditionally viewed as a
technique to generate genuinely EFAl, some of the octahedral alu-
minium, even in a strongly steamed zeolite can be inserted back
into the framework. Therefore, counting all octahedral aluminium
as EFAl is erroneous.
Al3þ þ H2 O þ ðSi2O2AlÞ� ! AlOH2þ þ Si2OðHÞ2Al ð1Þ
AlOH2þ þ H2 O þ ðSi2O2AlÞ� ! AlðOHÞþ
2 þ Si2OðHÞ2Al
ð2Þ
AlðOHÞþ �
2 þ H2 O þ ðSi2O2AlÞ ! AlðOHÞ3 þ Si2OðHÞ2Al
ð3Þ
The term ‘extra-framework aluminium’ has often been used in
a way that does not distinguish species entirely dislodged from the
framework from partially dislodged framework-associated species.
Consequently, apprehension of trends for the number of Lewis acid
sites (Box 1) is not straightforward. This calls for a more judicious
usage of the terms ‘extra-framework’ and ‘framework associated’
aluminium.
Lewis acidity of framework aluminium. Lewis acidity originating
from framework aluminium is poorly understood. A tetrahedral
1052 Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
NAture MAterIALS
aluminium atom that is part of the framework is not under-
coordinated and cannot be intuitively envisioned as a Lewis acid
site. However, multiple reports pointing to framework-based Lewis
acidity exist20,30,34. The origin of these acid sites can be framework
aluminium or defects in the framework, including those created by
dehydroxylation of bridging hydroxyl groups63.
Aluminium ions can take several coordination environments,
ranging from tetrahedral and penta-coordination to octahedral
geometry. It is hypothesized that framework tetrahedral aluminium
can act as a Lewis acid site by expanding its coordination to five
on interaction with a base such as pyridine (structure J in Fig. 2)34.
While this is yet to be experimentally established, the model is built
on the premise that the access of a basic molecule to a framework
aluminium atom is hindered by the strongly competitive interaction
of the base with a nearby proton21,34. However, the interaction of
the base with framework aluminium can be facilitated if the bridg-
ing OH group is in one cavity and the base can attack aluminium
from the opposite side. For example, pyridine can probe aluminium
through the supercage if the OH group is localized in the sodalite
cage in zeolite Y34.
Lewis acidity can also arise from perturbed or distorted frame-
work aluminium. In ferrierite and chabazite zeolites, perturbed
framework aluminium species are proposed to be (SiO)3AlOH
groups (structure K in Fig. 2), which result in the broadening
of the 27Al MAS NMR line shape at around 40 ppm (ref. 20).
These species dehydroxylate at relatively mild temperatures
yielding three-coordinated Lewis acidic aluminium (structure L
in Fig. 2)20.
Studying Lewis–Brønsted synergy in zeolites. There are many dif-
ferent possible origins for Lewis acidic aluminium in zeolites, and
as elaborated above, it is necessary to be scrupulous to differenti-
ate between the different types of Lewis acid sites. This is relevant
not only for reactions that are catalysed only by Lewis acid sites
but also for applications that exploit the synergy between Lewis
and Brønsted acid sites, which can enhance catalytic properties in,
for example, dealuminated zeolites64. The enhanced activity in the
conversion of hydrocarbons was initially attributed to several fac-
tors, namely the stabilization of the negative charge on the lattice
due to the EFAl species65, the polarization of reactants by Lewis
acid sites40 and the confinement effects of zeolite pores66. At pres-
ent, the working hypothesis is that the synergy between Brønsted
and Lewis acid sites is due to the close location of both sites in
the zeolite pore27,67,68. The proximity of Brønsted and Lewis acid
sites is experimentally confirmed in qualitative terms, primarily
through two-dimensional double-quantum MAS NMR spectros-
copy. However, more precise information on the location of dif-
ferent EFAl species (structures B, C, M and N in Fig. 2) has not
been established, which is highly desirable from a fundamental and
a practical point of view. Furthermore, the challenges in demar-
cating truly EFAl species from framework-associated aluminium
sites and three-coordinated aluminium with adsorbed water, all of
which take up octahedral geometry, severely hampers the analysis
of Lewis–Brønsted synergy41,60.
Conclusions and outlook
A close analysis of the assortment of proposals for Lewis acidic
aluminium in zeolites uncovers fundamental differences. While
attributing Lewis acidic property to EFAl is a widely accepted con-
jecture, the literature data reveal that in many cases a correlation
between the amount of EFAl and the number of Lewis acid sites
does not hold. From this, we identify inconsistencies in the usage
of the term ‘extra-framework aluminium’, and note that distinguish-
ing framework-associated aluminium from EFAl is paramount.
The properties of different aluminium species are liable to change
on sample treatment. Publications that discuss how the relative
NAture MAterIALS Perspective
Structure under catalytically Lewis and Brønsted sites: Relative strength and location Rational synthesis of Lewis acid sites
relevant conditions interconversion and synergy of Lewis acid sites

NMR Si Si Si
Reactant Product Al Si Al Al Al Si
FTIR
– – – Si Si Si Si Si Al
– Solvent – Si Si Si
–

In situ and operando Probe molecules of Controlling aluminium distribution

characterization: NMR and FTIR different sizes and basicity and thermal treatment
FTIR, NMR and XAS Probe molecules desorbed Theory under relevant conditions
at different temperatures and dynamics

Study evolution of aluminium structure from precursor species to aluminium Lewis site

In situ XRD
and XAS. Framework Al with BAS
FTIR and
Temperature

NMR

Ad
at

Co ate

Co bas
hy

so
He

Under-coordinated AI

ol

ol
dr

rb
Framework Al EFAl

e
Framework-associated Al

Fig. 3 | Future research directions on Lewis acidic aluminium in zeolites. A summary of the expected developments, featuring a list of the most pressing
questions that need to be answered and the techniques that could be used to address them. BAS, Brønsted acid site.

quantities of framework-associated and EFAl change on sample
treatment are scarce, with the understanding of the changes that
occur in the number, location and structure of Lewis acidic alumin-
ium on changing synthesis conditions remaining abstruse.
Structure under catalytically relevant conditions. While the
chemical structures of Lewis acidic aluminium species have been
reported in both dehydrated environments and under ambient
conditions, there is a pressing need to study aluminium structure
under relevant reaction conditions through in situ and operando
characterization (Fig. 3). In this context, in situ XAS and X-ray dif-
fraction (XRD) are two techniques that can track the evolution of
aluminium structure and distinguish between species that are par-
tially or entirely dislodged from the framework. XAS can reveal
the presence of tetrahedral, octahedral and under-coordinated
aluminium during all stages of the zeolite treatment58,60, while
Rietveld refinement of XRD patterns can identify migration of
aluminium to extra-framework positions and reveal occupancy
of extra-framework cations as a function of temperature42. The
removal of aluminium from the framework should be reflected by a
decrease in the d-spacing, but since framework-associated alumin-
ium is only partially dislodged from the framework, it is expected
to show a slightly different decrease. However, the difference can
be very small69,70, making detection and interpretation challenging.
Correlations between the number of Lewis acid sites and activ-
ity in a reaction are well established, but a deeper understanding of
the effect of active site structure is missing. Admittedly, elaboration
of this structure-to-performance relationship requires advanced
characterization methods that enable in situ characterization. MAS
NMR spectroscopy with double and triple quantum resonance
enables the study of proximity and anisotropy of aluminium sites
that are associated with Brønsted and Lewis acidity71. Furthermore,
due to the high symmetry of aluminium sites in a solvent-containing
environment, which leads to substantial narrowing of NMR signals,
the use of these techniques can be naturally extended to study active
sites under ‘working’ reaction conditions. This can aid in better
analysis of the mechanism of interconversion of extra-framework
and framework-associated aluminium sites.
Interconversion and synergy between Lewis and Brønsted acid
sites. The precise characterization of diverse aluminium Lewis acid
sites, as well as their proximity and interaction with Brønsted acid
sites and the zeolite framework, are of primary importance. While
27
Al MAS NMR and FTIR spectroscopy can estimate the total num-
ber of Lewis acid sites21,23,30,72, they are barely sensitive to the strength
or structure of the acid sites. Furthermore, both these techniques
are not entirely robust under all conditions. For instance, 27Al MAS
NMR is challenging to execute under dehydrated conditions, where
highly distorted aluminium local environments occur and are diffi-
cult to detect. In this context, measuring NMR on other nuclei, such
as 1H and 29Si, including two-dimensional correlation spectros-
copy, can shed light on the local aluminium environment. Another
rapidly developing branch of NMR spectroscopy is the analysis of
adsorbed probe molecules through 13C, 15N and 31P nuclei, which
directly accesses the acidity of aluminium centres. 27Al–31P or
27
Al–15N rotational-echo, double-resonance (REDOR) and transfer
of population in double-resonance (TRAPDOR) experiments can
be used to identify and quantify Brønsted and Lewis acid sites when
trimethylphosphine and pyridine are used as probe molecules,
respectively73,74. Recently, low-temperature 15N dynamic nuclear
polarization surface-enhanced NMR spectroscopy of adsorbed
pyridine revealed the plurality of acid sites in ɣ-alumina and has a
high potential for studying zeolites75. REDOR may also be used to
measure Al–N bond distances to evaluate the binding of the probe
molecule to Lewis acid sites76. Likewise, insensitive nuclei enhance-
ment by polarization transfer (INEPT) is another two-dimensional
correlation experiment that helps elucidate the coordination num-
ber of Lewis acid sites77.
Relative strength and location of Lewis acid sites. Infrared spec-
troscopy of adsorbed probe molecules remains an extensively
used technique to study acid sites in zeolites. However, pyridine,

Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials 1053

Perspective
which is an often-used probe molecule, is a strong and unselec-
tive base, making the differentiation of Lewis acid sites of similar
acidity impossible. In contrast, weaker bases, such as nitrogen and
carbon monoxide, are capable of differentiating multiple Lewis
acid sites, including three-coordinated and octahedral aluminium
species28,78,79. Tin and zirconium sites in zeolites selectively inter-
act with acetonitrile, and likewise, aluminium species can be dif-
ferentiated using FTIR spectroscopy of adsorbed nitriles80. The
use of nitriles with alkyl groups of varying basicity and size, such
as acetonitrile, pivalonitrile and benzonitrile, makes it plausible to
assess the relative strength and location of aluminium Lewis acid
sites (Fig. 3). Similar insights can be achieved by combining infra-
red spectroscopy with temperature-programmed desorption of
probe molecules81. Likewise, ultraviolet–visible diffuse reflectance
spectroscopy of zeolites adsorbed with molecules, such as naphtha-
lene82, is another tool to study acid sites83. However, this technique
has not been able to reveal the origin of Lewis acid sites, or deter-
mine whether these sites are inherent to the zeolite or are genuinely
extra-framework82.
A special emphasis should be placed on the correlation of data
obtained using infrared spectroscopy with catalytic data and NMR,
as the NMR data are typically obtained for air-exposed samples,
while infrared measurements are done after complete dehydration
in vacuum. This discrepancy should be mitigated, by, for instance,
measuring multiple-quantum MAS NMR, or related techniques,
for dehydrated samples84, or infrared spectra for materials with
pre-adsorbed water23. Such experiments bridge the gap between
Lewis acid sites present under reaction conditions and those
detected by conventional spectroscopic methods under starkly dif-
ferent conditions. NMR and FTIR spectroscopy are largely focused
on studying the final structure of Lewis acidic aluminium bonded
to a basic probe molecule. Therefore, one of the limitations of these
techniques is that it only provides partial information, often of the
initial and final structures, while being largely blind to the evolution
in aluminium structure during sample pre-treatment. Techniques
that are more robust and can be used in an in situ, time-resolved
fashion need to be harnessed.
Rational synthesis of Lewis acid sites. Steaming at high tem-
perature was one of the first methods used to generate Lewis acid
sites in aluminium-containing zeolites, with later on other de- and
re-alumination methods23,30,85–87 being used. These are all simple and
inexpensive procedures, which can be easily implemented for zeo-
lites of any topology and Si/Al ratio. The formation of Lewis acid
sites of a certain strength and specific location in the pore struc-
ture of a zeolite is governed by the distribution of aluminium in the
framework. Therefore, the control of aluminium distribution, mor-
phology and presence of defects in the parent zeolite88 dictates the
quality of the final Lewis acid sites (Fig. 3). Headway in the rational
synthesis of Lewis acidic zeolites, complemented by a methodical
characterization of the active sites, will help to resolve unanswered
aspects of catalytic applications that exploit Lewis acid sites in zeo-
lites. Knowledge of structural proximity and structure under reac-
tion conditions will greatly contribute to understanding the role of
Lewis acid sites in catalysis by zeolites.
Received: 22 October 2019; Accepted: 29 June 2020;
Published online: 21 September 2020
References
1. Barrer, R. M. Hydrothermal Chemistry of Zeolites Vol. 269 (Academic Press,
1982).
2. Fyfe, C. A., Gobbi, G. C., Klinowski, J., Thomas, J. M. & Ramdas, S. Resolving
crystallographically distinct tetrahedral sites in silicalite and ZSM-5 by
solid-state NMR. Nature 296, 530–533 (1982).
3. Haag, W. O., Lago, R. M. & Weisz, P. B. The active site of acidic
aluminosilicate catalysts. Nature 309, 589–591 (1984).
1054 Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
NAture MAterIALS
4. Martínez, A., Prieto, G., García‐Trenco, A. & Peris, E. in Zeolites and
Catalysis: Synthesis, Reactions and Applications (eds Čejka, J., Corma, A. &
Zones, S.) 649–685 (Wiley, 2010).
5. Vogt, E. T. C. & Weckhuysen, B. M. Fluid catalytic cracking: recent
developments on the grand old lady of zeolite catalysis. Chem. Soc. Rev. 44,
7342–7370 (2015).
6. Tian, P., Wei, Y., Ye, M. & Liu, Z. Methanol to olefins (MTO): from
fundamentals to commercialization. ACS Catal. 5, 1922–1938 (2015).
7. Bjørgen, M. et al. Methanol to gasoline over zeolite H-ZSM-5: improved
catalyst performance by treatment with NaOH. Appl. Catal. A 345,
43–50 (2008).
8. Minachev, K. M., Garanin, V. I., Kharlamov, V. V., Isakova, T. A. & Senderov,
E. E. Catalytic properties of synthetic mordenite in the isomerization,
hydrogenation, and hydroisomerization of certain hydrocarbons. Russ. Chem.
Bull. 18, 1611–1615 (1969).
9. Jacobs, P. A., Dusselier, M. & Sels, B. F. Will zeolite‐based catalysis be as
relevant in future biorefineries as in crude oil refineries? Angew. Chem. Int.
Ed. 53, 8621–8626 (2014).
10. Moreno-Recio, M., Santamaría-González, J. & Maireles-Torres, P. Brönsted
and Lewis acid ZSM-5 zeolites for the catalytic dehydration of glucose into
5-hydroxymethylfurfural. Chem. Eng. J. 303, 22–30 (2016).
11. Dapsens, P. Y., Mondelli, C. & Pérez-Ramírez, J. Design of Lewis-acid centres
in zeolitic matrices for the conversion of renewables. Chem. Soc. Rev. 44,
7025–7043 (2015).
12. Otomo, R., Yokoi, T., Kondo, J. N. & Tatsumi, T. Dealuminated Beta zeolite as
effective bifunctional catalyst for direct transformation of glucose to
5-hydroxymethylfurfural. Appl. Catal. A 470, 318–326 (2014).
13. Suganuma, S., Hisazumi, T., Taruya, K., Tsuji, E. & Katada, N. Influence of
acidic property on catalytic activity and selectivity in dehydration of glycerol.
ChemistrySelect 2, 5524–5531 (2017).
14. Lewis, J. D., Van de Vyver, S. & Román‐Leshkov, Y. Acid–base pairs in Lewis
acidic zeolites promote direct aldol reactions by soft enolization. Angew.
Chem. Int. Ed. 127, 9973–9976 (2015).
15. Perego, C., Carati, A., Ingallina, P., Mantegazza, M. A. & Bellussi, G.
Production of titanium containing molecular sieves and their application in
catalysis. Appl. Catal. A 221, 63–72 (2001).
16. Hammond, C., Conrad, S. & Hermans, I. Simple and scalable preparation of
highly active Lewis acidic Sn‐β. Angew. Chem. Int. Ed. 51, 11736–11739 (2012).
17. Sushkevich, V. L., Ivanova, I. I. & Taarning, E. Ethanol conversion into
butadiene over Zr-containing molecular sieves doped with silver. Green.
Chem. 17, 2552–2559 (2015).
18. Astorino, E., Peri, J. B., Willey, R. J. & Busca, G. Spectroscopic characterization
of silicalite-1 and titanium silicalite-1. J. Catal. 157, 482–500 (1995).
19. Corma, A., Domine, M. E., Nemeth, L. & Valencia, S. Al-free Sn-beta zeolite
as a catalyst for the selective reduction of carbonyl compounds (Meerwein–
Ponndorf–Verley reaction). J. Am. Chem. Soc. 124, 3194–3195 (2002).
20. Brus, J. et al. Structure of framework aluminum Lewis sites and perturbed
aluminum atoms in zeolites as determined by 27Al{1H} REDOR (3Q) MAS
NMR spectroscopy and DFT/molecular mechanics. Angew. Chem. Int. Ed. 54,
541–545 (2015).
21. Busca, G. Acidity and basicity of zeolites: a fundamental approach.
Microporous Mesoporous Mater. 254, 3–16 (2017).
22. Zhang, Y. et al. Promotion of protolytic pentane conversion on H-MFI zeolite
by proximity of extra-framework aluminum oxide and Brønsted acid sites.
J. Catal. 370, 424–433 (2019).
23. Ravi, M., Sushkevich, V. L. & van Bokhoven, J. A. Lewis acidity
inherent to the framework of zeolite mordenite. J. Phys. Chem. C. 123,
15139–15144 (2019).
24. Klinowski, J., Fyfe, C. A. & Gobbi, G. C. High-resolution solid-state nuclear
magnetic resonance studies of dealuminated zeolite Y. J. Chem. Soc. Faraday
Trans. 1 81, 3003–3019 (1985).
25. Bevilacqua, M. & Busca, G. A study of the localization and accessibility of
Brønsted and Lewis acid sites of H-mordenite through the FT-IR spectroscopy
of adsorbed branched nitriles. Catal. Commun. 3, 497–502 (2002).
26. Marques, J. P. et al. Infrared spectroscopic study of the acid properties of
dealuminated BEA zeolites. Microporous Mesoporous Mater. 60, 251–262 (2003).
27. Yu, Z. et al. Insights into the dealumination of zeolite HY revealed by
sensitivity‐enhanced 27Al DQ‐MAS NMR spectroscopy at high field. Angew.
Chem. Int. Ed. 49, 8657–8661 (2010).
28. Catana, G., Baetens, D., Mommaerts, T., Schoonheydt, R. A. & Weckhuysen,
B. M. Relating structure and chemical composition with lewis acidity in
zeolites: a spectroscopic study with probe molecules. J. Phys. Chem. B 105,
4904–4911 (2001).
29. Woolery, G. L., Kuehl, G. H., Timken, H. C., Chester, A. W. & Vartuli, J. C.
On the nature of framework Brønsted and Lewis acid sites in ZSM-5. Zeolites
19, 288–296 (1997).
30. Gil, B., Zones, S. I., Hwang, S.-J., Bejblová, M. & Čejka, J. Acidic properties of
SSZ-33 and SSZ-35 novel zeolites: a complex infrared and MAS NMR study.
J. Phys. Chem. C. 112, 2997–3007 (2008).
NAture MAterIALS
31. Jacobs, P. A. & Beyer, H. K. Evidence for the nature of true Lewis sites in
faujasite-type zeolites. J. Phys. Chem. 83, 1174–1177 (1979).
32. Lohse, U., Löffler, E., Hunger, M., Stöckner, J. & Patzelova, V. Hydroxyl
groups of the non-framework aluminium species in dealuminated Y zeolites.
Zeolites 7, 11–13 (1987).
33. Weitkamp, J. & Puppe, L. Catalysis and Zeolites: Fundamentals and
Applications (Springer Science & Business Media, 2013).
34. Phung, T. K. & Busca, G. On the Lewis acidity of protonic zeolites.
Appl. Catal. A 504, 151–157 (2015).
35. Derouane, E. G. et al. The acidity of zeolites: concepts, measurements and
relation to catalysis: a review on experimental and theoretical methods for
the study of zeolite acidity. Catal. Rev. 55, 454–515 (2013).
36. Shannon, R. D. et al. The nature of the nonframework aluminum species
formed during the dehydroxylation of HY. J. Phys. Chem. 89, 4778–4788 (1985).
37. Bhering, D. L., Ramírez-Solís, A. & Mota, C. J. A. A density functional theory
based approach to extraframework aluminum species in zeolites. J. Phys.
Chem. B 107, 4342–4347 (2003).
38. Li, S. et al. Brønsted/Lewis acid synergy in dealuminated HY zeolite: a
combined solid-state NMR and theoretical calculation study. J. Am. Chem.
Soc. 129, 11161–11171 (2007).
39. Dimitrijevic, R., Lutz, W. & Ritzmann, A. Hydrothermal stability of zeolites:
determination of extra-framework species of HY faujasite-type steamed
zeolite. J. Phys. Chem. Solids 67, 1741–1748 (2006).
40. Zholobenko, V. L. et al. On the possible nature of sites responsible for the
enhancement of cracking activity of HZSM-5 zeolites dealuminated under
mild steaming conditions. Zeolites 10, 304–306 (1990).
41. van Bokhoven, J. A., Koningsberger, D. C., Kunkeler, P., Van Bekkum, H. &
Kentgens, A. P. M. Stepwise dealumination of zeolite βeta at specific T-sites
observed with 27Al MAS and 27Al MQ MAS NMR. J. Am. Chem. Soc. 122,
12842–12847 (2000).
42. Agostini, G. et al. In situ XAS and XRPD parametric Rietveld refinement to
understand dealumination of Y zeolite catalyst. J. Am. Chem. Soc. 132,
667–678 (2009).
43. Macedo, A., Raatz, F., Boulet, R., Janin, A. & Lavalley, J. C. in Studies in Surface
Science and Catalysis Vol. 37 (eds Grobet, P. J. et al.) 375–383 (Elsevier, 1988).
44. Menezes, S. M. C. et al. Characterization of extra-framework species of
steamed and acid washed faujasite by MQMAS NMR and IR measurements.
Appl. Catal. A 207, 367–377 (2001).
45. Yi, X. et al. Origin and structural characteristics of tri-coordinated
extra-framework aluminum species in dealuminated zeolites. J. Am. Chem.
Soc. 140, 10764–10774 (2018).
46. Liu, C., Li, G., Hensen, E. J. M. & Pidko, E. A. Nature and catalytic role of
extraframework aluminum in faujasite zeolite: a theoretical perspective.
ACS Catal. 5, 7024–7033 (2015).
47. Li, G. & Pidko, E. A. The nature and catalytic function of cation sites in
zeolites: a computational perspective. ChemCatChem 11, 134–156 (2019).
48. Bourgeat-Lami, E. et al. Study of the state of aluminium in zeolite-β. Appl.
Catal. 72, 139–152 (1991).
49. Haouas, M., Kogelbauer, A. & Prins, R. The effect of flexible lattice
aluminium in zeolite beta during the nitration of toluene with nitric acid and
acetic anhydride. Catal. Lett. 70, 61–65 (2000).
50. Omegna, A., van Bokhoven, J. A. & Prins, R. Flexible aluminum coordination
in alumino–silicates. Structure of zeolite H–USY and amorphous silica–
alumina. J. Phys. Chem. B 107, 8854–8860 (2003).
51. Wouters, B. H., Chen, T. H. & Grobet, P. J. Reversible tetrahedral–octahedral
framework aluminum transformation in zeolite Y. J. Am. Chem. Soc. 120,
11419–11425 (1998).
52. Abraham, A. et al. Influence of framework silicon to aluminium ratio on
aluminium coordination and distribution in zeolite Beta investigated by 27Al
MAS and 27Al MQ MAS NMR. Phys. Chem. Chem. Phys. 6, 3031–3036 (2004).
53. Busco, C., Bolis, V. & Ugliengo, P. Masked Lewis sites in proton-exchanged
zeolites: a computational and microcalorimetric investigation. J. Phys. Chem.
C. 111, 5561–5567 (2007).
54. Xu, B., Rotunno, F., Bordiga, S., Prins, R. & van Bokhoven, J. A. Reversibility
of structural collapse in zeolite Y: alkane cracking and characterization.
J. Catal. 241, 66–73 (2006).
55. Remy, M. J., Genet, M. J., Poncelet, G., Lardinois, P. F. & Notté, P. P.
Investigation of dealuminated mordenites by X-ray photoelectron
spectroscopy. J. Phys. Chem. 96, 2614–2617 (1992).
56. Collignon, F., Jacobs, P. A., Grobet, P. & Poncelet, G. Investigation of the
coordination state of aluminum in β zeolites by X-ray photoelectron
spectroscopy. J. Phys. Chem. B 105, 6812–6816 (2001).
57. Esquivel, D., Cruz-Cabeza, A. J., Jiménez-Sanchidrián, C. & Romero-Salguero,
F. J. Local environment and acidity in alkaline and alkaline-earth exchanged β
zeolite: structural analysis and catalytic properties. Microporous Mesoporous
Mater. 142, 672–679 (2011).
58. van Bokhoven, J. A. In-situ Al K-edge spectroscopy on zeolites:
instrumentation, data-interpretation and catalytic consequences. Phys. Scr.
2005, 76–79 (2005).
Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
Perspective
59. Altwasser, S., Jiao, J., Steuernagel, S., Weitkamp, J. & Hunger, M. in Studies in
Surface Science and Catalysis Vol. 154 (eds van Steen, E., Claeys, M. &
Callanan, L. H.) 3098–3105 (Elsevier, 2004).
60. van Bokhoven, J. A., Van der Eerden, A. M. J. & Koningsberger, D. C.
Three-coordinate aluminum in zeolites observed with in situ X-ray
absorption near-edge spectroscopy at the Al K-edge: flexibility
of aluminum coordinations in zeolites. J. Am. Chem. Soc. 125,
7435–7442 (2003).
61. Rybakov, A. A., Larin, A. V. & Zhidomirov, G. M. Influence of alkali cations
on the inter-conversion of extra-framework aluminium species in
dealuminated zeolites. Microporous Mesoporous Mater. 189, 173–180 (2014).
62. Jiao, J., Altwasser, S., Wang, W., Weitkamp, J. & Hunger, M. State of
aluminum in dealuminated, nonhydrated zeolites Y investigated by
multinuclear solid-state NMR spectroscopy. J. Phys. Chem. B 108,
14305–14310 (2004).
63. Ward, J. W. The nature of active sites on zeolites: I. The decationated Y
zeolite. J. Catal. 9, 225–236 (1967).
64. Mirodatos, C. & Barthomeuf, D. Superacid sites in zeolites. J. Chem. Soc.
Chem. Commun. 39–40 (1981).
65. Lunsford, J. H. Surface interactions of NaY and decationated Y zeolites with
nitric oxide as determined by electron paramagnetic resonance spectroscopy.
J. Phys. Chem. 72, 4163–4168 (1968).
66. van Bokhoven, J. A. et al. An explanation for the enhanced activity for light
alkane conversion in mildly steam dealuminated mordenite: the dominant
role of adsorption. J. Catal. 202, 129–140 (2001).
67. Yu, Z. et al. Brønsted/lewis acid synergy in H-ZSM-5 and H–MOR zeolites
studied by 1H and 27Al DQ-MAS solid-state NMR spectroscopy. J. Phys.
Chem. C. 115, 22320–22327 (2011).
68. Li, S. et al. Extra-framework aluminium species in hydrated faujasite zeolite
as investigated by two-dimensional solid-state NMR spectroscopy and
theoretical calculations. Phys. Chem. Chem. Phys. 12, 3895–3903 (2010).
69. Dzwigaj, S. & Che, M. Incorporation of Co(ii) in dealuminated BEA zeolite at
lattice tetrahedral sites evidenced by XRD, FTIR, diffuse reflectance UV–vis,
EPR, and TPR. J. Phys. Chem. B 110, 12490–12493 (2006).
70. Hajjar, R., Millot, Y., Man, P. P., Che, M. & Dzwigaj, S. Two kinds of
framework Al sites studied in BEA zeolite by X-ray diffraction, Fourier
transform infrared spectroscopy, NMR techniques, and V probe. J. Phys.
Chem. C. 112, 20167–20175 (2008).
71. Zheng, A., Li, S., Liu, S.-B. & Deng, F. Acidic properties and structure–
activity correlations of solid acid catalysts revealed by solid-state nmr
spectroscopy. Acc. Chem. Res. 49, 655–663 (2016).
72. Farneth, W. E. & Gorte, R. J. Methods for characterizing zeolite acidity.
Chem. Rev. 95, 615–635 (1995).
73. Kao, H.-M. & Grey, C. P. Probing the Brønsted and Lewis acidity of zeolite
HY: a 1H/27Al and 15N/27Al TRAPDOR NMR study of monomethylamine
adsorbed on HY. J. Phys. Chem. 100, 5105–5117 (1996).
74. Kao, H.-M., Liu, H., Jiang, J.-C., Lin, S.-H. & Grey, C. P. Determining the
structure of trimethylphosphine bound to the Brønsted acid site in zeolite
HY: double-resonance NMR and ab initio studies. J. Phys. Chem. B 104,
4923–4933 (2000).
75. Moroz, I. B., Larmier, K., Liao, W.-C. & Copéret, C. Discerning γ-alumina
surface sites with nitrogen-15 dynamic nuclear polarization surface
enhanced NMR spectroscopy of adsorbed pyridine. J. Phys. Chem. C. 122,
10871–10882 (2018).
76. Grey, C. P. & Kumar, B. S. A. 15N/27Al double resonance NMR study of
monomethylamine adsorbed on zeolite HY. J. Am. Chem. Soc. 117,
9071–9072 (1995).
77. Kao, H.-M. & Grey, C. P. Determination of the 31P–27Al J-coupling constant
for trimethylphosphine bound to the Lewis acid site of zeolite HY. J. Am.
Chem. Soc. 119, 627–628 (1997).
78. Hadjiivanov, K. I. & Vayssilov, G. N. Characterization of oxide surfaces and
zeolites by carbon monoxide as an IR probe molecule. Adv. Catal. 47,
307–511 (2002).
79. Wischert, R., Copéret, C., Delbecq, F. & Sautet, P. Dinitrogen: a selective
probe for tri-coordinate Al “defect” sites on alumina. Chem. Commun. 47,
4890–4892 (2011).
80. Boronat, M., Concepción, P., Corma, A., Renz, M. & Valencia, S.
Determination of the catalytically active oxidation Lewis acid sites in Sn-beta
zeolites, and their optimisation by the combination of theoretical and
experimental studies. J. Catal. 234, 111–118 (2005).
81. Jin, F. & Li, Y. A FTIR and TPD examination of the distributive properties of
acid sites on ZSM-5 zeolite with pyridine as a probe molecule. Catal. Today
145, 101–107 (2009).
82. Moissette, A., Vezin, H., Gener, I. & Brémard, C. Generation and migration
of electrons and holes during naphthalene sorption in acidic Al-ZSM-5
zeolites. J. Phys. Chem. B 107, 8935–8945 (2003).
83. Marquis, S., Moissette, A., Vezin, H. & Brémard, C. Long-lived radical
cation–electron pairs generated by anthracene sorption in non Brønsted
acidic zeolites. J. Phys. Chem. B 109, 3723–3726 (2005).
1055
Perspective
84. Jiao, J. et al. Characterization of framework and extra-framework aluminum
species in non-hydrated zeolites Y by 27Al spin-echo, high-speed MAS, and
MQMAS NMR spectroscopy at B0 = 9.4 to 17.6 T. Phys. Chem. Chem. Phys.
7, 3221–3226 (2005).
85. Maier, S. M., Jentys, A. & Lercher, J. A. Steaming of zeolite BEA and its effect
on acidity: a comparative NMR and IR spectroscopic study. J. Phys. Chem. C.
115, 8005–8013 (2011).
86. Oumi, Y. et al. Effect of the framework structure on the dealumination–
realumination behavior of zeolite. Mater. Chem. Phys. 78, 551–557 (2003).
87. Jia, C., Massiani, P. & Barthomeuf, D. Characterization by infrared and
nuclear magnetic resonance spectroscopies of calcined beta zeolite. J. Chem.
Soc. Faraday Trans. 89, 3659–3665 (1993).
88. Dědeček, J., Tabor, E. & Sklenak, S. Tuning the aluminum distribution in
zeolites to increase their performance in acid‐catalyzed reactions.
ChemSusChem 12, 556–576 (2019).
89. Pu, X., Liu, N.-w & Shi, L. Acid properties and catalysis of USY zeolite with
different extra-framework aluminum concentration. Microporous Mesoporous
Mater. 201, 17–23 (2015).
90. Gruver, V. & Fripiat, J. J. Lewis acid sites and surface aluminum in aluminas
and mordenites: an infrared study of CO chemisorption. J. Phys. Chem. 98,
8549–8554 (1994).
91. Janin, A. et al. FT IR study of the silanol groups in dealuminated HY zeolites:
nature of the extraframework debris. Zeolites 11, 391–396 (1991).
92. Niwa, M., Sota, S. & Katada, N. Strong Brønsted acid site in HZSM-5 created
by mild steaming. Catal. Today 185, 17–24 (2012).
93. Zholobenko, V. L. et al. On the nature of the sites responsible for the
enhancement of the cracking activity of HZSM-5 zeolites dealuminated under
mild steaming conditions: part 2. Zeolites 11, 132–134 (1991).
94. Anand, R., Maheswari, R. & Hanefeld, U. Catalytic properties of the novel
mesoporous aluminosilicate AlTUD-1. J. Catal. 242, 82–91 (2006).
1056 Nature Materials | VOL 19 | October 2020 | 1047–1056 | www.nature.com/naturematerials
NAture MAterIALS
95. DeCanio, S. J., Sohn, J. R., Fritz, P. O. & Lunsford, J. H. Acid catalysis by
dealuminated zeolite-Y: I. Methanol dehydration and cumene dealkylation.
J. Catal. 101, 132–141 (1986).
96. Anunziata, O. A., Martínez, M. L. & Costa, M. G. Characterization and acidic
properties of Al-SBA-3 mesoporous material. Mater. Lett. 64, 545–548 (2010).
97. Xia, Z. et al. Post synthesis of aluminum modified mesoporous TUD-1
materials and their application for FCC diesel hydrodesulfurization catalysts.
Catalysts 7, 141–160 (2017).
98. Raatz, F., Freund, E. & Marcilly, C. Study of small-port and large-port
mordenite modifications. Part 2.—Ion-exchange properties of thermally
treated ammonium forms. J. Chem. Soc. Faraday Trans. 1 81, 299–310 (1985).
99. Kunkeler, P. J. et al. Zeolite Beta: the relationship between calcination procedure,
aluminum configuration, and Lewis acidity. J. Catal. 180, 234–244 (1998).
Acknowledgements
The authors gratefully acknowledge the ESI Platform of the Paul Scherrer Institute and
ETH Zurich for financial support.
Competing interests
The authors declare no competing interests.
Additional information
Correspondence should be addressed to J.A.v.
Reprints and permissions information is available at www.nature.com/reprints.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in
published maps and institutional affiliations.
© Springer Nature Limited 2020