Microporous and Mesoporous Materials 299 (2020) 109841

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Microporous and Mesoporous Materials

journal homepage: http://www.elsevier.com/locate/micromeso

Mechanism of formation of framework Fe3þ in bimetallic Ag-Fe mordenites

- Effective catalytic centers for deNOx reaction
M.G. Shelyapina a, *, J. Gurgul b, K. Łątka c, P. Sa �pez d, D. Bogdanov a, Y. Kotolevich d,
�nchez-Lo
d d
V. Petranovskii , S. Fuentes
a
Saint Petersburg State University, 7/9 Universitetskaya nab., Saint Petersburg, 199034, Russia
b
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, PL-30239, Krakow, Poland
c
M. Smoluchowski Institute of Physics, Jagiellonian University, Łojasiewicza 11, 30-348, Krak�ow, Poland
d
Centro de Nanociencias y Nanotecnología, Universidad Nacional Aut� onoma de M�exico, Ensenada, Baja California, C.P. 22860, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: As it was reported in our previous study (P. S�

anchez-L�opez et al., 2019), mono- and bimetallic systems of Ag, Fe,
Ion-exchange mordenite and Ag-Fe supported on mordenites exhibit a nontrivial dependence of deNOx activity from the preparation
Ag-Fe bimetallic systems procedure. In this work we report on the results of our comprehensive study of the sample composition, structure
M€ossbauer spectroscopy
and morphology to reveal issues of the observed synergetic effect. It was found that both the order of the ion
Framework Fe
Ag nanoparticles
exchange reactions and processing temperature affect the distribution and state of silver and iron species in the
mordenite matrix. In the Ag-containing samples silver is accumulated on the surface in the form of X-ray
amorphous nanoparticles of 2–10 nm in size; however, charge compensating Agþ cations are also present. The
M€ossbauer spectroscopy study of the iron-containing samples evidences the isomorphous substitution of Al3þ by
Fe3þ in the mordenite framework. The portion of this framework Fe3þ correlates with catalytic deNOx activity of
the studied materials. Hydrated extra-framework Fe2þ cations are M€ ossbauer silent at room temperature, but
their presence is evident from the increasing of the a/b ratio caused by the contraction of the main mordenite
channel upon iron cations loading. Based on the reported results we propose a mechanism of the isomorphous
substitution of the framework Al3þ by Fe3þ promoted by Agþ. This mechanism leads to creation of new effective
catalytic centers for deNOx reaction, which are (i) framework Fe3þ activated by nearby Agþ and (ii) a very few
nanosized Ag particles on the Fe-mordenite surface.

1. Introduction may be non-uniform in volume of the catalyst particle, having a different

Heterogeneous catalysts based on zeolites are of a complex nature,
which makes particularly difficult to evaluate the structure of their
active centers. This complexity is somewhat inherited from the method
of their preparation, which usually involves the exchange of metal ions
in aqueous solution, and the associated complex surface chemistry. The
metal-carrier interface often plays a dominant role in supported cata­
lysts. When the used fragments are extremely small and consist of one or
several atoms, the effects of the metal-carrier interface are maximized.
Since the precipitated particles are small and often heterogeneous in
structure, it is difficult to isolate the contribution of each of the proposed
centers, to understand their individual structure and the influence of
neighboring atoms, despite improved methods of synthesis and char­
acterization [1]. In addition, the distribution of the obtained species
composition on the surface, in the subsurface layer and in the volume
[2].
Monometallic de-NOx catalysts, based on zeolites modified by silver
or iron, have been extensively studied (see [3] and References inside).
Both metals represent complex behavior, which depends, except of the
support, on the nature of stabilized species and their relative amount.
For example, relative amount of Ag nanoparticles (AgNPs) over Agþ
influence selectivity of NO to N2 conversion [4]. Fe-modified zeolites
can contain a wide range of extra-framework species, including isolated
iron ions in various oxidation states, mono-, bi- or oligonuclear
iron-oxo-complexes or iron oxide nanoclusters in the zeolite voids, or
relatively bulky nanoparticles outside the microporosity, i.e. in meso­
porosity and on the surface of zeolite crystals. The structure and location
of iron-containing extra-framework cation sites are still debated [5], as

* Corresponding author. Department of Nuclear Physics Research Methods, Saint Petersburg State University, 198504, Ulyanovskaya 1, Peterhof, Russia.
E-mail address: marina.shelyapina@spbu.ru (M.G. Shelyapina).

https://doi.org/10.1016/j.micromeso.2019.109841
Received 11 August 2019; Received in revised form 6 October 2019; Accepted 28 October 2019
Available online 31 October 2019
1387-1811/© 2019 Published by Elsevier Inc.
M.G. Shelyapina et al.
well as the role of substituted Fe in the framework. The reactivity of
zeolite catalysts can be optimized by introducing heteroatoms either
into the framework, or at the extra-framework positions, which leads to
the formation of acidic centers of different nature and different strengths
(Brønsted acidic, Lewis acidic and redox catalytic centers) [6,7]. Un­
derstanding the nature of such formations is crucial for the development
of new and improved zeolite-based catalysts [5,8].
For the preparation of such catalysts, one can use various methods of
ion exchange; among others, solid phase exchange using protonated
forms of zeolites, or exchange in a polar or non-polar organic solvents
are mentioned. However, the most commonly used are conventional
exchange processes in aqueous solutions, modifying the temperature,
concentration, pH, and the duration of the process [9], as well as
applying the external action such as microwave assisted ion-exchange
[10–12]. Experimental results on the production of iron-containing ze­
olites confirmed that the preparation methods have a significant influ­
ence on the composition and distribution of iron species [13]. However,
such exchange in the case of iron salts is problematic, since iron (III) ions
have a large hydration shell, and for this reason they hardly penetrate
into the pores of the zeolite. Exchange with the use of aqueous solutions
of iron (II) salts usually leads, first of all, to the oxidation of iron (II) to
iron (III). Additional problems are caused by a small amount of highly
soluble iron salts [3].
Unlike iron, monovalent silver cations are stable in aqueous solution;
therefore, ion exchange can be easily carried out in zeolites. Similarly,
the reversible oxidation-reduction of silver provides a useful system for
studying the formation mechanisms of spatially well-defined metal
clusters. Since synergism is often regarded as a useful tool for influ­
encing catalysis, Ag catalysts modified with transition metals are of
great interest because of the influence of the promoter element on the
formation of clusters and nanoparticles on zeolites, as well as their
simultaneous participation in the catalytic process. Thus, an under­
standing of the physicochemical properties and active phases in these
systems will improve the design of catalysts and other advanced
materials.
In our previous study it has been found that the activity of bimetallic
Ag-Fe catalysts on a zeolite carrier in relation to the reduction of NOx
essentially exceeds the activity of monometallic ones [14]. Moreover,
the catalytic properties of specific samples very much depend on the
order of the ion exchange, and less significantly on the temperature of
the ion exchange treatment. The main aim of the present work is to
reveal the issues of such a synergetic effect that bimetallic systems
exhibit.
Here we report on the results of our detailed study of physico­
chemical properties of mono (Ag, Fe) and bimetallic (Ag-Fe) catalysts
carried out by applying complimentary methods (X-ray diffraction
analysis, electronic microscopy, Mo €ssbauer spectroscopy, textural
analysis).
2. Experimental
Monometallic Ag, Fe, and bimetallic Ag-Fe systems were prepared
from sodium mordenite with а Si/Al atomic ratio of 6.5, supplied by
Zeolyst International (CBV-10A product). For the silver and iron pre­
cursors 0.1 N aqueous solutions of silver nitrate, AgNO3, �99.0%,
FagaLab, and iron (II) perchlorate hydrate, Fe(ClO4)2 H2O, � 98.0%,
Sigma-Aldrich, were used. To obtain monometallic systems Agþ or Fe2þ
cations were introduced into Naþ-mordenite by applying a conventional
ion-exchange procedure from corresponding aqueous solutions at 20 or
60 � C for 1 day. After the ion exchange procedure, the samples were
filtered, thoroughly washed with deionized H2O and dried at 110 � C for
20 h. All processing steps were carried out under conditions that prevent
direct light from entering the samples, in order to avoid possible spon­
taneous reduction of silver ions. The obtained monometallic samples
were labeled as Ag-MOR-T and Fe-MOR-T with T ¼ 20 or 60 depending
on the preparation temperature. The starting material was labeled as Na-
2
Microporous and Mesoporous Materials 299 (2020) 109841
MOR.
The bimetallic systems were synthetized by three different ways: (i)
subsequent two ion-exchange procedures, firstly treated with Agþ so­
lution, secondly with Fe2þ solution, the obtained samples were labeled
as AgFe-MOR-T; (ii) vice versa, the obtained samples were labeled as
FeAg-MOR-T; (iii) and a single stage ion exchange procedure from Agþ
and Fe2þ mixture solution in a volume ratio of 1:1, the samples were
labeled as mAgFe-MOR-T.
The chemical composition of the zeolite samples before and after ion-
exchange procedures was examined by two different techniques: X-ray
Photoemission Spectroscopy (XPS) to probe surface and Inductively
Coupled Plasma - Optical Emission Spectroscopy (ICP-OES) to study
bulk composition.
The ICP-OES study were carried out applying a Varian Vista-MPX
equipment (Varian Inc., USA), using argon to generate plasma and ni­
trogen to clean the optical system. Samples were pretreated by degass­
ing, following dissolving in HNO3 and HF mixture at 40 � C overnight and
addition of H3BO3 solution at 40 � C for 5 h.
The XPS analysis was done using a Combined Auger, X-ray and Ul­
traviolet Photoelectron spectrometer Thermo Fisher Scientific ESCAlab
250Xi with monochromatic AlKα radiation (photon energy 1486.6 eV). A
total energy resolution was about 0.55 eV. Spectra were recorded in the
constant pass energy mode at 100 eV for survey spectrum and 50 eV for
element core level spectrum, using XPS spot size of 650 μm. The study
was done at ambient temperature in UHV with pressure of the order of
1 � 10 9 mbar.
The X-ray diffraction (XRD) analysis was done using a diffractometer
Bruker « D8 DISCOVER» with CuKα long focused X-Ray sealed tube. Scan
range was from 5.00 to 50.00 2θ degree, with step width of 0.02� .
Quantification was done using the DIFFRAC.SUITE software package.
The sample morphologies were determined by SEM and TEM anal­
ysis. SEM studies were carried out applying Zeiss Merlin equipment in
high resolution mode at 21 kV. TEM was done using a JEOL 2010 mi­
croscope operating at accelerating voltage 200 kV using LaB6 filament.
To prepare the probe, the sample was dispersed in isopropanol using
ultrasound, and putting a drop of this suspension on supported carbon
film. The particle size was determined from HR-TEM micrographs.
The textural properties were determined from nitrogen adsorp­
tion–desorption isotherms at 196� С (77 K) recorded using a Micro­
meritics TriStar 3000 apparatus (Micromeritics Instrument Corporation,
Version 1.03). Before the experiments, the samples were degassed at
300 � C in vacuum for 5 h. The volume of adsorbed N2 was normalized to
standard temperature and pressure. The specific surface area of the
samples was calculated using the Brunauer-Emmett-Teller (BET)
method for nitrogen adsorption data in the P/P0 range of 0.005–0.250.
The average pore diameter was calculated using the Barret-Joyner-
Halenda (BJH) method for the adsorption and desorption branches of
the N2 isotherms. The total pore volume was obtained from isotherms at
P/P0 ¼ 0.99.
The iron containing samples were investigated by means of
Mo €ssbauer spectroscopy employing the 14.4 keV 57Fe gamma resonance
transition. A M€ ossbauer system that consists of the Janis top loaded
liquid helium cryostat (Janis Research Company, Wilmington, MA
01887 USA) integrated with a conventional constant-acceleration
spectrometer (Science Engineering & Education Co. USA) of the Kan­
keleit type in transmission geometry was used. During measurements,
100 mCi Mo €ssbauer 57Co(Rh) γ-ray source and the absorbers were kept
at room temperature. The absorbers were made of the fine powdered
materials placed in a thin-walled (~0.1 mm) cylindrical plastic con­
tainers. The used absorber thicknesses of about 65 mg cm 2 were
calculated from the optimisation procedure [15]. The resonance
14.4 keV gamma rays (for a given measurement and the energy scale
calibration) were detected simultaneously by means of two independent
LND Kr/Co2 proportional gas counters attached at opposite sides of the
driving system. The drive velocity calibration was performed with a
second 57Co(Rh) source against a standard metallic iron foil at room
M.G. Shelyapina et al. Microporous and Mesoporous Materials 299 (2020) 109841

temperature. 3.2. Structure and morphology studied by XRD, SEM and TEM

3. Results The XRD patterns of the prepared materials before and after the ion-
exchange proceeded at 20 � C is shown in Fig. 1(a) (as the samples pre­
3.1. Elemental analysis pared at 20 and 60 � C exhibit similar patterns, the data for T ¼ 60 � C are
moved into Supplementary Materials, Fig. S1(a)). They confirm that all
The chemical composition of the studied zeolites both on the surface the studied samples keep the mordenite crystalline structure [16].
and in bulk is listed in Table 1. In the starting material, Na-MOR, the However, two main changes as compared to the standard mordenite
surface is enriched with Al. Observed by ICP-OES an excess of Na points XRD pattern are observed: (i) a redistribution of peak intensities after
out at an incomplete rinse of the sample after synthesis, and the surface ion-exchange procedures, much more pronounced after exchange with
is slightly more polluted with Na. silver; (ii) slight changes of all the lattice parameters, see Table 2. Be­
For the Ag-MOR-T samples Si/Al ratio within the experimental error sides, in several samples, namely, AgFe-MOR-T and mAgFe-MOR-T, an
is kept untouched, as compared to Na-MOR. The Ag/Al ratio determined additional diffraction peak at 38.2� of 2θ appears.
from XPS is much greater than 1; simultaneously Na goes away, but it is According to SEM studies the applied ion-exchanged procedures do
never completely removed. This points out that a part of silver is in form not change the size and morphology of mordenite: particles of
of ion exchangeable cations equilibrating extra-charge of the zeolite 60–100 nm, which form agglomerates of about а few microns. This
framework. By comparing ICP-OES and XPS data one can conclude that correlates well with the estimation of the average crystallite size of
a significant part of Ag is accumulated on the surface. Increase of tem­ about 60 nm obtained from the well-known Scherrer formula. However,
perature of the ion exchange treatment leads to a little deeper Ag for all the Ag-containing samples on the mordenite surface additional
exchange. particles of few nm size were detected. The SEM images for selected
The ion exchange of sodium for iron is less effective. In the Fe-MOR-T materials are shown in Fig. 1(c–e), the images for all the studied samples
samples a half of Na remains after exchange. A slight enrichment of the can be found in Supplementary Materials, Fig. S2. High resolution TEM
surface by Fe for Fe-MOR-60 is observed. images confirm the presence of Ag nanoparticles of 2–10 nm on the
When preparing bimetallic materials, various methods were used: surface of mordenite with distance between particles of about 5 nm, see
sequential treatment in different order or exchange from a mixed solu­ Fig. 1(f–h).
tion. Subsequent treatment of monometallic Ag-MOR-T in iron
perchlorate solution leads to partial removing of silver, more pro­ 3.3. N2 adsorption-desorption
nounced for the surface. Simultaneously the Na content decreases that
may refer to the presence of ion-exchangeable Fe. The textural properties of the studied compounds are shown in
The treatment of the Fe-MOR-T samples in the AgNO3 solution leads Table 3. The initial mordenite in sodium form had a surface area of
to a higher Ag content as compare to AgFe-MOR-T with an accumulation 429 m2/g (according to the Langmuir method); this result is very well
of Ag on the surface. However, an impact of temperature is observed: at consistent with the surface area provided by the supplier, 425 m2/g.
low temperature the Ag accumulation is more noticeable; contrary, the After ion exchange with silver and iron ions at both temperatures, the
concentration of Fe on the surface is greater at 60 � C. specific surface area and pore volume underwent not very significant
The samples obtained from the mixture of AgNO3 and Fe(ClO4)2 changes, most noticeable for the Fe-MOR material. The exchange for
solutions exhibit similar element distribution as it was at subsequent silver in Na-MOR slightly reduced the surface area, and the exchange for
treatment, but with lower precipitation of Fe on the surface. iron increased it (see Table 3). These results demonstrate that ion ex­
change affects the texture of zeolite. In the first case, a decrease in
surface area may be associated with a partial blockage of pores of
mordenite by the resulting silver species, such as clusters and nano­
particles. In the second case, samples containing Fe showed an increase
Table 1 in surface area of approximately 60 m2/g as compared to Na-MOR. This
Chemical composition (atomic ratio) in the bulk (ICP-OES) and on the surface indicates a high dispersion of iron ions on the surface of mordenite, their
(XPS) of the studied samples. smaller number (since one doubly charged iron cation replaces two
Sample Si/Al Ag/Al Fe/Al Na/Al singly charged sodium cations), and the possible formation of micro­
XPS ICP XPS ICP XPS ICP XPS ICP pores, as was observed for the Fe/mordenite catalyst [17].
The results of determining the pore volume in monometallic mate­
Na-MOR 5.4 6.52 – – – – 1.40 1.29
(2) (6) (8) (3) rials followed the same trend as the specific surface area with respect to
Ag-MOR- 5.8 6.29 8.2 0.72 – – 0.24 0.35 the exchange for silver and iron. The micropore volume values were
20 (2) (5) (4) (2) (2) (2) stable for all the samples (about 0.14 cm3/g) and slightly differed for the
AgFe- 6.8 6.63 3.6 0.60 0.43 0.14 NDa 0.16 FeAg-MOR-T and Fe-MOR-T samples (Table 3). Regarding the influence
MOR-20 (2) (6) (2) (2) (3) (1) (1)
of the temperature used during the ion exchange procedure, this
FeAg- 7.5 6.54 4.6 0.72 0.41 0.10 0.09 0.18
MOR-20 (3) (6) (2) (2) (3) (1) (1) (1) parameter did not have a serious effect on the pore volume of materials.
mAgFe- 6.6 6.52 4.2 0.62 0.17 0.10 0.19 0.27 In the AgFe-MOR-T and FeAg-MOR-T bimetallic systems, at both tem­
MOR-20 (2) (6) (2) (2) (1) (1) (1) (1) peratures, no direct correlation of surface area values was observed, in
Fe-MOR- 6.1 6.40 0.18 0.16 0.56 0.58
– –
contrast to their monometallic analogues. In the case of simultaneous
20 (2) (5) (1) (1) (3) (2)
Ag-MOR- 5.1 6.38 7.2 0.84 – – 0.25 0.20 exchange (mAgFe-MOR-T), the obtained surface areas had intermediate
60 (2) (5) (3) (2) (2) (1) values with respect to monometallic materials. These results of N2
AgFe- 7.1 6.36 4.6 0.56 0.56 0.14 0.09 0.16 adsorption on mono- and bimetallic materials indicate that a rather
MOR-60 (3) (5) (2) (2) (3) (1) (1) (1) complicated interaction occurs between the silver and iron precursors
FeAg- 8.0 6.55 3.9 0.69 0.83 0.11 0.13 0.23
and the Na-MOR support, which is sensitive to the order of introduction
MOR-60 (3) (5) (2) (2) (4) (1) (1) (1)
mAgFe- 7.9 6.52 4.0 0.63 0.19 0.11 0.25 0.25 of the components.
MOR-60 (3) (5) (2) (2) (1) (1) (2) (1)
57
Fe-MOR- 6.0 6.40 – – 0.27 0.18 0.57 0.56 3.4. Fe M€
ossbauer studies
60 (2) (5) (2) (1) (3) (2)
a
ND – not detectable. The iron containing samples were investigated by means of

3
M.G. Shelyapina et al.
Fig. 1. Full XRD patterns of the studied samples synthetized at 20 � C (a) and a selected range with expected fcc-Ag (111) diffraction peak (b). SEM (c–e) and TEM
(f–h) images for Ag-MOR-20 (c,f), FeAg-MOR-20 (d,g) and Fe-MOR-20 (e,h).
Mo €ssbauer spectroscopy to probe oxidation state and local environment
of iron. The room temperature 57Fe Mo €ssbauer spectra for selected
materials are shown in Fig. 2. The patterns for all the studied Fe-
containing mordenites can be found in Supplementary Materials,
Fig. S3.
The Mo €ssbauer spectra were analyzed numerically by fitting a hy­
perfine parameter distribution (HPD) using the Voigt-line-based method
of Rancourt and Ping [18]. In this method, the HPD for a given crystal
site corresponding to similar structural, chemical and magnetic prop­
erties is constructed by a sum of Gaussian components for the quadru­
pole splitting (QS) distributions and, if necessary, the magnetic
4
Microporous and Mesoporous Materials 299 (2020) 109841
hyperfine field Bhf distributions. The isomer shift (IS) can be linearly
coupled to the primary hyperfine parameters (QS, Bhf).
Despite the general shape of all spectra is similar and represent a
doublet, their careful analysis reveals some differences concerning the
number, width and asymmetry of the doublets. The spectra are super­
imposition of at least two Mo €ssbauer signals, which can be fitted by
symmetric quadrupole doublets using the numerical procedure
described above. All samples (containing 57Fe with natural abundance)
show Fe(III) as main iron species. Their hyperfine parameters derived
from the Mo€ssbauer spectra, namely, IS relative to α-Fe foil, the average
quadrupole splitting <QS> ¼ e2qQ/2 and its Gaussian width (σ) are
M.G. Shelyapina et al. Microporous and Mesoporous Materials 299 (2020) 109841

Table 2 values of σ-parameter confirm this remark.

The X-ray mordenite lattice parameters, unit cell volume and a/b ratio for the The analysis shows that samples contain more than 70% of Fe3þ ions
studied samples. in tetrahedral surroundings, whereas the remaining iron is in octahedral
Sample a (Å) b (Å) c (Å) V (Å3) a/b ones. The octahedral components, Fe3þ(Oh), is characterized by
Na-MOR 18.103 20.434 7.5152 2780.0 0.8859
IS > 0.38 mm/s, high QS and σ parameters much higher than that
(2) (2) (1) (6) (3) observed for Fe3þ(Td)1,2. It can be attributed to Fe3þoxides of hydroxides
Ag-MOR-20 18.120 20.431 7.5083 2779.6 0.8869 particles formed at the mordenite surface. It is worth noting that
(2) (2) (1) (6) (3) Fe3þ(Oh) is absent in FeAg-MOR-60 and mAgFe-MOR-60.
AgFe-MOR-20 18.131 20.423 7.5076 2780.0 0.8878
In the 57Fe Mo€ssbauer spectra of Fe-MOR-60 and Fe-MOR-20 one can
(2) (2) (1) (6) (3)
FeAg-MOR-20 18.122 20.421 7.5065 2777.9 0.8874 also find some additional components of magnetic or superparamagnetic
(2) (2) (1) (6) (3) character. The lack of well-defined magnetic sextets does not allow us to
mAgFe-MOR- 18.124 20.423 7.5067 2778.6 0.8874 differentiate it precisely. However, one can conclude that the magnetic
20 (2) (2) (1) (6) (3) hyperfine field is much lower than existing in bulk Fe2O3, which is
Fe-MOR-20 18.133 20.423 7.5123 2782.0 0.8879
(2) (2) (1) (6) (3)
characteristic for the relaxation phenomena, and can be related to the
Ag-MOR-60 18.117 20.426 7.5064 2777.8 0.8870 existence of ultrafine particles of Fe2O3 and/or other iron oxide phases
(2) (2) (1) (6) (3) of superparamagnetic character [23,24].
AgFe-MOR-60 18.127 20.415 7.5044 2777.1 0.8879
(2) (2) (1) (6) (3)
4. Discussion
FeAg-MOR-60 18.115 20.421 7.5048 2776.2 0.8871
(2) (2) (1) (6) (3)
mAgFe-MOR- 18.118 20.415 7.5049 2775.9 0.8875 The reported experimental data evidence that in the studied mate­
60 (2) (2) (1) (6) (3) rials both the order of ion exchange reaction and processing temperature
Fe-MOR-60 18.119 20.400 7.5056 2774.3 0.8882
affect the quantity of Ag and Fe loaded into the mordenite, as well as
(2) (2) (1) (6) (3)
their states and locations.
According to the bulk elemental analysis, only a part of Ag or Fe is
ion-exchangeable, see Table 1. For all the samples Ag is to a large extent
Table 3 accumulated on the surface. In the Fe-MOR-T samples the Fe/Al ratio
The textural properties of Na-MOR before and after the ion exchange with Ag
determined from XPS and ICP-OES is very similar that indicates that iron
and Fe.
is rather homogeneously spread over the sample. In mAgFe-MOR-T iron
Sample SBETa SLangb Vporec Vmicrod DBJHe is slightly accumulated on the surface. In bimetallic samples prepared by
[m2/g] [m2/g] [cm3/g] [cm3/g] [Å]
the sequential exchange the Fe concentration on the surface is increased.
Na-MOR 243.3 429.5 0.20 0.14 32.7 The analysis of the XRD peak intensities and their variations for Ag-
Ag-MOR-20 269.5 421.6 0.18 0.14 26.3 containing samples shown in Fig. 1(a) confirms the presence of Agþ in
AgFe-MOR- 275.4 430.6 0.18 0.14 26.7
20
ion-exchangeable positions in the mordenite lattice. According to
FeAg-MOR- 267.5 419.8 0.18 0.13 27.6 theoretical calculations of XRD patterns for ion-exchanged mordenites
20 the decrease of (200), (020) and (150) diffraction peaks intensities is
mAgFe- 279.2 437.1 0.18 0.14 26.4 related to local structural rearrangements, caused by the exchange of
MOR-20
Naþ for Agþ cations, the latter prefer to be located in the main channel
Fe-MOR-20 317.6 496.8 0.21 0.16 26.4
(12-membered-ring) [25].
Ag-MOR-60 237.2 418.8 0.19 0.14 31.9 The sodium to iron exchange keeps the diffraction peaks almost
AgFe-MOR- 240.6 424.7 0.19 0.14 32.6
60
untouched. According to theoretical calculations it may point to an
FeAg-MOR- 276.2 487.3 0.21 0.15 31.2 isomorphous substitution of some portion of Al3þ by Fe3þ in tetrahedral
60 positions in addition to the cationic exchange with Naþ [25]. The pos­
mAgFe- 251.5 443.7 0.20 0.14 31.8 sibility of such an isomorphic substitution in iron containing zeolites, in
MOR-60
general [25–30], and mordenites [25,28,29], in particular, was dis­
Fe-MOR-60 282.2 497.6 0.22 0.16 31.3
cussed in a number of works, and is in line with our 57Fe Mo €ssbauer
a
SBET is the specific surface area calculated by BET method within the P/P0 study that suggest a perceptible presence of framework Fe3þ in the
range of 0.005–0.250. studies materials, see Table 4.
b
SLang is the specific surface area calculated by Langmuir method.
c The existence of free Fe3þ ion-exchanged cations in zeolites is quite
Vpore is the cumulative pore volume determined at the relative pressure of
questionable. Several studies suggested that two bridging Fe3þ centers
0.99.
d
Vmicro is the micropore volume calculated from t-plot method.
can be formed [31–33], but it requires high temperature treatment (for
e
DBJH is BJH pore diameter calculated by the desorption branches of the N2 example, in zeolite A upon heating in O2 an oxidation of Fe2þ to Fe3þ
isotherms. with further formation of a Fe3þ-O-Fe3þ dimer occurs [31]). Normally,
in zeolites the extra-framework iron is mostly Fe2þ [30]. However, it is
listed in Table 4. quite problematic to determine it by Mo €ssbauer spectroscopy, because of
For all the studied samples at least two different Fe(III) species were the fact that in fully hydrated conditions free Fe2þ is expected to be in a
determined. The quadrupole doublets with low value of isomer shift, [Fe(H2O)6]2þ metal-aqua-complex, and at room temperature due to its
fast motion such a complex is Mo €ssbauer silent. Our 57Fe Mo €ssbauer
IS � 0.3 mm/s, are typical of Fe(III) species and strongly suggests
tetrahedral surrounding of iron [19–22]. The major component, labeled experiment was limited by room temperature conditions only. Low
as Fe3þ(Td)1, has the QS value in the range of 0.59–0.78 mm/s with quite temperature measurements, when the mobility is decreased, typically
reasonable values of the Gaussian width of the QS distribution, reveal the presence of “naked” Fe2þ in iron containing zeolites [34–36].
σ < 0.24 mm/s. These species with low IS and low QS can be attributed The proof that Fe2þ ions are among non-structural extra-lattice cat­
to the well-defined framework sites with high symmetry, which are Fe3þ ions necessary to maintain charge balance in the zeolite structure is a
in a high spin state. The second component, Fe3þ(Td)2, with essentially self-consistent change in the content of all cations, primarily sodium, in
higher <QS>, is less intensive, and present not in all samples. One can the prepared samples, see Table 1. In our previous work we demon­
rely it to the adjacent iron present near to defect sites. Much higher strated that in Cu-exchanged mordenite obtained from sodium,
ammonia or protonated forms, in which Cu2þ substitute for singly

5
M.G. Shelyapina et al. Microporous and Mesoporous Materials 299 (2020) 109841

Fig. 2. Room temperature 57Fe M€ ossbauer spectra and their decomposition for the AgFe-MOR-20 (a) and FeAg-MOR-20 (b) samples. The light grey and middle grey
components are related to the Fe3þ in tetrahedral sites. The dark grey component corresponds to Fe3þ in octahedral sites.

Table 4
Hyperfine parameters derived from the room-temperature57Fe M€
ossbauer
spectra for the studied Fe-containing samples.
Sample IS (mm/ <QS> σ (mm/ Area Site
s) (mm/s) s) (%)

AgFe-MOR- 0.25 0.66 0.20 57 Fe3þ(Td)1

20 0.28 1.39 0.36 26 Fe3þ(Td)2
0.54 2.97 1.38 17 Fe3þ(Oh)

FeAg-MOR- 0.26 0.71 0.28 84 Fe3þ(Td)1

20 0.41 2.05 1.08 16 Fe3þ(Oh)

mAgFe- 0.26 0.78 0.22 74 Fe3þ(Td)1

MOR-20 0.51 2.28 1.38 26 Fe3þ(Oh)

Fe-MOR-20 0.27 0.65 0.19 46 Fe3þ(Td)1

0.28 1.40 0.37 33 Fe3þ(Td)2
0.76 2.59 0.53 11 Fe3þ(Oh)
10 Magnetic
oxides

AgFe-MOR- 0.26 0.70 0.20 76 Fe3þ(Td)1

60 0.38 1.76 0.87 24 Fe3þ(Oh)

FeAg-MOR- 0.24 0.59 0.03 74 Fe3þ(Td)1

60 0.23 1.04 0.04 26 Fe3þ(Td)2

mAgFe- 0.25 0.74 0.24 77 Fe3þ(Td)1

MOR-60 0.17 0.45 2.26 23 Fe3þ(Td)2

Fe-MOR-60 0.27 0.61 0.19 39 Fe3þ(Td)1

0.28 1.37 0.39 31 Fe3þ(Td)2 Fig. 3. The a/b ratio for the studied compounds versus Fe/Al determined from
0.77 2.58 0.76 8 Fe3þ(Oh) ICP-OES. Solid line represents linear fit of the data for the Fe-containing com­
22 Magnetic pounds. Dashed line corresponds for the similar fit obtained for Cu-exchanged
oxides
mordenites with Cu2þ in the main channel.

charged cations, there is a strong correlation between the copper loading
and the a/b ratio of the mordenite lattice parameters [11,37]. A linear
increasing of the a/b ratio indicates that upon copper loading, the main
channel becomes more and more elliptical due to electrostatic interac­
tion of copper cations with negatively charged mordenite framework
[11]. In the present study, when exchanging singly charged cations for
Fe2þ, with an ionic radius close to that for Cu2þ, one can expect similar
results.
Fig. 3 shows the a/b ratio for all the studied mono- and bimetallic
samples plotted versus the Fe/Al as determined from ICP-OES. Despite in
the studied iron-containing samples a part of iron is accumulated on the
surface, see Table 1, the linear increase of the a/b ratio with iron
loading, evidences that a part of iron is in ion-exchangeable state, which
correlate with decrease of Na content. Moreover, the slope of the
dependence is the same as that one reported for Cu2þ [11] in the mor­
denite with the same Si/Al atomic ratio. However, in Fe-containing
samples studied in the present work, iron was partly accumulated on
the surface in various oxide of hydroxide forms, in addition to the partial
isomorphous substitution of Al3þ by Fe3þ discussed above. These data all
together point out that the share of ion exchangeable iron is lower that
one plotted in Fig. 3, and hence the slope of the a/b dependence on the
ion-exchangeable iron content would be steeper. So, one can conclude

6
M.G. Shelyapina et al. Microporous and Mesoporous Materials 299 (2020) 109841

that Fe2þ more effectively contracts the main channel of mordenite than 3 nm.
Cu2þ, in other words the effective charge of the Fe2þ cation is greater According to SEM and TEM analysis on the surface of all the silver-
than that of Cu2þ. The reason for such a difference in behavior of containing samples AgNPs are formed, and both their size and size
formally doubly charged cations located in the channels of the same distribution depend on the preparation method. The size distribution of
zeolite may be caused by the different structures of solvation layers AgNPs as determined from TEM analysis is shown in Fig. 4. In Ag-MOR-T
around Cu2þ and Fe2þ cations [38], and their different localization in it can be perfectly described by a Gaussian function, Figs. 4(a,e). For Ag-
the channel. MOR-20 the average particle size is 4.2 nm; the increasing of prepara­
Further analysis of Fig. 3 allows us to make some more comments. tion temperature results in particle enlargement up to 5.9 nm, that is due
First, for FeAg-MOR-60 and Ag-MOR-60 the lattice parameters, and to acceleration of the chemical reaction with increasing temperature.
hence their ratio, coincide within the experimental error. It points out Interestingly, the presence of iron leads to a systematic decrease in the
that at the treatment of Fe-MOR-60 at the AgNO3 solution the iron ions size of AgNPs. In case of FeAg-MOR-T this agrees with the observed
are completely displaced from their ion-exchangeable positions that
results to an important precipitation of iron-containing sediments on the
surface (see XPS data in Table 1). For Fe-MOR-20 a part of ion-
exchangeable iron persists. Second, for Ag-MOR-T the a/b value is
essentially higher that one for the starting material, Na-MOR. This
correlates with redistribution of peak intensities in the XRD patterns and
works in favor that Agþ enters into the main mordenite channel [25],
whereas Naþ comes out of the small one [39]. The quantity of the
ion-exchangeable Agþ in Ag-MOR-20 and Ag-MOR-60, however, should
be the same. It is difficult to estimate its amount directly, but evaluation
from remaining sodium yields that about 80% of Naþ was substituted by
Agþ. All this reasoning lead to a fundamental question about the nature
of ion exchange processes and the affinity of different cations to the
same ion-exchange centers. However, this is beyond the scope of this
work and will be discussed separately.
Moving forward, by analyzing the data reported in Table 3 one can
conclude that the incorporation of iron in the zeolite led to an increase in
surface area. This indicates both the absence of blocking of pores by non-
framework species, and the integrity of the crystal structure, which
correlates with X-ray data (see X-ray diffraction pattern for Fe-MOR-20,
Fig. 1 (a)). This suggests a finely dispersed state of iron on the surface of
the zeolite, i.e., the absence of oxide-hydroxide agglomerates in the
channels of the zeolite. In the case of Ag-containing samples, the pres­
ence of silver nanoparticles on the surface of mordenite was clearly
observed in microphotographs of all samples, showing that the forma­
tion of a certain amount of silver nanoparticles is an unavoidable phe­
nomenon under these sample preparation conditions. This observation is
consistent with the results of X-ray diffraction, which showed an addi­
tional peak of about 38.1–38.2� in 2θ (Fig. 1 (b)) in the diffraction
patterns of the bimetallic samples mAgFe-MOR-20 and AgFe-MOR-20,
those referred to plane (111) of metallic silver particles. Therefore, a
decrease in the specific surface of Ag-containing samples can be directly
related to the presence of Ag nanoparticles (AgNPs) that block pores or
cavities of the zeolite.
Let us now discuss AgNPs, which are formed on the mordenite par­
ticles, and the role of Fe in their formation. As one can see from Fig. 1(a)
for several Ag-containing samples an additional peak at 38.2� of 2θ,
which does not belong to the mordenite lattice, appears. It can be
attributed to the (111) line of the fcc lattice of metallic Ag. For better
visualization the region near this peak is plotted separately in Fig. 1(b)
(the XRD patterns for the samples synthetized at 60 � C can be found in
Supplementary Materials, Fig. S1(b)). This diffraction peak appears on
two occasions: after subsequent processing of Ag-MOR-T by the solution
of Fe(ClO4)2 or after ion-exchange from a mixed solution (AgNO3 and Fe
(ClO4)2). For the latter the diffraction peak is more intensive. Using the
Scherrer formula one can estimate the size of metal Ag particles as about
100 nm. This is comparable and even greater than size of mordenite
particles. Appearance of large silver crystallites can be issued from a
redox reaction: reduction of Agþ by Fe2þ with formation Fe3þ. However,
we remind that according to XPS for all the Ag-containing samples there
is an essential surface enrichment with silver (about one order of
magnitude compared to bulk). Moreover, the most important enrich­
ment is observed for Ag-MOR-T, for which the metal silver peaks are Fig. 4. Size distribution of the Ag nanoparticles on the mordenite surface for
absent in the XRD patterns. It means that either silver on the mordenite the studied silver containing samples. The averaged particle size <d1,2> as
surface is X-ray amorphous [40] or the size of nanoparticles is less than determined from Gaussian fit is shown.

7
M.G. Shelyapina et al.
reducing the size of AgNPs on iron-modified substrates [41–43].
The samples AgFe-MOR-T and mAgFe-MOR-T, which were prepared
by treatment of Ag-containing samples in a Fe2þ solution (sequentially
or simultaneously with treatment in an Agþ solution), are a special case.
Only in these samples large AgNPs (of about 100 nm) appear on the XRD
patterns, Fig. 1(b). We suggest the following mechanism of their for­
mation that supposes participation of Fe cations in the ion-exchange
process: AgNPs of a few nm size that have been already formed (AgFe-
MOR-T) or are forming (mAgFe-MOR-T) on the surface of mordenite
particles increase and precipitate out, whereas a new layer of AgNPs
grows up from Ag washed out from the bulk mordenite particles. And in
presence of iron these new appeared particles are smaller as compared to
Ag-MOR-T (similar to FeAg-MOR-T).
Another interesting point, in the samples prepared at 20 � C the
presence of iron results in a bimodal distribution of the size of AgNPs,
Fig. 4(b–d), more pronounced for mAgFe-MOR-20. Quite often such a
bimodal distribution leads to modification of electronic, catalytic or
bactericide properties of Ag nanoparticles [44,45].
Thus, it is obvious that in the studied bimetallic materials there is a
complex system of interactions between components, and each of the
components, both Ag and Fe, is presented in the form of mixture of
different species. The integral properties of the sample are a super­
position of the contributions of individual components with an addi­
tional synergetic interaction between some of them. The catalytic
properties of the mono- and bimetallic Ag-Fe mordenites have been
studied in Ref. [14], in which the catalytic test and evaluating the ac­
tivity of the studied samples are described in detail. A distinct impact of
the preparation method on the NO conversion was evidenced. Ag and Fe
alone are not good catalysts; however, bimetallic samples exhibit a
remarkable synergism. The question is, what are the interactions or
process responsible for catalytic activity of bimetallic samples.
It was found that FeAg-MOR-20 exhibits the best catalytic activity
[14]. According to the present studies, this sample, in comparison with
others, is characterized by: (i) the minimal size of AgNPs, 2.4 nm in
accordance with TEM, Fig. 4 (c); (ii) the maximum proportion of the
tetrahedral Fe3þ in the framework, which is 84% of the total Fe detected
by Mo €ssbauer, Table 4. Fig. 5 represents a correlation between the
maximal NO conversion and the share of the framework Fe3þ(Td)1. As
one can see, the data can be perfectly fitted by the linear function. The
Fig. 5. Correlation between the presence of framework Fe3þ sites in mordenite
and its catalytic deNOx activity. Solid line represents the linear fit.
8
Microporous and Mesoporous Materials 299 (2020) 109841
role of framework Fe in catalysis was discussed in several studies [29,30,
46,47]. The catalytic activity is governed by the acidity of the catalytic
center [30,47]. Isomorphous substitution Al3þ by Fe3þ in the zeolite
framework modulates acid strength of the existing catalytic sites or
create new. For example, in isomorphously substituted Fe-containing
mordenites prepared by hydrothermal synthesis the replacement of
Al3þ by Fe3þ leads to formation two kinds of Brønsted acidic sites, Si
(OH)Al and Si(OH)Fe, with higher and lower acid strength, respectively
[48]. The introduction of Fe into the framework of H-mordenite by
ion-exchange procedure with following calcination results to reduction
of the acid strength and as a consequence an increase of the catalytic
performance [29]. The similar effect was observed in MFI zeolites [46].
In Ref. [49] Fe3þ cations were also suggested as the species responsible
for the enhancement the catalytic activity in various Fe zeolites (MOR,
FER, HEU, CHA) obtained from ammonia form by conventional
ion-exchange procedure with subsequent calcination. The authors did
not discuss the framework Fe3þ but its electron spin resonance signal at
g ¼ 4.29 should be assigned to Fe3þ isomorphously substituted in the
tetrahedral positions [28].
The framework Fe3þ ions in zeolites are usually obtained during the
hydrothermal synthesis [28,48] or by post-synthesis isomorphous sub­
stitution (e.g. by an NH4F attack of the zeolite framework, which in­
volves the removal of aluminum lattice and the substitution by iron
introduced as FeF3 [46], or conventional ion-exchange procedure with
further calcination [29,47,49]). In the present work, in the Fe-MOR-T
samples obtained by ion-exchange procedure without further calcina­
tion, the share of the framework Fe3þ is minimal, as compared to
bi-metallic samples. It allows us to conclude, that presence of Ag stim­
ulates the introducing of Fe3þ into the mordenite framework.
In order to understand the role of the second component and the
order of introduction of the components, it should be reminded that
when preparing a bimetallic sample, the firstly prepared monometallic
one is placed into the excess of the second component. When synthe­
tizing the Fe-MOR-T samples Fe2þ is in a solution of the corresponding
salt. Iron in the oxidation state 2 þ can be only treated as an ion-
exchanged cation. However, during the ion-exchange process some
part of Fe2þ oxidizes to Fe3þ (the presence of oxygen, water and impu­
rities provokes the oxidation) and in this state there is an opportunity for
isomorphic substitution of Al3þ by Fe3þ. The Mo €ssbauer study confirms
that such an attack takes place. The competing process is the formation
of precipitates (oxides and/or hydroxides) on the surface. And, as one
can see, the largest number of different varieties is formed in the Fe-
MOR-T samples. The further treatment in AgNO3 leads to the oxidation
of the additional amount of ion-exchangeable Fe2þ cations (Fe2þ þ Agþ
→ Fe3þ þ Ag0) and the following processes take place: (i) the newly
formed Fe3þ situated near [AlO4]– attacks this site removing Al from the
lattice (that is confirmed by the ICP-OES), (ii) Ag0 diffuses on the surface
forming AgNPs, (iii) the vacated site of Fe2þ is occupied by Agþ. In other
words, the presence of silver leads to a decrease in variety of Fe species
(most of which are washed off the surface) and to a selective formation
of more active forms of iron.
In AgFe-MOR-T the Fe3þ substitution for Al3þ is less effective as there
is no excess of Agþ ions. In the mixture solution a certain balance is
established, a non-selective redox process goes directly in the solution
and the reaction products settle on the surface. However, in all the
bimetallic samples there is an additional oxidation of iron (of different
efficiency) and its introducing into the zeolite framework, which cor­
relates with the increase of catalytic performance.
Summing up, the reported in our previous work catalytic activity of
Ag, Fe and AgFe systems on mordenite [14] the better performance of
the bimetallic ones, especially FeAg-MOR-T, is caused mainly by the
framework Fe3þ that is additionally activated by Ag þ place nearby.
AgNPs of a few nm in size on the surface of Fe-mordenite particles can be
additional catalytic center. However, it should be noted that the pure
silver samples, Ag-MOR-T are not very active.
M.G. Shelyapina et al.
5. Conclusion
The results of our comprehensive study of the composition, structure
and morphology of mono- and bimetallic systems of Ag, Fe, and Ag-Fe
supported on mordenites can be summarized as follows:
� both the order of the ion exchange reactions and processing tem­
perature affect the quantity of Ag and Fe loaded into the mordenite,
their states and locations;
� Ag is accumulated on the surface in the form of X-ray amorphous
nanoparticles of 2–10 nm in size; however, charge compensating
cations Agþ are also present; the treatment in the excess of Fe2þ leads
to formation of crystalline AgNPs of about 100 nm in size;
� hydrated extra-framework Fe2þ cations are Mo €ssbauer silent at room
temperature, but their presence is evident from the increasing of the
a/b ratio caused by the contraction of the main mordenite channel
upon iron cations loading;
� incorporation of iron in the zeolite led to an increase in surface area.
It points out that extra-framework iron oxide or hydroxide species
are finely dispersed on the zeolite surface without formation ag­
glomerates in the mordenite channels;
� in the studied iron-containing mordenites the isomorphous substi­
tution of Al3þ by Fe3þ was confirmed by M€ ossbauer spectroscopy; the
portion of this framework Fe3þ in the studied mordenite samples
correlates with their catalytic deNOx activity;
� based on the reported results a mechanism of the isomorphous sub­
stitution of the framework Al3þ by Fe3þ promoted by Agþ was pro­
posed. This mechanism results to creating new effective catalytic
centers for deNOx reaction, which are (i) framework Fe3þ activated
by nearby Agþ and (ii) a very few nanosized Ag particles on the Fe-
mordenite surface.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The synthesis, TEM and textural studies were carried out at CNyN
UNAM, the Mo €ssbauer spectroscopy studies were done at Jagiellonian
University. Other investigations were carried out at the Research Park of
Saint Petersburg State University: Centre for Physical Methods of Sur­
face Investigation, Centre for X-ray Diffraction Studies, Interdisciplinary
Resource Centre for Nanotechnology. This work was supported by the
Russian Foundation for Basic Research (project No. 18-53-34004) and
DGAPA-UNAM IN107817 Grant.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2019.109841.
References
[1] I. Ogino, Understanding atomically dispersed supported metal catalysts: structure
and performance of active sites, Catalysis 31 (2019) 166–197, https://doi.org/
10.1039/9781788016971-00166.
[2] Y.M. Zhukov, M.G. Shelyapina, A.Y. Efimov, E.V.Z. Zhizhin, V. Petranovskii,
Recognition of depth composition profiles of copper-exchanged mordenites
applying analytical methods with different depth vision, Mater. Chem. Phys. 236
(2019) 1–5, https://doi.org/10.1016/j.matchemphys.2019.121787, 121787.
[3] P. Granger, V.I. Parvulescu, Catalytic NOx abatement systems for mobile sources:
from three-way to lean burn after-treatment technologies, Chem. Rev. 111 (2011)
3155–3207, https://doi.org/10.1021/cr100168g.
[4] V.I. P^
arvulescu, B. Cojocaru, V. P^
arvulescu, R. Richards, Z. Li, C. Cadigan,
P. Granger, P. Miquel, C. Hardacre, Sol-gel-entrapped nano silver catalysts-
9
Microporous and Mesoporous Materials 299 (2020) 109841
correlation between active silver species and catalytic behavior, J. Catal. 272
(2010) 92–100, https://doi.org/10.1016/j.jcat.2010.03.008.
[5] G. Li, E.A. Pidko, The nature and catalytic function of cation sites in zeolites: a
computational perspective, ChemCatChem 11 (2019) 134–156, https://doi.org/
10.1002/cctc.201801493.
[6] M. Iwasaki, K. Yamazaki, K. Banno, H. Shinjoh, Characterization of Fe/ZSM-5
DeNOx catalysts prepared by different methods: relationships between active Fe
sites and NH3-SCR performance, J. Catal. 260 (2008) 205–216, https://doi.org/
10.1016/j.jcat.2008.10.009.
[7] L. Ma, H. Chang, S. Yang, L. Chen, L. Fu, J. Li, Relations between iron sites and
performance of Fe/HBEA catalysts prepared by two different methods for NH3-
SCR, Chem. Eng. J. 209 (2012) 652–660, https://doi.org/10.1016/j.
cej.2012.08.042.
[8] N. Viswanadham, S.K. Saxena, A.H. Al-Muhtaseb, Cu functionalized nano
crystalline ZSM-5 as efficient catalyst for selective oxidation of toluene, Mater.
Today Chem. 3 (2017) 37–48, https://doi.org/10.1016/j.mtchem.2017.01.001.
[9] N. Spencer, J. Thornton (Eds.), Ion Exchange: Theory and Applications, Nova
Science Publishers, Incorporated, 2017.
[10] Y.M. Zhukov, A.Y. Efimov, M.G. Shelyapina, V. Petranovskii, E.V. Zhizhin,
A. Burovikhina, I.A. Zvereva, Effect of preparation method on the valence state and
encirclement of copper exchange ions in mordenites, Microporous Mesoporous
Mater. 224 (2016) 415–419, https://doi.org/10.1016/j.micromeso.2015.12.058.
[11] Y.M. Zhukov, M.G. Shelyapina, I.A. Zvereva, A.Y. Efimov, V. Petranovskii,
Microwave assisted versus convention Cu2þ exchange in mordenite, Microporous
Mesoporous Mater. 259 (2018) 220–228, https://doi.org/10.1016/j.
micromeso.2017.10.013.
[12] L.Y. Meng, B. Wang, M.G. Ma, K.L. Lin, The progress of microwave-assisted
hydrothermal method in the synthesis of functional nanomaterials, Mater. Today
Chem. 1–2 (2016) 63–83, https://doi.org/10.1016/j.mtchem.2016.11.003.
[13] H. Zhou, M. Ge, H. Zhao, S. Wu, M. Li, Y. Su, Selective catalytic reduction of nitric
oxide with propylene over Fe/Beta catalysts under lean-burn conditions, Catalysts
9 (2019) 205–1–17, https://doi.org/10.3390/catal9020205.
[14] P. S� anchez-L�opez, Y. Kotolevich, S. Miridonov, F. Ch� avez-Rivas, S. Fuentes,
V. Petranovskii, Bimetallic AgFe systems on mordenite: effect of cation deposition
order in the NO reduction with C3H6/CO, Catalysts 9 (2019) 58–1–17, https://doi.
org/10.3390/catal9010058.
[15] G.J. Long, T.E. Cranshaw, G. Longworth, The ideal M€ ossbauer effect absorber
thickness, M€ ossbauer Eff. Ref. Data J. 6 (1983) 42–49.
[16] C. Baerlocher, L.B. McCusker, Database of zeolite structures, n.d. http://www.
iza-structure.org/databases/. (Accessed 6 July 2019).
[17] M.M. Mohamed, Catalytic properties of Fe ion-exchanged mordenite toward the
ethanol transformation: influence of the methods of preparation, J. Mol. Catal. A
Chem. 200 (2003) 301–313, https://doi.org/10.1016/S1381-1169(03)00093-1.
[18] D.G. Rancourt, J.Y. Ping, Voigt-based methods for arbitrary-shape static hyperfine
parameter distributions in M€ ossbauer spectroscopy, Nucl. Instrum. Methods Phys.
Res. B. 58 (1991) 85–97, https://doi.org/10.1016/0168-583X(91)95681-3.
[19] R.G. Burns, Mineral M€ ossbauer spectroscopy: correlations between chemical shift
and quadrupole splitting parameters, Hyperfine Interact. 91 (1994) 739–745,
https://doi.org/10.1007/BF02064600.
[20] P. Fejes, J.B. Nagy, K. L� az�
ar, J. Hal�asz, Heat-treatment of isomorphously
substituted ZSM-5 (MFI) zeolites, Appl. Catal. Gen. 190 (2000) 117–135, https://
doi.org/10.1016/s0926-860x(99)00298-7.
[21] P. Fejes, I. Kiricsi, K. L�
az�ar, I. Marsi, A. Rockenbauer, L. Korecz, Attempts to
produce uniform Fe(III) siting in Fe content SOD and LTA zeolites: an EPR and
M€ ossbauer study, Appl. Catal. Gen. 242 (2003) 63–76, https://doi.org/10.1016/
S0926-860X(02)00506-9.
[22] R.M. Mih� alyi, K. L�
az�ar, M. Koll�ar, F. L�
onyi, G. P�
al-Borb� ely, A.
� Szegedi, Structure,
acidity and redox properties of MCM-22 ferrisilicate, Microporous Mesoporous
Mater. 110 (2008) 51–63, https://doi.org/10.1016/j.micromeso.2007.09.001.
[23] A. Meagher, V. Nair, R. Szostak, A M€ ossbauer ferrisilicates study of ZSM-5-type
ferrisilicates, Zeolites 8 (1988) 3–11, https://doi.org/10.1016/S0144-2449(88)
80022-8.
[24] B. Fultz, M€ ossbauer spectrometry, in: E. Kaufmann (Ed.), Charact. Mater., second
ed., John Wiley, New York, 2012, pp. 1–21.
[25] P. S� anchez-L�opez, J. Antúnez-García, S. Fuentes-Moyado, D.H. Galv� an,
V. Petranovskii, F. Ch� avez-Rivas, Analysis of theoretical and experimental X-ray
diffraction patterns for distinct mordenite frameworks, J. Mater. Sci. 54 (2019)
7745–7757, https://doi.org/10.1007/s10853-019-03407-w.
[26] P. Ratnasamy, R. Kumar, Ferrisilicate analogs of zeolites, Catal. Today 9 (1991)
329–416, https://doi.org/10.1016/0920-5861(91)80001-P.
[27] Z. Gabelica, S. Valange, Synthesis of MFI metallosilicate zeolites using metallic
amino complexes as mineralizing agents : an overview, Microporous Mesoporous
Mater. 30 (1999) 57–66.
[28] Y.S. Ko, H.T. Jang, W.S. Ahn, Hydrothermal synthesis and characterization of Fe
(III)-substituted mordenites, Korean J. Chem. Eng. 25 (2008) 1286–1291.
[29] H. Zhou, W. Zhu, L. Shi, H. Liu, S. Liu, S. Xu, Y. Ni, Y. Liu, L. Li, Z. Liu, Promotion
effect of Fe in mordenite zeolite on carbonylation of dimethyl ether to methyl,
Catal. Sci. Technol. 5 (2015) 1961–1968, https://doi.org/10.1039/C4CY01580K.
[30] J.A. Van Bokhoven, C. Lamberti, Structure of aluminum, iron, and other
heteroatoms in zeolites by X-ray absorption spectroscopy, Coord. Chem. Rev.
277–278 (2014) 275–290, https://doi.org/10.1016/j.ccr.2014.05.013.
[31] J.P. Lange, K. Klier, U.v.-vis-n.i.r. Studies of Fe(II)-A zeolite, Zeolites 14 (1994)
462–468, https://doi.org/10.1016/0144-2449(94)90173-2.
[32] L. Capek,
� V. Kreibich, J. D�ede�cek, T. Grygar, B. Wichterlov� a, Z. Sobalík, J.
A. Martens, R. Brosius, V. Tokarov� a, Analysis of Fe species in zeolites by UV-VIS-
NIR, IR spectra and voltammetry. Effect of preparation, Fe loading and zeolite type,
M.G. Shelyapina et al.
Microporous Mesoporous Mater. 80 (2005) 279–289, https://doi.org/10.1016/j.
micromeso.2004.12.014.
[33] P.J. Smeets, J.S. Woertink, B.F. Sels, E.I. Solomon, A. Robert, Transition metal ions
in zeolites: coordination and activation of oxygen, Inorg. Chem. 49 (2010)
3573–3583, https://doi.org/10.1021/ic901814f.
[34] A. Wang, Y. Wang, E.D. Walter, R.K. Kukkadapu, Y. Guo, G. Lu, R.S. Weber,
Y. Wang, C.H.F. Peden, F. Gao, Catalytic N2O decomposition and reduction by NH3
over Fe/Beta and Fe/SSZ-13 catalysts, J. Catal. 358 (2018) 199–210, https://doi.
org/10.1016/j.jcat.2017.12.011.
[35] F. Gao, M. Koll�ar, R.K. Kukkadapu, N.M. Washton, Y. Wang, J. Szanyi, C.H.
F. Peden, Fe/SSZ-13 as an NH3-SCR catalyst: a reaction kinetics and FTIR/
M€ ossbauer spectroscopic study, Appl. Catal. B Environ. 164 (2015) 407–419,
https://doi.org/10.1016/j.apcatb.2014.09.031.
[36] F. Gao, Y. Zheng, R.K. Kukkadapu, Y. Wang, D. Eric, B. Schwenzer, J. Szanyi, C.H.
F. Peden, Iron loading effects in Fe/SSZ-13 NH3-SCR catalysts : nature of the Fe-
ions and structure-function relationships, ACS Catal. 6 (2016) 2939–2954, https://
doi.org/10.1021/acscatal.6b00647.
[37] M.G. Shelyapina, E.A. Krylova, Y.M. Zhukov, I.A. Zvereva, I. Rodriguez-Iznaga,
V. Petranovskii, S. Fuentes-Moyado, Comprehensive analysis of the copper
exchange implemented in ammonia and protonated forms of mordenite using
microwave and traditional methods, Sci. Rep. (2019) 1–25.
[38] W.R. Fawcett, Charge distribution effects in the solution chemistry of polyatomic
ions, Condens. Matter Phys. 8 (2005) 413–424, https://doi.org/10.5488/
CMP.8.2.413.
[39] E.A. Krylova, M.G. Shelyapina, P. Nowak, H. Hara� nczyk, M. Chislov, I.A. Zvereva,
A.F. Privalov, M. Becker, M. Vogel, V. Petranovskii, Mobility of water molecules in
sodium- and copper-exchanged mordenites: thermal analysis and 1H NMR,
Microporous Mesoporous Mater. 265 (2018) 132–142, https://doi.org/10.1016/j.
micromeso.2018.02.010.
[40] S. Liu, W. Huang, S. Chen, S. Avivi, A. Gedanken, Synthesis of X-ray amorphous
silver nanoparticles by the pulse sonoelectrochemical method, J. Non-Cryst. Solids
283 (2001) 231–236, https://doi.org/10.1016/S0022-3093(01)00362-3.
10
Microporous and Mesoporous Materials 299 (2020) 109841
[41] A. Busiakiewicz, A. Kisielewska, I. Piwo, D. Batory, The effect of Fe segregation on
the photocatalytic growth of Ag nanoparticles on rutile TiO2(001), Appl. Surf. Sci.
401 (2017) 378–384, https://doi.org/10.1016/j.apsusc.2017.01.008.
[42] J. Xiao, H. Zhang, C. Mao, Y. Wang, L. Wang, Z. Lu, Ferric ion-assisted in situ
synthesis of silver nanoplates on polydopamine-coated silk, J. Colloid Interface Sci.
479 (2016) 244–250, https://doi.org/10.1016/j.jcis.2016.06.070.
[43] D. Li, G. Yang, P. Li, J. Wang, P. Zhang, Promotion of formaldehyde oxidation over
Ag catalyst by Fe doped MnOx support at room temperature, Catal. Today 277
(2016) 257–265, https://doi.org/10.1016/j.cattod.2016.02.040.
[44] G.A. Sotiriou, A. Teleki, A. Camenzind, F. Krumeich, A. Meyer, S. Panke, S.
E. Pratsinis, Nanosilver on nanostructured silica : antibacterial activity and Ag
surface area, Chem. Eng. J. 170 (2011) 547–554, https://doi.org/10.1016/j.
cej.2011.01.099.
[45] S. Yang, H. Wang, H. Yu, S. Zhang, Y. Fang, S. Zhang, F. Peng, A facile fabrication
of hierarchical Ag nanoparticles-decorated N-TiO2 with enhanced photocatalytic
hydrogen production under solar light, Int. J. Hydrogen Energy 41 (2016)
3446–3455, https://doi.org/10.1016/j.ijhydene.2015.12.190.
[46] M.M. Diallo, S. Laforge, Y. Pouilloux, J. Mijoin, Highly efficient dehydration of
glycerol to acrolein over isomorphously substituted Fe-MFI zeolites, Catal. Lett.
148 (2018) 2283–2303, https://doi.org/10.1007/s10562-018-2470-9.
[47] P. Boro�n, L. Chmielarz, J. Gurgul, K. Łątka, B. Gil, B. Marszałek, S. Dzwigaj,
Influence of iron state and acidity of zeolites on the catalytic activity of FeHBEA,
FeHZSM-5 and FeHMOR in SCR of NO with NH3 and N2O decomposition,
Microporous Mesoporous Mater. 203 (2015) 73–85, https://doi.org/10.1016/j.
micromeso.2014.10.023.
[48] P. Wu, T. Komatsu, T. Yashima, Isomorphous substitution of Fe3þ in the framework
of aluminosilicate mordenite by hydrothermal synthesis, Microporous Mesoporous
Mater. 20 (1998) 139–147, https://doi.org/10.1016/S1387-1811(97)00005-X.
[49] R.Q. Long, R.T. Yang, Selective catalytic reduction of NO with ammonia over Fe3þ
-exchanged mordenite (Fe–MOR): catalytic performance , characterization , and
mechanistic study, J. Catal. 285 (2002) 274–285, https://doi.org/10.1006/
jcat.2002.3521.