C. R.

Chimie 18 (2015) 351–357

Contents lists available at ScienceDirect

Comptes Rendus Chimie

www.sciencedirect.com

GeCat 2014: Advances and prospects in heterogeneous catalysis

Degradation of VOCs and NOx over Mg(Cu)–AlFe mixed oxides

derived from hydrotalcite-like compounds
Dégradation de composés organiques volatils et d’oxydes d’azote sur des
oxydes mixtes Mg(Cu)–AlFe issus de la voie hydrotalcites
Raya Mrad a, Renaud Cousin a, Najat Aoun Saliba b, Lucette Tidahy a,
Stéphane Siffert a,*
a
Université du Littoral Côte d’Opale, Unité de chimie environnementale et interactions sur le vivant (UCEIV), 59375 Dunkerque cedex,
France
b
Chemistry Department, American University of Beirut, P.O. Box 11-0236, Riad El-Solh, Beirut 1107 2020, Lebanon

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

Article history: A series of Mg(Cu)–AlFe mixed oxides derived from hydrotalcite-like compounds has been
Received 1st July 2014 prepared. These solids were characterized by various physicochemical methods and their
Accepted after revision 25 August 2014 catalytic performances were tested towards the catalytic oxidation of propene and the
Available online 2 February 2015
simultaneous elimination of propene and NOx. X-ray diffraction (XRD) and scanning
electron microscopy (SEM) confirmed the formation of the hydrotalcite structure for all
Keywords: the solids, except for Cu4AlFe HT, for which a mixture of the hydrotalcite and the malachite
Heterogeneous catalysis phases is observed. The XRD study of the calcined samples revealed the existence of metal
Hydrotalcite-like compounds
oxides and spinels of types MgO, CuO, -Fe2O3 or/and Fe3O4, MgFe2O4 and CuFe2O4. During
Copper
propene oxidation, it was shown that the increase in the copper content enhanced the
VOC
NOx
activity of the solids. However, Cu2Mg2AlFe 500, with the highest amount of surface
copper species, exhibited the best activity towards the simultaneous elimination of
propene and NO. Indeed surface Cu species are the active sites, while bulk Cu species could
provide the adsorption sites for nitrogen species.
ß 2014 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.

R É S U M É

Mots clés : Une série d’oxydes mixtes Mg(Cu)–AlFe dérivée de composés hydrotalcites a été préparée.
Catalyse hétérogène Ces solides ont été caractérisés par différentes techniques physicochimiques, puis leur
Hydroxydes doubles lamellaires performance catalytique a été testée vis-à-vis de l’oxydation catalytique du propène et de
Cuivre l’élimination simultanée du propène et des NOx. L’étude par diffraction de rayons X (DRX)
COV
et la microscopie électronique à balayage (MEB) ont confirmé l’obtention de la structure
NOx
hydrotalcite pour tous les solides, à l’exception du solide Cu4AlFe HT, pour lequel les
phases hydrotalcite et malachite sont observées. L’étude par DRX des échantillons calcinés

* Corresponding author.
E-mail address: [email protected] (S. Siffert).

http://dx.doi.org/10.1016/j.crci.2014.08.005
1631-0748/ß 2014 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.
352 R. Mrad et al. / C. R. Chimie 18 (2015) 351–357

a révélé l’existence d’oxydes métalliques et de spinelles des types MgO, CuO, -Fe2O3 ou/et
Fe3O4, MgFe2O4 et CuFe2O4. Lors de l’oxydation du propène, il est montré que
l’augmentation de la quantité de cuivre améliore l’activité des solides. Cependant, le
solide Cu2Mg2AlFe 500 ayant le plus grand nombre d’espèces de cuivre en surface a
présenté la meilleure activité vis-à-vis de l’élimination simultanée du propène et du NO. En
effet, les espèces cuivriques présentes en surface sont les sites actifs, alors que les espèces
cuivre dans la masse du solide semblent être des sites d’adsorption pour les espèces
d’azote.
ß 2014 Académie des sciences. Publié par Elsevier Masson SAS. Tous droits réservés.

1. Introduction 6 H2O (PANREAC, 98%), Al(NO3)39 H2O (ACROS, 99%) and

Fe(NO3)39 H2O (ACROS, 99%), was added dropwise into a
Volatile organic compounds (VOCs) and nitrogen oxides vigorously stirred deionized water solution. During synth-
(NOx) arising from industrial gases are dangerous pollu- esis, temperature and pH were maintained constant at
tants and have a detrimental effect on the environment respectively 60 8C and 8 by dropwise addition of a solution
and on human health. One of the most prominent results of of Na2CO3 1 M and NaOH 2 M. The obtained solution was
VOCs and NOx emission is the formation of ground-level stirred at 60 8C for a further hour, and then placed in the
ozone, following the reaction between NOx and VOCs in the oven for 18 h. The precipitate was then filtered, washed
presence of sunlight. Excessive O3 in the air can cause several times with hot deionized water (55 8C) and dried at
breathing problems, trigger asthma, reduce lung function 60 8C for 48 h. The samples were denoted CuxMg4–xAlFeHT
and cause lung diseases [1]. To overcome the problem, (0 < x < 4). The solids were then calcined at 500 8C under a
catalytic devices appear as an efficient technology for flow of air (2 Lh1).
complete oxidation of VOCs or/and NOx reduction. Copper X-ray diffraction experiments were performed at room
and iron species have been reported to be active in the temperature using a Bruker D8 Advance diffractometer
selective oxidation of propene and/or in the reduction of equipped with a copper anode emitting a Ka radiation
NOx [2–4]. Moreover, their excellent low-temperature (l = 1.5406 Å) and a LynxEye detector. A step size of 0.028
activity and cost effectiveness makes them a good and a count time of 4 s per step were used for data collection.
substitute for noble metal catalysts. However, the most The crystalline phases were identified by comparing the
popular copper based catalyst, Cu-ZSM-5, discovered by diffractograms with the database of the Joint Committee on
Iwamoto et al. in 1993 [5], was believed to be the most Powder Diffraction Standards (JCPDS) established by the
promising catalyst for NOx decomposition, thus it did not International Center for Diffraction Data (ICDD).
appear resistant to H2O and SO2 present in flue gases from The specific surface area of the dried and the calcined
coal combustion [4]. samples was determined by low-temperature nitrogen
In the past decade, mixed oxides derived from layered adsorption (196 8C) using the Brunauer–Emmett–Teller
double hydroxides (LDHs) known as hydrotalcite-like (BET) method, with a thermo-Electron QSurf M1 sorpt-
compounds (HTLCs) have attracted much attention due ometer, while the Barett–Joyner–Halenda (BJH) pore
to their large surface areas, good thermal stability, high diameters were determined by Sorptomatic 1990 sorption
dispersion, and basic character [6]. Among many applica- analyzer. Prior to the measurements, each sample was
tions, they are known to be powerful for hydrocarbons degassed at 400 8C for 3 h.
oxidation [7–9] and/or NOx reduction with hydrocarbons Scanning electron microscopy analysis was performed
[2] or ammonia [10]. on a Mira4 Tescan instrument equipped with an energy
In this work, a series of CuxMg4–xAlFe catalysts derived dispersive X-ray spectrometer (SEM-EDX). Samples were
from hydrotalcite-like compounds was synthesized, then adhered on aluminum stubs covered with 12-mm carbon
characterized by various techniques. Subsequently, their adhesive tabs and then coated by a thin film of gold. Typical
performance was investigated in propene oxidation and in working parameters were an accelerating voltage of 20 kV,
the simultaneous elimination of propene and NO. Previous and a beam current of 60 mA.
studies [2,11] showed that mixed oxides derived from The reducibility of the calcined samples was studied by
LDHs are potential catalysts for HC-SCR, other ones [3,4] H2 temperature-programmed reduction (TPR). H2-TPR
demonstrated that copper and iron are very active species experiments were carried out in an Altamira AMI
in this process. However, this work is the first to show the 200 apparatus. Prior to the experiments, samples
roles of copper and iron species coexisting in a single solid (10 mg) were activated under argon at 150 8C for 1 h.
via hydrotalcite route in the HC-SCR. The samples were then heated from ambient temperature
to 900 8C under a H2 flow (5 vol.% in argon-30 mL min1) at
2. Experimental a heating rate of 5 8C min1.
In each test, a flow of the reaction mixture (6000 ppm
Mg(Cu)–AlFe hydrotalcite-like samples with a molar propene + air for propene test and 6000 ppm prope-
ratio equal to 2 were synthetized by a co-precipitation ne + 1000 ppm NO + air for propene–NO test) passes
method. An aqueous solution containing appropriate through 100 mg of a catalyst placed in a fixed-bed reactor.
amounts of Mg(NO3)26 H2O (FLUKA, 99%), Cu(NO3)2 The reaction products (NO, CO and CO2) were analyzed
 R. Mrad et al. / C. R. Chimie 18 (2015) 351–357 353

(b) CT
(a)
T

MM M MM M Cu AlFe HT C T TC TC T T Cu AlFe 500

T C
H C T T T
Intensity (a.u.)

Intensity (a.u)
H H H
H HH Cu MgAlFe HT
Cu MgAlFe 500

Cu Mg AlFe HT Cu Mg AlFe 500

S CuMg AlFe 500

CuMg AlFe HT S
P
MS P
Mg AlFe HT Mg AlFe 500

20 40 60 80 100 20 30 40 50 60 70 80
2θ (degree) 2θ (degree)

Fig. 1. (Color online.) X-ray diffraction (XRD) patterns of: a: CuxMg4–xAlFe HT hydrotalcite-like compounds; b: CuxMg4–xAlFe 500-mixed oxide catalysts. H:
hydrotalcite; M: malachite; P: MgO (periclase); T: CuO (tenorite); M: Fe3O4 (magnetite) and/or -Fe2O3 (maghemite); S: MgFe2O4 (magnesium iron oxide);
C: CuFe2O4 (cuprospinel).

with Xentra 4900C analyzer (Servomex). The measure- hydrotalcite and the malachite phases are transformed
ment of NO2 is done indirectly using a NO2 to NO converter into a mixture of oxides and spinels of type: MgO (JCPDS
BÜNOx (Bühler Technologies). Hence, the NOx quantity is 75-1525), CuO (JCPDS 80-0076), -Fe2O3 (JCPDS 04-0755)
obtained (NOx = NO2 + NO). Propene oxidation and N2O or/and Fe3O4 (JCPDS 65-3107), MgFe2O4 (JCPDS 36-0398)
formation were checked using a Varian CP-4900 microGC. and CuFe2O4 (JCPDS 77-0010). However, with further
increasing of Cu content, the diffraction peaks of CuO and
3. Results and discussion CuFe2O4 get sharper and replace those of MgO and
MgFe2O4. Similar diffractograms were obtained by
The XRD patterns of the CuxMg4–xAlFe precursors, Jablonska et al. [10] after calcination of Cu–Mg–Fe HTLCs
presented in Fig. 1a, are characteristic of the hydrotalcite- at 600˚ C.
like structure without any reflection of the other possible The physical properties of the as-synthesized and
phases. Except for the sample where all the magnesium is calcined hydrotalcite-like compounds were evaluated by
replaced with copper, the presence of the malachite phase BET and by N2 adsorption/desorption measurements, and
(Cu2(OH)2CO3) is also revealed due to the Jahn–Teller the results are listed in Table 1. As can be seen, the surface
effect in the Cu2+. Indeed, Carpentier et al. [12] reported area of the samples given by the BET technique decreases
that when all the magnesium in the precursor is replaced after calcination. The areas of the calcined hydrotalcites
by copper, the malachite phase is preferentially formed. ranged from 49 to 80 m2g1; however SBET decreases
The formation of layered materials is evidenced by the gradually with increasing the copper content. This result
sharp, symmetric, strong lines at low 2u values and weaker, can be related to the higher crystallization of the samples
less symmetric lines at high 2u values [2,12]. The with higher copper species, as it was revealed by XRD. The
diffraction peaks at 2u  118, 238, 348, 398, 468, 608, 618 results from N2 adsorption/desorption experiments
can be attributed to the (003), (006), (012), (015), (018), showed that all the samples exhibited type-IV isotherms,
(110) and (113) crystal planes for HT phase, respectively which are characteristic of mesoporous materials. Average
[13]. Fig. 1b shows the X-ray diffractograms recorded pore diameters, as well as pore volumes, are presented in
for the CuxMg4–xAlFe 500 solids. After calcination, the Table 1.

Table 1
Physical properties of the various samples.

Samples BET surface area of BET surface area of calcined Pore volume Average pore
dried samples (m2g1) samples at 500 8C (m2g1) (cm3g1) diameter (nm)

Mg4AlFe 117 80 0.62 3.37

CuMg3AlFe 95 75 0.49 1.98

Cu2Mg2AlFe 78 70 0.26 2.12

Cu3MgAlFe 82 51 0.19 1.96

Cu4AlFe 76 49 0.15 1.94

BET: Brunauer–Emmett–Teller.
354 R. Mrad et al. / C. R. Chimie 18 (2015) 351–357

Fig. 2. Scanning electron microscopy (SEM) micrographs of the CuxMg4–xAlFe HT samples: a: Mg4AlFe HT; b: CuMg3AlFe HT; c: Cu2Mg2AlFe HT; d:
Cu3MgAlFe HT; e and f: Cu4AlFe HT.

The sharp decrease in the pore volume is related to the summarized in Table 2. The peaks below 200 8C (peak a
sintering and the formation of spinel phases when copper and peak b) correspond to the stepwise reduction of highly
is substituted for magnesium. According to Valente et al. dispersed CuO species (isolated copper ions and small
[14], the porosity of the calcined samples is due to two clusters) i.e., Cu2+ ! Cu+ and Cu+ ! Cu0 [2]. Moreover, the
different processes: small intraparticle porosity is gener- peaks at 217 8C, 222 8C and 263 8C are attributed to more
ated by a ‘‘cratering’’ process, and the interparticle pores aggregated copper oxide phases such as bulky CuO [3] and
are created by the irregular stacking of the plate-like the reduction of CuFe2O3 into metallic copper and Fe2O3
particles. (peaks d and ). On the other hand, the peaks at higher
The morphology of the hydrotalcite-like compounds is temperatures are ascribed to the reduction of Fe2O3 into
revealed by SEM and is shown in Fig. 2. SEM images show Fe3O4 and of Fe3O4 into 3 FeO (peak w) [15]. It can be noted
highly crystalline particles. All the samples, with the that H2 consumption increases with enhancing the copper
exception of Cu4AlFe HT, showed a flower-like hierarchical content.
morphology typical of LDHs. Similar shapes were obtained The catalytic activity of CuxMg4–xAlFe 500 was studied
by Gennequin et al. [6] for Mg–Al hydrotalcite. However, in the oxidation of propene.
Cu4AlFe HT showed a mixture of crystalline and irregular Fig. 4a represents the conversion of propene versus
nanoflakes structures, in accordance with the XRD results, temperature for the different supports in the absence of
which revealed the presence of both hydrotalcite and NO. The light-off curves (temperatures in which 50% of the
malachite phases. propene is converted) and the intrinsic activity are shown
The redox properties of the samples were investigated in Table 3. The temperature used for the calculation of the
by temperature-programmed reduction, with the H2-TPR intrinsic activity corresponds to a propene conversion of
profiles shown in Fig. 3. The curves of the catalysts display 20% of the catalyst that exhibited the best activity. It was
two reduction regions: the reduction of the copper oxide observed that the introduction of copper enhanced the
species present in the forms of CuO and CuFe2O4 occurs in catalytic performance, which attests to the fact that
the low-temperature range (T < 350 8C), while the reduc- copper and iron oxide species as well as the spinel phase
tion of iron oxide phases present in the forms of -Fe2O3 CuFe2O4 play an important role in this process. Compared
or/and Fe3O4 appears at higher temperatures (T > 350 8C) to the other supports, Mg4AlFe showed the lowest
[10]. The reduction peaks due to copper and iron species catalytic activity. However, the better activity of the
were deconvolved, and the curve-fitting results are samples with high copper content is due to their higher
 R. Mrad et al. / C. R. Chimie 18 (2015) 351–357 355

Cu4AlFe 500

H2 Consumption (a.u.)
H2 Consum ption (a.u)

Cu3MgAlFe 500

Cu2Mg2AlFe 500

CuMg3AlFe 500
Mg4AlFe 500

200 400 600 800 300 400 500 600

Temperature (º C) Temperature (º C)

Fig. 3. (Color online.) H2-temperature-programmed reduction (TPR) profiles of the calcined samples.

Table 2
The temperature and the H2 consumption corresponding to the peaks in H2-TPR.

Samples Temperature (8C) [H2 consumption (mmolg1)] Total H2 consumption (mmolg1)

a b d w
Mg4AlFe 500 368 (729.9) 729.9

CuMg3AlFe 500 134 (538.3) 170 (2453.6) 371 (1970.6) 4962.5

Cu2Mg2AlFe 500 133 (757.8) 174 (8326.6) 401 (1290.6) 10375

Cu3MgAlFe 500 138 (698.4) 175 (6892.7) 222 (899.1) 397 (2449.5) 10939.7

Cu4AlFe 500 145 (1901.6) 177 (3043.2) 217 (2128.8) 263 (3576.9) 426 (1753.1) 12403.6

TPR: temperature-programmed reduction.

Fig. 4. (Color online.) Catalytic performance of the catalysts CuxMg4–xAlFe 500 as a function of temperature: a: propene conversion (%) in the absence of NO;
b: NOx conversion (—) and propene conversion (---).
356 R. Mrad et al. / C. R. Chimie 18 (2015) 351–357

Table 3
Light-off temperatures and intrinsic activities of propene conversion in the absence and in the presence of NO over the Mg(Cu)–AlFe mixed oxide catalysts.

Catalysts Mg4AlFe 500 CuMg3AlFe 500 Cu2Mg2AlFe 500 Cu3MgAlFe 500 Cu4AlFe 500

T50 (8C) without NO 419 247 231 227 228

1 2 9 7 7 6
Intrinsic activity (mols m ) 4.9 10 2.37 10 6.41 10 1.49 10 1.13 106

T50 (8C) with NO 395 315 245 250 253

1 2 8 7 7 6
Intrinsic activity (mols m ) 1.2 10 2.57 10 8.98 10 1.96 10 1.16 106

NO: nitrogen oxide.

reducibility, which promotes a redox cycle favorable to catalysts depended on their chemical composition,
the oxidation of propene in the presence of air, as shown mainly on the presence of copper oxide phases, and
in the TPR profiles. on their redox properties.
Concerning propene oxidation, it is to be noted that It should be noted that N2, CO2, and H2O were the main
when the conversion is complete, H2O and CO2 are the only products of the reactions; however, traces of CO and N2O in
products observed. the reaction products were also found.
Calcined hydrotalcites were then tested as catalysts in
the simultaneous elimination of propene and NO. Fig. 4b 4. Conclusion
shows the conversion of NOx (—) and propene conversion
(- - -) as a function of the reaction temperature. With Mg(Cu)–AlFe hydrotalcite-like compounds with differ-
increasing temperature, NO conversion enhanced until a ent copper contents were successfully synthesized. Their
maximum was reached. After that, it declined, because thermal decomposition at 500 8C leads to the formation of
propene is nearly completely oxidized. When Cu loading metal oxides and spinels that play a major role in propene
was increased (from x = 1 to x = 2), the maximum of NO oxidation and NOx reduction. In propene oxidation, the
conversion increased and T50 decreased. After reaching an increase in copper loading enhanced the catalytic perfor-
optimum value for copper content (x = 2), the maximum mance of the supports. This was explained by a higher
NO conversion started to decrease and T50 increased (Table reducibility of those solids and to the presence of oxide
3). This can be explained by the fact that, when the copper phases such as CuO and CuFe2O4. As for the simultaneous
quantity in the sample increase, this leads to the elimination of C3H6 and NO, the Cu2Mg2AlFe 500 presented
aggregation of the surface CuO, thus blocking the active the highest activity; this is mainly due to the presence of
sites for propene oxidation and NO reduction. Further- well-dispersed surface copper and iron species. Hence,
more, during the simultaneous elimination of C3H6 and increasing copper concentrations leads to agglomerated
NO, the competition on the metallic sites makes NO copper species, thus reducing the activity of the catalysts.
reduction more difficult. Hence, the best activity is The coexistence of copper and iron in a single material
obtained for Cu2Mg2AlFe 500, where the maximum of leads to an interesting activity for NOx reduction by
NO conversion is 21% at 255 8C and T50 is 245 8C. This propene, but the Cu/Fe ratio should still be adjusted to
catalyst exhibited the best activity because it contains the increase the catalytic properties.
highest amount of surface copper species. A study by Yuan
et al. [2] showed similar results in the catalytic reduction of
NO by C3H6 over CuxTi1 mixed oxides derived from Acknowledgements
hydrotalcite-like compounds catalysts. They showed
that surface Cu species are the active sites, while bulk Cu This work has been supported by the Lebanese National
species could provide the adsorption sites for nitrogen Council for Scientific Research, the Université du Littoral
species. Moreover, Worch et al. [16] studied the SCR of Côte d’Opale, the Institut de recherche en environnement
NO with propene over transition metal oxides (Fe-, Cu-, industriel (IRENI), and the European Union (Interreg
V-, and Ce-) supported on Al2O3, phosphated Al2O3, or 4 France–Wallonie–Flandre project, REDUGAZ).
SAPO-11. The results shown in Fig. 4b presented a
relatively better NO conversion and propene oxidation References
rates at lower temperatures compared to the study of
[1] European Environment Agency, Air Quality in Europe - Report 2012,
Worch et al. Therefore, it is to be pointed out that the European Environment Agency (EEA web site), 2012.
presence of both copper and iron species in a single solid [2] D. Yuan, X. Li, Q. Zhao, J. Zhao, M. Tade, S. Liu, J. Catal. 309 (2014) 268.
has resulted in lower temperatures of complete propene [3] J. Liu, X. Li, Q. Zhao, D. Zhang, P. Ndokoye, J. Mol. Catal. A: Chem. 378
(2013) 115.
conversion and in a better NO conversion. Other studies
[4] A. Łamacz, A. Krztoń, G. Djéga-Mariadassou, Appl. Catal., B 142 (2013)
[10,15] showed that mixed metal oxides of Cu, Mg, Al 268.
and Fe derived from hydrotalcite-like compounds, [5] M. Iwamoto, N. Mizuno, H. Yahiro, Stud. Surf. Sci. Catal. 75 (1993) 1285.
tested in the selective catalytic oxidation of ammonia [6] C. Gennequin, T. Barakat, H.L. Tidahya, R. Cousin, J.-F. Lamonier, A.
Aboukaı̈s, S. Siffert, Catal. Today 157 (2010) 191.
to dinitrogen, are active in the process of NO reduction [7] E. Genty, R. Cousin, S. Capelle, C. Gennequin, S. Siffert, Eur. J. Inorg.
with ammonia to N2 and N2O. The activity of the Chem. 2012 (2012) 2802.
 R. Mrad et al. / C. R. Chimie 18 (2015) 351–357 357

[8] C. Gennequin, S. Kouassi, L. Tidahy, R. Cousin, J.F. Lamonier, G. Garcon, P. [12] J. Carpentier, S. Siffert, J.F. Lamonier, H. Laversin, A. Aboukaı̈s, J. Porous
Shirali, F. Cazier, A. Aboukaı̈s, S. Siffert, C.R. Chimie 13 (2010) 494. Mater. 14 (2007) 103.
[9] J. Carpentier, J.-F. Lamonier, S. Siffert, H. Laversin, A. Aboukaı̈s, Stud. [13] W. Gao, Y. Zhao, J. Liu, Q. Huang, S. He, C. Li, J. Zhao, M. Wei, Catal. Sci.
Surf. Sci. Catal. 142 (2002) 1197. Technol. 3 (2013) 1324.
[10] M. Jabłonska, L. Chmielarz, A. Wegrzyn, K. Guzik, Z. Piwowarska, S. [14] J.S. Valente, J. Hernandez-Cortez, M.S. Cantu, G. Ferrat, E. Lopez-Salinas,
Witkowski, R.I. Walton, P.W. Dunne, F. Kovanda, J. Therm. Anal. Catal. Today 150 (2010) 340.
Calorim. 114 (2013) 731. [15] L. Chmielarz, M. Jabłonska, A. Struminski, Z. Piwowarska, A. Wegrzyn, S.
[11] D. Yuan, X. Li, Q. Zhao, J. Zhao, S. Liu, M. Tade, Appl. Catal., A 451 (2013) Witkowski, M. Michalik, Appl. Catal., B 130 (2013) 152.
176. [16] D. Worch, W. Suprun, R. Glaser, Catal. Today 176 (2011) 309.