Catalysis Today xxx (xxxx) xxx–xxx

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Catalysis Today
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Activity of an iron Colombian natural zeolite as potential geo-catalyst for

NH3-SCR of NOx
John-Freddy Gelvesa, Ludovic Dorkisb, Marco-A. Márquezc, Andrés-Camilo Álvarezd,
⁎
Lina-María Gonzálezd, , Aída-Luz Villad
a
Grupo de investigación competitividad y sostenibilidad para el desarrollo, Facultad de Ingeniería, Universidad Libre seccional Cúcuta, Cúcuta, Colombia
b
Grupo de investigación en Catálisis y Nanomateriales, Facultad de Minas, Departamento de Materiales y Minerales, Universidad Nacional de Colombia sede Medellín,
Medellín, Colombia
c
Grupo de Mineralogía Aplicada y Bioprocesos, Facultad de Minas, Departamento de Materiales y Minerales, Universidad Nacional de Colombia sede Medellín, Medellín,
Colombia
d
Environmental Catalysis Research Group, Engineering Faculty, Chemical Engineering Department, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín,
Colombia

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

Keywords: The Selective Catalytic Reduction of NOx by ammonia (NH3–SCR of NOx) was studied over an iron Colombian
Geo-catalysts natural zeolite (Nat-zeo) based geo-catalysts after several treatments (H-zeo-Fe3+ and H-zeo-Fe2+) under lean,
NH3-SCR dry and wet conditions. Nat-zeo from the Combia geological formation in Colombia (South America) was treated
Nitrogen oxides with NH4NO3, calcined in air for obtaining H-zeo-Fe3+ and then reduced with hydrogen to obtain the H-zeo-
Selective catalytic reduction
Fe2+ catalyst. Catalysts were characterized by XRD, FTIR, Mössbauer spectroscopy, SEM/EDX, XRF BET,
Iron catalysts
H2–TPR, NH3–TPD, and NOx–TPD. H-zeo-Fe3+ showed better catalytic performance than Nat-zeo and H-zeo-
Fe2+ in the NOx conversion. The presence of Fe3+ ions and the acidity in the catalyst explains partially the high
activity towards NOx reduction. Water inhibits the NO and improves the NO2 adsorption on the catalyst H-zeo-
Fe3+ surface according with the NOx-TPD analysis. After 30 h on-stream, under wet conditions, the H-zeo-Fe3+
catalyst showed a decreased in the NOx conversion. The decrease of activity could be related with the loss of
catalyst surface acidity detected by NH3-TPD analysis after reaction and with the contraction of the zeolite
channels due to the metaheulandite phase formation that was confirmed by XRD, BET and FTIR analysis.

1. Introduction compared with commercial V2O5 catalysts [8,9], and operates at a

Motor vehicles are the main emission source of nitrogen oxides
(NOx) into the atmosphere, which reached dangerous levels and pro-
jected emission values above 1.6 Mt/year only in European light duty
diesel vehicles [1]. NOx are known to cause the formation of acid rain,
photochemical smog, and ground-level ozone [2,3]. Ground-level ozone
is a very potent greenhouse gas and it has a direct warming effect on
climate [3,4]. Several researches are addressed in decreased NOx ve-
hicular emissions varying the engine type, operating conditions, and
fuel used [5]. Notwithstanding, these efforts for reducing NOx emis-
sions do not solve completely the problem, and even increase them
[5,6]. In the treatment of NOx from exhausts, the three major tech-
nologies are lean NOx traps (LNT), ammonia (or urea) Selective Cata-
lytic Reduction (NH3-SCR) and Hydrocarbon Selective Catalytic Re-
duction (HC-SCR) [7]. The leading technology is the NH3-SCR using
zeolites with Fe and Cu ions, which have better hydrothermal stability
wider range of temperatures [8–10]. The iron-based catalysts have at-
tracted attention owing to high NH3-SCR activity, low cost and lack of
toxicity relative to vanadium [10]. Iron oxides catalysts have been used
in the NH3-SCR, but they show low-temperature activity (between 150
and 300 °C) due to the low surface area and acidity [9,10]. On the other
hand, iron-based zeolites have high activity at temperatures above
300 °C and in comparison with copper-based zeolites, they produce
fewer amounts of side products such as N2O and have better hydro-
thermal stability [11].
Volcanic rocks containing natural zeolites have been mined world-
wide for more than 1000 years for use as cements and building stone.
Since the 1950’s, natural zeolites have found a variety of applications in
adsorption, catalysis, building industry, agriculture, soil remediation,
and energy [12,13]. The use of natural zeolites for environmental ap-
plications is gaining new research interests mainly due to their prop-
erties, and significant worldwide occurrence. A conversion of NOx

⁎
Corresponding author.
E-mail address: lina.gonzalez@udea.edu.co (L.-M. González).

https://doi.org/10.1016/j.cattod.2018.01.025
Received 26 September 2017; Received in revised form 11 January 2018; Accepted 21 January 2018
0920-5861/ © 2018 Elsevier B.V. All rights reserved.

Please cite this article as: Gelves, J.-F., Catalysis Today (2018), https://doi.org/10.1016/j.cattod.2018.01.025
J.-F. Gelves et al.
above 80% in NH3-SCR was obtained over natural chabazite with iron,
however low stability of the material was observed under hydrothermal
conditions [14]. The presence of an iron-rich natural zeolite (around
12 wt% of Fe2O3) with heulandite (HEU) framework mixed with small
amounts of the zeolites chabazite (CHA), phillipsite (PHI) and morde-
nite (MOR) was recently reported in the andesitic basalts from the
Combia geological formation in Colombia (South America) [15]. This
natural zeolite showed activity for the simultaneous NOx and o-di-
chlorobenzene removal (conversions of: NO around 5% and o-DCB
around 25% at 550 °C) using methane as reducing agent under wet and
lean conditions [16].
The present study aim is to report the characterization and potential
of an iron Colombian natural zeolite [15] as geo-catalyst for NH3-SCR
of NOx under lean and hydrothermal conditions. The natural zeolite
was tested in the reaction without any treatment and after the proton
incorporation for obtaining an acid material. Because Fe3+ and Fe2+
species may have a different effect on NH3-SCR of NO reaction [18–20],
this effect was also evaluated on the natural zeolite used as catalyst. The
fresh catalysts were characterized by X-ray powder diffraction (XRD),
Fourier transform infrared spectroscopy (FTIR), Mössbauer spectro-
scopy, scanning electron microscopy with energy dispersive X-Ray
spectroscopy (SEM/EDX), X-ray fluorescence spectroscopy (XRF), BET
surface area, temperature-programmed reduction under hydrogen (H2-
TPR), and temperature-programmed desorption of ammonia (NH3-TPD)
and nitrogen oxides (NOx-TPD). The catalyst with the best performance
in the NH3-SCR of NO reaction was tested during 30 h on-stream for
evaluation of its durability; furthermore, the material was characterized
after reaction by XRD, FTIR, BET, and NH3-TPD.
2. Experimental
2.1. Catalyst preparation
2.1.1. Extraction of natural zeolite
Natural zeolite used in this work as Geo-catalyst was collected from
the riverbed of the creek “La Sucia”, located north of the La Pintada
municipality in the state of Antioquia-Colombia (South America) that is
part of the volcanic member of the Combia geological formation [15].
The separation process of the zeolite from the rock was performed with
dense liquids method [21] using LST heavy liquid from Central Che-
mical Consulting − Australia (density of 2.25 g cm−3 operating at room
temperature) [22]. Initially the rock was manually grinded in an agate
mortar, sieved in a Tyler 20 mesh (< 840 μm), and settled in the LST
heavy liquid. The material rich in the zeolites (with a density less than
2.25 g cm−3) floated and was separated by filtration. Subsequently, it
was cleaned in an ultrasonic bath with distilled water (Elma LC20/H)
for 5 min in order to remove residues of LST bonded to the surface of
the zeolites. Finally the solid was dried at 110 °C in an oven, milled and
sieved to a diameter < 250 μm (120 Tyler mesh). This material was
coded as Nat-zeo.
2.1.2. Synthesis of H-zeo-Fe3+ and H-zeo-Fe2+ materials
In order to facilitate the ammonium ion exchange in the Nat-zeo
material, the solid was treated with a 0.5 M solution of NaCl (Merck
99.5%) at 90 °C and 400 rpm magnetic agitation speed, with a ratio of
(1 g of Nat-zeo) (10 mL of solution)−1. The process was performed for
5 days, renewing the solution every 24 h [17]; then the sample was
washed with distilled water until negative presence of chlorine. Finally,
the solid was filtrated and dried at 110 °C for 24 h. The sodium rich
material obtained was then exchanged with ammonium nitrate
(NH4NO3) (Merck 99%) using a similar procedure as described above.
The solid material was calcined in a muffle furnace at 360 °C during 6 h.
The final material was coded H-zeo-Fe3+. H-zeo-Fe2+ catalyst was
obtained by reduction of H-zeo-Fe3+ with 50 mL min−1 of 10% H2/Ar
flow with a heating rate of 10 °C min−1 and at 600 °C for 2 h.
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Catalysis Today xxx (xxxx) xxx–xxx
2.2. Catalyst characterization
XRD patterns were performed at 5° ≤ 2θ ≤ 55° in a Rigaku Miniflex
II diffractometer, with graphite monochromator using Cu Kα radiation
at 30 KV and 15 mA, the scan step was 0.02°, and the counting time per
step was 2 s. The software used for qualitative and semi-quantitative
analysis (Rietveld refinement) was PANalytical Xpert Highscore Plus.
The American Mineralogist Crystal Structure Database was used for
identifying the crystalline phases in the material. The FTIR spectra were
recorded in a Shimadzu 8400S spectrophotometer. Spectra were col-
lected at room temperature, in KBr pellets ((1 mg sample) (100 mg KBr
pressed at 10 t)−1), using 48 scans, at 4 cm−1 of resolution in trans-
mittance mode, in the range of 4000 and 400 cm−1. The software used
for the analysis was IR Solution v.1.4. Local iron ion configurations in
the Nat-zeo were determined by Mössbauer spectroscopy. The
Mössbauer spectra were collected in transmission geometry at room
temperature, using a conventional Wissel™ Mössbauer spectrometer,
equipped with a 57Co (Rh) source working at constant acceleration. The
Mössbauer 57Fe spectrum was calibrated by α-Fe as standard. The
spectrum was adjusted and analyzed using the Recoil program in order
to obtain the hyperfine parameters (hyperfine field, quadrupole and
isomeric change). External morphology of the natural zeolite was
evaluated with JEOL scanning electron microscopy, model JSM-
5910LV. The chemical microanalysis was done using SEM coupled with
EDX from INCA Oxford instruments (accelerating voltage of 15 kV,
counting time of 80 s and working distance of 10 mm). The chemical
composition of the natural zeolite was performed in an Axios X-ray
fluorescence spectrometer from PANalytical, using the software
WROXI. For the XRF analysis, the sample was compacted into a pellet at
20 t pressure. The surface area, pore volume and pore size distribution
were determined by BET analysis in an ASAP 2020 V4.00 (V4.00 J)
equipment from Micromeritics (sample degassed at 523 K for 12 h, and
N2 adsorption at 77 K). H2–TPR and NH3–TPD experiments were carried
out in an AutoChem II 2920 instrument (Micromeritics) equipped with
a thermal conductivity detector (TCD). H2–TPR of fresh samples were
obtained by flowing 50 mL min−1 of a mixture 10% H2/Ar and heating
from 50 to 1050 °C using a heating rate of 10 °C min−1. Before H2–TPR
analysis, the samples were treated under 50 mL min−1 of flowing argon
at 350 °C for 2 h. NH3–TPD was used to determine the total acidity of
samples. Before analysis the samples were flushed with flowing He
(50 mL min−1) for 2 h at 350 °C, then the sample was cooled to 50 °C.
The saturation adsorption of ammonia was performed at 50 °C by
flowing 50 mL min−1 of a gas mixture 5% NH3/He for 60 min. In order
to remove any physical adsorbed ammonia, the sample was flushed
with 50 mL min−1 of He for 2 h. Desorption of ammonia was obtained
by rising the temperature at 10 °C min−1 up to 700 °C. For NOx-TPD
analysis two types of experiments were performed: NO-TPD and NO2/
N2O-TPD in the presence or absence of water vapor. Prior to NOx-TPD,
50 mg of the sample was flushed with 50 mL min−1 of an inert gas at
350 °C for 2 h. In the NO-TPD, the sample was saturated with 500 ppm
of NO at 50 °C for 2 h in the presence of water vapor (0–5% vol). The
sample was flushed for 4 h and finally the temperature was raised to
550 °C at 5 °C min−1. A similar procedure was followed in the NO2/
N2O-TPD, the sample was saturated with a mixture of 350 ppm NO2 and
20 ppm N2O at 50 °C for 2 h in the presence of water vapor (0–5% vol).
The gas concentration was monitored with an Antaris IGS, Thermo
Scientific FTIR equipment, equipped with a MCT detector, KBr
beamsplitter, 2 m pathlength gas cell, 200 mL gas cell volume and a
ZnSe window. Data were collected with a spatial resolution of 0.5 cm−1
with 32 scans for each sampling. Gas cell was operated at atmospheric
pressure and the temperature was fixed at 150 °C in order to avoid
condensation of the reactants inside the gas cell. A quantification model
was developed by taking several spectrums of known gas mixtures and
adjusting the absorbance and concentrations data by means of partial
least square quantitative analysis, the software TQ Analyst 9.4.45
(Thermo Fisher Scientific Inc.) was used for this purpose.
J.-F. Gelves et al.
2.3. Catalytic reactions
Catalytic reactions were carried out in a quartz tube fixed–bed re-
actor (0.015 m i.d. × 0.4 m length) containing a frit to hold the powder
catalyst samples. The reactor was operated at atmospheric pressure
(0.84 atm) in steady state plug–flow mode. Reactor temperature was
varied from 150 to 550 °C. The reactant gases were fed using electronic
mass flow controllers (Sierra Instruments and Brooks 5850E) and mixed
in line before entering the reactor. Ammonia was entered 100 mm
above the bed to assure reaction just in the catalyst, and to minimize
homogenous reactions. The total flow was 100 mL min−1
(GSHV = 30000 h−1). The gas composition of the reactant mixture was
445 ppm NOx (400 ppm NO, 45 ppm NO2), 400 ppm NH3, 8% O2, 0–5%
H2O, and argon balance. Water vapor was introduced into the reaction
system by means of a saturator at 60 °C, using Ar as carrier gas. Gases
were analyzed by an Antaris IGS, Thermo Scientific FTIR, as described
above. NO and NH3 conversions were calculated according to Eqs. (1)
and (2), respectively.
[NO]in − [NO]out ⎞
NO Conversion (%) = 100 ⎛ ⎜ ⎟
⎝ [NO]in ⎠ (1)
[NH3]in − [NH3]out ⎞
NH3 Conversion (%) = 100 ⎛ ⎜ ⎟
⎝ [NH3]in ⎠ (2)
Durability test was carried out for 30 h of continues operation at the
temperature where the highest conversion was obtained with the cat-
alyst with the best performance.
3. Results and discussion
3.1. Catalysts characterization
3.1.1. XRD
X-ray diffraction (XRD) patterns of Nat-zeo, H-zeo-Fe3+, and H-zeo-
Fe2+ catalysts are shown in Fig. 1. According with XRD analysis is
possible to establish the presence of three crystalline phases in the Nat-
zeo material. Heulandite/clinoptilolite and plagioclase feldspar (anor-
tita and labradorite) are found as major phases, while celadonite ap-
pears as minority phase. By means of Rietveld refinement it can be
established that the heulandite (heulandite + clinoptilolite) phase re-
presents about 70 wt% of the composition of Nat-zeo material, followed
by calcium plagioclase 25 wt% (equal amount of anortite and
3
Catalysis Today xxx (xxxx) xxx–xxx
labradorite), and celadonite with 5 wt%. Similar composition in natural
zeolites used as catalysts has been previously reported [23–25]. The
XRD pattern of the acid catalyst H-zeo-Fe3+ shows much similarity with
the diffraction pattern of the starting Nat-zeo material. However, there
are two important changes in its pattern. The first one is associated with
the decrease in the intensity of the reflection planes of the heulandite
phase, Fig. 1. The second aspect is related with the presence the me-
taheulandite phase. The formation of this phase is associated with the
transformation of the heulandite phase at temperatures above 300 °C
[26], which in our case occur during the elimination of the NH4+ ions
at 360 °C. This dehydrated heulandite exhibits a decrease in the unit
cell parameters and in the size of the zeolitic channels [26].
In the case of the reduced catalyst H-zeo-Fe2+, the diffraction pat-
tern (Fig. 1) shows that the intensity of the reflection plane (020) of
metaheulandite (2θ around of 11°) increased in comparison with the
intensity in H-zeo-Fe3+ material. The increment of this phase can be
associated with the disappearance of the low stability phase of the
heulandite structure during the reduction process at 600 °C; which is
evidenced by the notorious decrease in the intensity of the peak at 10°.
3.1.2. FTIR
Infrared analysis corroborates the presence of the heulandite
structure in the catalysts, Fig. 2. The “fingerprint” region of the heu-
landite phase in the FTIR spectra of the three catalysts present the
characteristic vibrations of this zeolite, such as vibration of the pseu-
dolattice rings at 604 cm−1, the asymmetric stretching vibration of the
TO group at 1198 cm−1, and the stretching band of the TO4 group
(between 1020 and 1060 cm−1) [27,28]. However, a widening in the
band at 604 cm−1 and in the TO4 group bands is evidenced after the
heat treatment in the Nat-zeo (calcination of ammonium ions and re-
duction treatment). This widening is associated with a decreasing in the
crystallinity of the heulandite phase [27,28]. FTIR analysis also shows
the symmetrical stretching of the OH groups at 3620 cm−1 and
3440 cm−1 [27,28]. The presence of calcite or dolomite in the catalysts
is evidenced by the band at 1450 cm−1, which is associated with the
asymmetric tension of the CO3 group [27]. Calcite concentration in the
catalysts must be low since it was not identified by XRD.
In the case of the H-zeo-Fe3+ catalyst, the band at 1405 cm−1
corresponds to the vibration of some NH4+ ions that remain as ex-
change cations in the zeolite [29]. The presence of celadonite and
plagioclase is not very noticeable by FTIR, possibly due to the over-
lapping of the characteristic vibrations bands of the heulandite zeolite.
Fig. 1. XRD patterns of Nat-zeo, H-zeo-Fe2+, H-zeo-Fe3+ and H-zeo-
Fe3+, U (U: used, reaction conditions: 400 ppm NO, 45 ppm NO2,
400 ppm NH3, 8% O2, 5% H2O, and balance Ar, GHSV = 30000 h−1,
400 °C, 30 h on stream). O: orthoferrosilite, H: heulandite/clinoptilite,
C: celadonite, M: metaheulandite, P: plagioclase feldspar.
J.-F. Gelves et al.
Fig. 2. FTIR spectroscopy analysis of Nat-zeo, H-zeo-Fe2+, and H-zeo-Fe3+ catalysts
before and after reaction (reaction conditions: 400 ppm NO, 45 ppm NO2, 400 ppm NH3,
8% O2, 5% H2O, and balance Ar, GHSV = 30000 h−1, 400 °C, 30 h on stream).
However, the vibration band of the Mg-Fe3+ species of the celadonite at
3550 cm−1 was evidenced in the spectra of natural zeolite (Nat-zeo)
and in the catalyst H-zeo-Fe3+ (Fig. 2) [27,28]. In the reduced material
H-zeo-Fe2+ this band is no longer evident, possibly due to the trans-
formation of the celadonite to a new ortoferrosilite phase (according to
the result of XRD, see Fig. 1).
3.1.3. Mössbauer spectroscopy
Mössbauer spectroscopy was used to elucidate the chemical en-
vironment and the coordination of the iron ions present in natural
zeolite extracted (Nat-zeo). This technique allows checking the pre-
sence of the iron in the zeolite or in the minority phases such as cela-
donite (Fig. 3 and Table 1).
According with Fig. 3, the Mössbuaer spectrum of Nat-zeo catalyst
shows an asymmetric doublet with lower intensity in the left and high
dispersion in the baseline, which suggest a low iron content in the
sample. Based on these experimental results, it is possible to establish a
model considering two sites for the iron in the natural zeolite. The
values of the isomeric shift (IS), Table 1, lead us to conclude that the
iron in the Nat-zeo material is present as Fe3+ in agreement with lit-
erature reports [30–32]. The data adjustment allows to identify the
existence of quadrupole splitting in the material spectrum (Fig. 3). This
fact implies that the iron in this material is not located in an isometric
crystal structure. The distance between the peaks of the sites 1 and 2
Fig. 3. Experimental (EXP) and fitted (FIT) room temperature Mössbauer spectrum of
Nat-zeo catalyst. Spectrum was fitted using Recoil program.
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Table 1
Hyperfine parameters obtained from Mössbauer spectrum of Nat-zeo.
Site IS (mm s−1) ΔQ (mm s−1) W (mm s−1) Concentration (%)*
1 (doublet 1) 0.21 0.33 0.14 79
2 (doublet 2) 0.38 0.21 0.10 21
IS: isomer shift, ΔQ: quadruple splitting, W: width.
* Based on the peak area percentage calculated by the integration of the area under the
curve.
(see Fig. 3) allows to corroborate that the iron is found as Fe3+
[30,31,33]. According with the isomeric shift (IS) and quadrupole
splitting (ΔQ) we can establish that the iron in “site 1” is in a tetra-
hedral coordination, while in “site 2” is in octahedral coordination
[30,34]. An approximate concentration of the sites 1 and 2 is 79% and
21%, respectively (Table 1).
The hyperfine parameters obtained for Fe3+ ions at site 2 are quite
similar to those reported for the celadonite phase at octahedral sites.
Fe3+ in this environment has been associated with the IR vibration
band of (Fe3+-Mg)-OH at 3550 cm−1 observed in the FTIR analysis of
the Nat-zeo, Fig. 2 [35–37]. Respecting to the site 1, this iron could be
present in the structure (tetrahedral) of the zeolite and feldspar type
plagioclase [35].
3.1.4. SEM/EDX
Fig. 4 shows the morphology of the Nat-zeo material, which allows
the recognition of heulandite zeolite crystals with laminar habit and
predominance of the plane (020). This observation is in agreement with
the high intensity of peak at 2θ = 10° found in the XRD analysis (see
Fig. 1). The predominant laminar habit in the material could be related
with the presence of the potassium, Table 2, which acts as compensa-
tion cation in the structure [38]. The presence of celadonite film is
observed like a coating the surface of the zeolite crystals, Fig. 4b.
The chemical microanalysis displayed in Table 2 confirms the pre-
sence of heulandite phase due to the predominance of calcium and
potassium which are their characteristic compensation cations [38].
However, the presence of calcium as compensating cation reduces the
thermal stability of the heulandite structure [26,39]. In the case of the
celadonite film, the composition found (Table 2) is typical for this
material [15]. The content of Fe3+ present in the celadonite could
generate a synergistic effect with the acidic sites suitable for its use in
the selective catalytic reduction of NOx [18,23,24].
3.1.5. XRF
The chemical analysis by X-ray fluorescence, expressed as oxides, is
presented in Table 3. The main elements present in the natural material
are silicon and aluminum, in a Si/Al ratio of 3.76. This fact permits to
identify the phases of the zeolite group as a silica heulandite with
medium thermal stability [40].
The presence of calcium is associated with the existence of felds-
pathic and zeolitic phases according to the XRD analysis. Magnesium is
directly related to the presence of celadonite and in a lesser extent to
heulandite, as evidenced in EDX results. In the case of potassium, it can
be associated to the clinoptilolite [41], celadonite [42], and in small
amounts to heulandite [43] phases. The amount of iron (4.51 wt% as
Fe2O3 or 3.15 wt% as Fe) present in the natural material (Nat-zeo)
could be sufficient for being an active site in the NH3-SCR of NOx
[18,23,24]. Traces of Ba and Sr in the Nat-zeo are associated to the
heulandite phase [44]. Ti, Sr, Mn and other elements are also present;
these elements may come from residual phases of basalt after the
concentration process, which cannot be identified by FTIR and XRD, or
be present as compensation cations in some zeolite crystals.
3.1.6. BET analysis
The adsorption/desorption isotherm for the natural material (Nat-
J.-F. Gelves et al. Catalysis Today xxx (xxxx) xxx–xxx

Fig. 4. SEM analysis of Nat-zeo catalyst.

Table 2
EDX-Microanalysis of heulandite and celadonite phases in Nat-zeo.

Heulandite Celadonite

Element % Atomic Element % Atomic

O 54.59 O 52.84
Si 33.77 Si 26.06
Al 7.47 Al 5.45
Ca 3.08 Ca 0.84
K 0.95 K 2.16
Mg 0.14 Mg 4.86
Fe 0.00 Fe 7.77

Table 3
Chemical analysis of the Nat-zeo material by XRF.

Oxide Weight%

SiO2 63.31
Al2O3 14.90
CaO 5.48
Fe2O3 4.51
K2O 1.98
MgO 1.30
BaO 0.18
SrO 0.11
TiO2 0.07
MnO 0.06
SO3 0.04
CuO 0.03
As2O3 0.03
SnO2 0.02
V2O5 0.02
SeO2 0.010
Loss of ignition 7.96

zeo) is shown in Fig. 5a and the textural properties obtained from BET
analysis of the Nat-zeo and the catalyst H-zeo-Fe3+ before and after
reaction are presented in Table 4. The Nat-zeo material shows a typical
adsorption/desorption isotherm type IV associated to mesoporous ma-
terials, with an hysteresis loop H2 that indicates pores with narrow
mouths (ink-bottle pores), uniform channels and connectivity [40,45].
According with this BET analysis is also possible to establish that in Nat-
zeo material there is a mixture of microporous (monolayer-multilayer
adsorption in p/p0 lower than 0.6) and mesoporous (capillary con-
densation in mesoporous with p/p0 above 0.9). The mesoporosity in the
material can be associated with the presence of the minor phases of
phyllosilicates such as celadonite mica. Similarly, heulandite type
zeolite with lamellar morphology can generate mesoporosity in the
Fig. 5. N2 adsorption/desorption isotherms of a) Nat-zeo catalyst and b) H-zeo-Fe3+
catalyst before (solid line) and after reaction (dotted line with symbol) (reaction condi-
tions: 400 ppm NO, 45 ppm NO2, 400 ppm NH3, 8% O2, 5% H2O, and balance Ar,
GHSV = 30000 h−1, 400 °C, 30 h on stream).
regions where the cleavage planes are given (see Fig. 4a) [46,47].
An important change is observed in the Nat-zeo after the acid
treatment and calcination to obtain H-zeo-Fe3+, Fig. 5b. BET analysis of
H-zeo-Fe3+ displays a typical shape of a zeolitic material with an iso-
therm type I and the hysteresis loop of the type H4 [45,46]. In addition,
it is observed a lower average pore size of H-zeo-Fe3+ in comparison
with Nat-zeo material (Table 4).

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Table 4 around 150 °C and 510 °C which are associated to weak and strong acid
Textural parameters of Nat-zeo and H-zeo-Fe3+ catalysts before and after reaction. sites, respectively [53]. After the modification of the natural zeolite, by
ion exchange, is evident the increment in the total acid concentration in
Material SBETa db (Å) Amicroc(m2 g−1) Amesod(m2 g−1) Vpe(cm3 g−1)
(m2 g−1) the H-zeo-Fe3+ catalyst (Table 5). These changes are directly associated
with the type of compensation cation present in the zeolite structure,
Nat-zeof 30.61 193.8 3.41 20.51 0.029 since it modifies the electronegativity, the ability to form hydroxyl
H-zeo- 28.28 124.5 2.58 25.70 0.088
groups and the diffusion of the NH3 into the channels of the zeolite
Fe3+
fresh [54–56].
H-zeo- 26.94 136.7 5.59 21.35 0.092
Fe3+
3.2. Activity measurements
usedg

a
Specific surface area calculated by the Brunauer–Emmett–Teller (BET) method.
b
Average pore size, derived from the BJH adsorption (4 V/A).
c
Micropore area calculated by t-plot method.
d
Mesopore area calculated by t-plot method.
e
Total pore volume estimated from the N2 adsorbed amount at p/p0 = 0.99.
f temperature range between 300 °C and 450 °C. This activity can be
Analysis performed in a Tristar 3000 from Micromeritics.
g
After 30 h in reaction.
In comparison with many of the synthetic zeolites [48], the surface
area of natural materials can be considered low (Table 4); however,
these values are typically reported for heulandite and celadonite ma-
terials [49,50]. The mesoporosity of the material is reflected by the
average pore size of the material (193.8 Å) [49]. After the treatment for
obtaining the proton form in catalyst H-zeo-Fe3+, both the pore size
and the surface area decrease. This fact can be due to the changes in the
crystallinity observed by XRD and FTIR (Figs. 1 and 2, respectively).
3.1.7. H2–TPR
The H2–TPR profile of Nat-zeo, is presented in Fig. 6. In the natural
zeolite, Nat-zeo, the reduction profile showed the presence of two peaks
at 523 °C and 623 °C, associated with the reduction of cations or oxo-
cations Fe3+ to Fe2+ ions in different sites of the zeolite [18]. In the
case of Fe2+ sites detected in the Mössbauer analysis (Fig. 3), the TPR
analysis showed the peaks at 698 °C and 794 °C may associated with the
reduction of Fe2+ to Fe0 [18,51,52]. The peaks at 954 °C and 1021 °C
may be associated with some residual iron species located in the more
stable structure orthoferrosilite (observed in the XRD analysis) [18].
3.1.8. NH3–TPD
NH3–TPD profiles of Nat-zeo and H-zeo-Fe3+ fresh samples are
shown in Fig. 7, and ammonia consumptions for each material are
presented in Table 5. The acid–strength distribution is determined with
the ammonia desorbed peaks above 100 °C. Two peaks are observed at
The conversions of NO and NH3 as a function of temperature over
the natural zeolite and the modified materials (H-zeo-Fe3+ and H-zeo-
Fe2+) are compared in Figs. 8 and 9, respectively.
The Nat-zeo material showed a NO conversion around of 20% in the
associated with the presence of isolated Fe species on the zeolite fra-
mework [51], probably in tetrahedral positions, according with Moss-
bauer spectroscopy (Fig. 3) [57]. In addition, iron species have high
oxygen storage capacity and mobility based on their redox Fe2+/Fe3+
equilibrium [58].
In our case, with H-zeo-Fe3+ and H-zeo-Fe2+ catalysts (Fig. 8a), the
maximum NO conversion was attained at around 400 °C and then it
decreased because of NH3 oxidation (Fig. 9). Fe3+ and Fe2+ are active
species in the NOx reduction [59,60]. Here the catalyst H-zeo-Fe3+
showed the highest NO conversion. Fe3+ species improve the reactivity
of the catalyst [11,29,59]. This fact can be associated with the high
concentration of NO2 observed with this catalyst (Fig. 8b), that is the
determining step in the SCR process over zeolites [60,61]. NOx can be
converted according with the reactions 3 and 4, but in the presence of
NO2 the reaction is more efficient due to the existence of a fast SCR
reaction [9,59,61]. NO2 can be provided in the inlet gas or produced by
the oxidation of NO [59].
4NO + 4NH3 + O2 → 4N2 + 6H2 O (3)
NO + 2NH3 + NO2 → 2N2 + 3H2 O (4)
Oxidized Fe 3+
species interact with NO producing NO2; however,
this reaction is controlled by the NO2 desorption [59] and in our case its
presence in the gas-phase suggests a slow reduction rate. Regeneration
of the Fe2+ sites takes place by the presence of the oxygen in the stream
[58,59,62].
Acidity of the materials also plays an important role in the NH3-SCR
of NOx reaction; Wang and coworkers [9] reported than NH4+ ions

Fig. 6. H2–TPR of Nat-zeo catalyst.

6
J.-F. Gelves et al.
located at the Brönsted acid sites are unstable and react with the NO2
species generated at the surface to form intermediate species, which
further react with the NO to produce N2. Also, the key intermediates in
the reaction are NH and NH2 species, which can be generated when
NH3 is adsorbed on the Lewis acid sites [63].
On the other hand, according with Fig. 8b, there is formation of N2O
during the NO reduction over these catalysts and it is associated with
the presence of NO2 and its reaction with ammonia, Eq. (5) [61]. It is
noticeable that over the Nat-zeo catalyst the formation of N2O is the
highest (Fig. 8b).
2NO2 + 2NH3 → N2 O + N2 + 3H2 O
3+
NH3 conversion with the catalysts H-zeo-Fe and H-zeo-Fe2+
(Fig. 9) was almost 100% at temperatures above 400 °C. The conversion
observed at low temperatures over the Nat-zeo and H-zeo-Fe2+ cata-
lysts could be related with the NH3 adsorption at the beginning of the
reaction (temperatures above 150 °C) than starts to desorb at about
200 °C. At temperatures above 400 °C, oxidation of NH3 to NO is evi-
dent in iron zeolites although ammonia preferentially participates in
NO reduction [64].
Effect of water on the performance of the catalyst H-zeo-Fe3+ in the
NO and NH3 conversion is shown in Fig. 10a. Water affected NO con-
version in great extent and only good activity was observed between
400 and 450 °C. The effect of water at temperatures below 350 °C is
because competitive adsorption between H2O and NH3, and NH3 ad-
sorption is a key step of the NO reduction [65,66].
In the presence of water the formation of NO2 is improved and the
N2O is avoided (Fig. 10b). NO2 can react with water to form a mixture
of nitrous acid (HNO2) and nitric acid (HNO3) which likely remain
adsorbed on the active Fe sites required for the NO oxidation reaction
[65]. Regarding to NH3 conversion, the presence of water decreases
NH3 conversion until 500 °C, after this temperature the conversion
Table 5
Ammonia consumption and total acidity of Nat-zeo and H-zeo-Fe3+ catalysts before and after reaction.
Material Peak 1 Peak 2
T (°C) Acidity (μmol g−1
cat ) T (°C)
Nat-zeo 160 229.9 510
H-zeo-Fe3+ 183 920.6 526
H-zeo-Fe3+ used 170 665.6 500
Catalysis Today xxx (xxxx) xxx–xxx
Fig. 7. NH3–TPD profiles of Nat-zeo and H-zeo-Fe3+catalysts.
remained almost constant (Fig. 10a).
The NOx-TPD results over the catalyst H-zeo-Fe3+, Fig. 11, corro-
borate the facts described above. The NOx-TPD profiles of the catalysts
show bands between 100 °C and 550 °C. This indicates the presence of
weakly adsorbed NOx and the formation of different nitrogenated
species on the catalyst surface [67–70]. In the NO-TPD (Fig. 11a), the
peak at 103 °C could be attributed to physisorbed NOx; the peaks at 150
and 190 °C were due to the decomposition of monodentate nitrate
species or iron nitrosyl species [71,72]; and the broad peaks above
250 °C were due to the decomposition of nitrate species (bridging and
bidentate) with higher thermal stability [73,74]. The presence of water
(5)
vapor significantly inhibited the NO adsorption as we expected
(Fig. 11a) [73]. On the other hand, NO2 and N2O-TPD profiles
(Fig. 11b) show the importance of water in their adsorption on the H-
zeo-Fe3+ catalyst surface. NO2 presented two desorption broad peaks
between 50 and 300 °C and 330–550 °C. The amount of NO2 desorbed is
higher when the experiment was made in the presence of water, which
corroborates the formation of HNO2 and HNO3 on the active Fe sites
[65]. N2O desorption is observed at temperatures above 300 °C [74],
and the improvement in the adsorption capacity of the catalyst H-zeo-
Fe3+ in the presence of water can be related with the formation of Fe
(OH)2 species in the catalyst, that can absorb N2O [75].
3.3. Catalyst stability
A durability test of the catalyst H-zeo-Fe3+ at 400 °C under wet
conditions is shown in Fig. 12. After the first 4 h of reaction the NO
conversion decreased from 98% to 80% while the NH3 conversion in-
creased from 83% to 97%. With 30 h on stream the NO conversion
decreased until 65% and the NH3 conversion until 93%. However, the
loss of conversion in time seems to be frequent in catalysts made from
naturally occurring materials and in some zeolites [38,76,77]. Two
Peak 3 Total acidity (μmol g−1
cat )
Acidity (μmol g−1
cat ) T (°C) Acidity (μmol g−1
cat )
427.3 – – 657.2
1609.9 665 46.17 2576.7
155.7 – – 821.3
7
J.-F. Gelves et al.
Fig. 8. Catalytic activity of Nat-zeo, H-zeo-Fe2+, and H-zeo-Fe3+ catalysts on a) NO
conversion and b) NO2 (fully symbols) and N2O (open symbols) concentration. Reaction
conditions: 400 ppm NO, 45 ppm NO2, 400 ppm NH3, 8% O2, and balance Ar,
GHSV = 30000 h−1.
Fig. 9. NH3 conversion with Nat-zeo, H-zeo-Fe2+, and H-zeo-Fe3+ catalysts. Reaction
conditions: 400 ppm NO, 45 ppm NO2, 400 ppm NH3, 8% O2, and balance Ar,
GHSV = 30000 h−1.
causes could be associated to the blockage of active sites by the water
that affects the NO oxidation reaction [65], or the deactivation of the
NO/NH3 adsorption sites and the degradation of the structure by water
effects and reaction time.
In order to corroborate the previous approaches, infrared
8
Catalysis Today xxx (xxxx) xxx–xxx
Fig. 10. Effect of water with the H-zeo-Fe3+ catalyst on a) NO (fully symbols) and NH3
(open symbols) conversions and b) NO2 (fully symbols) and N2O (open symbols) con-
centration. Reaction conditions: 400 ppm NO, 45 ppm NO2, 400 ppm NH3, 8% O2, 5%
H2O and balance Ar, GHSV = 30000 h−1.
spectroscopy (Fig. 2), X-ray diffraction (Fig. 1), textural properties
(Table 4) and TPD-NH3 analysis (Table 5) were performed to establish
structural variations in the used H-zeo-Fe3+ catalyst. The XRD pattern
of the H-zeo-Fe3+ catalyst before and after 30 h reaction in presence of
water at 400 °C showed some structural variations in the catalyst, Fig. 1.
Two aspects are evident in the material, the first of them is an incre-
ment in the metaheulandite phase (2θ = 11°), which is derived from the
low thermal stable heulandite (as described in Section 3.1.1). The
second aspect is the decrease of the interplanar distance of the plane
(020) of the heulandite from 9.07 Å to 9.00 Å in the used catalyst
(Fig. 1). These two aspects suggest a decrease in the cross-sectional area
of the zeolite channels, affecting also the diffusion of the reactants to-
wards the active centers of the catalyst.
The FTIR of the used catalyst did not show new bands, Fig. 2. The
absence of the bands at 1387 cm−1 and 1242 cm−1 discards the for-
mation of solid deposit of nitrate (NO3−) and nitrite (NO2−) ions in the
used catalyst [24,57,78]. The band at 1405 cm−1 associated with the
vibration of the ammonium ions in the H-zeo-Fe3+ catalyst remains
after the durability test [78]. The presence of these ions in the fresh
catalyst is associated with the cation exchange process and the low
calcination temperature used (360 °C, 6 h), which is not sufficient for
their total decomposition towards NH3. In the case of the material after
reaction, a small increase in the intensity of the vibration of the NH4+
band is evidenced and it could be associated with the adsorption of NH3
on the Brönsted sites of the zeolite. Fig. 2 also shows changes in the
vibration band associated to the TO4 group (T: Si or Al) of the heu-
landite structure in the used catalyst, observed between 1020 cm−1 and
1070 cm−1 [28]. Mozgawa et al. [28] correlated the displacement of
this band with changes in the Si/Al ratio of the zeolite. It was
J.-F. Gelves et al. Catalysis Today xxx (xxxx) xxx–xxx

Fig. 11. NOx desorption profiles from the H-zeo-Fe3+ catalyst after: (A)
NO adsorption and (B) NO2/N2O adsorption at 50 °C under wet and dry
conditions.

Fig. 12. Durability test for H-zeo-Fe3+ catalyst. Reaction conditions: 400 ppm NO,
45 ppm NO2, 400 ppm NH3, 8% O2, 5% H2O, and balance Ar, GHSV = 30000 h−1, 500 °C,
30 h on stream.
established for the heulandite structure with high silicon content that
there is a shift of the band in the direction of the near infrared, whereas
an increase in the content of aluminum will lead to a displacement
towards the far infrared [28]. The TO4 band in the used catalyst shifted
from 1040 cm−1 to 1067 cm−1, compared with the material before
reaction, which could be associated to dealumination of the catalyst.
The dealumination process has been associated to the presence of water
vapor and the high reaction temperature (500 °C). This fact may lead to
the reduction of Brönsted acid sites, as well as the structural/textural
degradation of the zeolite, which may affect catalyst activity
[24,79,80]. However, the adsorption of water and ammonia during the
reaction can also cause this shifted since the OH or NH groups near to
the Si-O group generally lowers the stretching frequency due to the
hydrogen bonding [81]. In addition, the degradation of the tetrahedral
structure of the zeolite can be observed with the small widening of the
TO4 band after reaction (Fig. 2), indicating a decrease in crystallinity
[28]. This change in crystallinity was also observed by XRD (Fig. 1), but
due to the formation of metaheulandite.
The changes in the textural properties (Table 4) and in the acidity
(Table 5) of the catalyst H-zeo-Fe3+ after the reaction were evaluated.

9
J.-F. Gelves et al.
A slight reduction in the surface area of H-zeo-Fe3+ after durability test
is observed (Table 4 and Fig. 5b). This fact may be associated with the
structural changes of the zeolite (according to the XRD and FTIR ana-
lysis) that make difficult the entrance of the N2 to the channels of the
zeolite. Likewise, significant changes in the other textural parameters
are observed in Table 4, showing an increment in the micropore area,
average pore size and total pore volume. These changes could be as-
sociated with the dealumination process described above in the FTIR
analysis. Finally, the changes in the acidity of the material presented in
Table 5 allowed to reinforce the hypothesis that the dealumination by
the breaking of the SieOHeAl bonds, the decrease in the BET surface
area due to the metaheulandite formation, and the loss of crystallinity
contribute to decrease the acid centers of the H-zeo-Fe3+catalyst from
2576.7 to 821.3 μmol g−1 cat , which diminishes the amount of active sites
for NH3 adsorption, affecting the efficiency of the catalyst.
4. Conclusions
An iron Colombian natural zeolite composed mainly by heulandite
and celadonite phases was successfully evaluated as a potential geo-
catalyst for NH3-SCR of NOx. After the treatments for obtaining the acid
material and the Fe3+ and Fe2+ species, the NO conversion increased
with operating temperature window of 350–500 °C. Maximum conver-
sion increased from 21% in the natural zeolite until 76% in the presence
of Fe2+ species and to 86% with the Fe3+ species. The presence of Fe3+
favored the NO conversion, but with a 5% mol of water in the inlet
stream narrowed the operating window to 400–500 °C obtaining a
conversion near to 100% at 500 °C. NOx-TPD confirmed that water
inhibits the NO adsorption on the catalyst H-zeo-Fe3+ surface, but
improves that of NO2. At 500 °C under wet conditions after 30 h of
reaction the NO conversion decreases to 35% over the catalyst H-zeo-
Fe3+, which according with the FTIR, XRD and BET analysis can be
associated with a dealumination process, the contraction of the zeolite
channels due to the metaheulandite formation, and the acidity and
crystallinity losses.
Acknowledgments
JFG, LD and MAM acknowledge financial support to Universidad
Nacional de Colombia sede Medellín; ACA, LMG and ALV thank to
Universidad de Antioquia (UdeA) and Colciencias for financial support
through the project 1115-569-33782, and UdeA for project PURDUE
14-2-05.
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