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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
https://doi.org/10.1007/s11144-019-01719-1
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Catalytic activity ofmaghemite supported palladium
catalyst innitrobenzene hydrogenation
ViktóriaHajdu1· ÁdámPrekob1· GáborMuránszky1· IstvánKocserha2·
ZoltánKónya3· BélaFiser1,4· BélaViskolcz1· LászlóVanyorek1
Received: 29 October 2019 / Accepted: 31 December 2019 / Published online: 9 January 2020
© The Author(s) 2020
Abstract
A maghemite supported palladium catalyst was prepared and tested in nitroben-
zene hydrogenation. The catalyst support was made by a newly developed com-
bined technique, where sonochemical treatment and combustion have been used. As
a first step, maghemite nanoparticles were synthesized. Iron(II) citrate was treated
in polyethylene glycol by high-intensity ultrasound cavitation to get a homogene-
ous dispersion, then the product was combusted. The produced powder contained
maghemite nanoparticles with 21.8 nm average particle size. In the second step
of catalyst preparation, the magnetic nanoparticles were dispersed in the ethanolic
solution of palladium(II) nitrate. The necessary energy for the reduction of Pd2+
ions was achieved in the “hot spots” by acoustic cavitation, thus catalytically active
palladium was formed. The prepared maghemite supported Pd catalyst have been
tested in nitrobenzene hydrogenation at three different temperatures (283K, 293K
and 303K) and constant pressure (20bar). At 293K and 303K, the conversion
and selectivity of nitrobenzene was above 99% and 96%, respectively. However, the
selectivity was only 73% at 273K because the intermediate species (azoxybenzene
and nitrosobenzene) have not been transformed to aniline. All in all, the prepared
catalyst is successfully applied in nitrobenzene hydrogenation and easily separable
from the reaction media.
Keywords Magnetic catalyst· Selectivity· Nitrobenzene· Aniline
Introduction
Several different complex catalysts have been successfully applied in the hydro-
genation of nitro groups, such as carbon (C), silica (SiO2) or alumina (Al2O3) sup-
ported Pd, Pt, Ru, Rh, Ni, Fe or bimetallic systems [1–13]. The easy handling and
* László Vanyorek
kemviki@uni-miskolc.hu
Extended author information available on the last page of the article
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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
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separability are very important properties for the catalysts. These can be improved
by introducing magnetic features (e.g. magnetic catalyst supports), which will allow
the easy and efficient removal of the catalysts after the reactions. For this reason,
magnetic systems have been widely used in various applications. Magnetite (Fe3O4)/
silica composite catalyst was used for esterification of palmitic acid with metha-
nol [14]. Pd, Pr–Cu and Pr6O11 decorated Fe3O4/SiO2 catalyzed the reduction of
2,4-dinitrophenylhydrazine, 4-nitrophenol and chromium(VI) ions, Mizoroki–Heck
coupling reaction, and the catalytic ozonation of acetochlor [15–17]. Magnetite/
carbon support was applied in Suzuki–Miyaura cross-coupling of 4-iodotoluene
and phenylboronic acid and aniline synthesis by palladium [18, 19]. By magnetite/
alumina supported Pd catalyst the hydrogenation of nitrate in water and 4-nitro-
phenol can be achieved [20, 21]. Magnetic iron oxides can be combined with dif-
ferent layered double hydroxides (Fe3O4-LDH), complex magnesium silicates
(Fe3O4-sepiolite) and hydroxyapatite (γ-Fe2O3-HAP) to use as a support for Pd and
these catalytic systems can be applied to catalyze the Heck reaction between iodo-
benzene and styrene, and the reduction of nitroarenes and nitrobenzene [22–24].
Magnetite itself is also a promising catalyst support as it was proved by the applica-
bility of Ag/Fe3O4, Ag–Ni/Fe3O4, Pd/Fe3O4 and Rh/Fe3O4 systems in the synthesis
of 3,4-dihydropyrimidinones. 2,4-dihydropyrano[2,3-c]pyrazoles, and the hydro-
genation of soybean oil and nitroarenes [25–28]. The two main components of the
catalysts mentioned above are the support and the catalytically active metal. The
catalysts are prepared through several steps, including the activation of metal, within
which metal (e.g. palladium ions) ions or their complex ions are reduced to the cata-
lytically active form (e.g. Pd0). In the case of Pd ions, the activation (reduction) can
be done on the supports in aqueous solution by molecular hydrogen (6atm, 75°C)
or by using NaBH4 in ethanol but the ethylene glycol is also efficient [21, 24, 29].
In our work, a simplified reduction step was applied during the catalyst produc-
tion (palladium(II) nitrate to Pd0) by applying alcohol and acoustic cavitation. The
high energy of the ultrasonic treatment in liquids generates acoustic cavitation,
which leads to the formation of micro vapor-bubbles. The collapse of the formed
bubbles leads to „hot spots” where intense local heating (~ 5000K), high pressure
(~ 1000atm), enormous heating and cooling rates (> 109K/s) and liquid jet streams
(~ 400km/h) appear in a small volume [30]. The energy in the „hot spots” can cover
the needs of the reduction of metal ions to metals in the presence of a reducing agent
[31–36]. By using of ultrasonic cavitation, palladium nanoparticles were deposited
on the surface of maghemite in methanol phase. Owing to the magnetic properties
of the maghemite, this is a remarkable catalyst support in liquid phase hydrogena-
tion because the catalyst easily separated from the reaction media by magnetic field.
Experiment
Materials
Iron(III) citrate hydrate (FeC6H5O7⋅H2O, PanReac AppliChem) as precursor and
polyethylene glycol (PEG400, Sigma Aldrich) were applied for the synthesis of
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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
maghemite. Palladium(II) nitrate dihydrate (Pd(NO3)2⋅2H2O, Merck) and absolute
ethanol (VWR) was used to synthesize catalytically active palladium.
Application ofmaghemite supported palladium catalyst
Maghemite nanoparticles, as catalyst supports were synthesized by a combustion
method. 3.5 g iron(III) citrate hydrate was dispersed in 20g polyethylene glycol
(PEG 400, Sigma Aldrich) by using a Hielscher Ultrasound tip homogenizer. The
iron precursor containing dispersion was heated up and burned at 500°C in a calcin-
ing furnace for two hours.
The before-synthetized maghemite was applied for catalyst preparation by using
a Hielscher Ultrasound tip homogenizer (UIP1000hDT). The palladium precursor
(0.125g) was solved in 50ml abs. ethanol, and 1.00g maghemite was added to the
solution. The ethanolic dispersion was sonicated by using the homogenizer (115W,
19.43kHz) for 2min. Then, the catalyst was removed from the dispersion with a Nd
magnet, washed with ethanol, and dried at 105°C overnight.
Characterization techniques ofthenanoparticles
Maghemite and palladium nanoparticles were examined by using high-resolution
transmission electron microscopy (HRTEM, FEI Technai G2 electron microscope,
200kV). The samples were prepared by dropping their aqueous suspension on 300
mesh copper grids (Ted Pella Inc.). The diameters of the nanoparticles were meas-
ured on the HRTEM images, based on the original scale bar by using the ImageJ
software. X-ray diffraction (XRD) measurements were used to identify and quantify
the crystalline phases, by applying a Rigaku Miniflex II diffractometer with Cu Kα
radiation source (30kV, 15mA). The palladium content was determined with a Var-
ian 720 ES inductively coupled optical emission spectrometer (ICP-OES), by using
a Merck Certipur ICP multi-element standard IV.
Catalytic tests
The catalytic hydrogenation was carried out in a Büchi Uster Picoclave reactor, in a
200ml stainless steel vessel with heating jacket. The hydrogen pressure was 20bar
and the reactions were carried at 283 K, 293 K and 323 K. Sampling took place
after the beginning of hydrogenation at 5, 10, 15, 20, 30, 60, 120, 180, and 240min.
The initial concentration of nitrobenzene was 0.125moldm−3 in methanol. The total
amount of the solution was 150ml and 0.2g catalyst was used during each test. Ani-
line formation was followed by applying Agilent 7890A gas chromatograph coupled
with Agilent 5975C Mass Selective detector. Analytical standards (aniline, nitroben-
zene, nitrosobenzene, azoxybenzene, dicyclohexylamine, o-toluidine, cyclohexy-
lamine and n-methylaniline) were provided by Dr. Ehrenstorfer and Sigma Aldrich.
The efficiency of the catalytic hydrogenation was compared by calculating the con-
version (X%) of nitrobenzene based on the following equation (Eq.1):
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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
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The selectivity (S%) of the catalyst was calculated as follows (Eq.2):
re naniline and nnitrobenzene are the corresponding chemical amounts of the compounds.
By assuming that the process is a first order reaction, based on the initial and
measured nitrobenzene concentrations (c0 and ck, mol/dm3), the reaction rate con-
stant (k) was calculated at different temperatures by non-linear regression (Fig.4)
according to the following (Eq.3):
Results anddiscussion
Surface morphology andphase composition ofthecatalyst
The reduction of palladium ions to elemental Pd have been confirmed by XRD
measurements (Fig.1a). Reflections at 40° and 48.8° 2θ degrees were identified on
the XRD pattern, which are attributed to the Pd(111) and Pd(200) phases (Fig.1a,
red line). Other reflections were also identified such as the peaks at 24.1°, 30.3°,
35.7°, 43.3°, 54°, 57.3° and 63° 2θ degrees, which are assigned to the presence of
(210), (220),(100), (400), (422), (511) and (400) planes of maghemite (γ-Fe2O3)
crystalline phase. The average size of the maghemite particles was found to be
21.8nm (Fig.1b). Palladium nanoparticles were deposited onto the surface of the
maghemite crystals. The palladium deposition onto the surface of the maghemite led
to the aggregation of the magnetic particles, the size of the nanocomposite aggre-
gates are between 70–200nm. The palladium particles on the maghemite aggregates
(1)
X
%=
consumed
nnitrobenzene
initial n
nitrobenzene
×
100.
(2)
S
%=
n
aniline
n
nitrobenzene
×
100
(3)
ck
=c
0
∗e
−k∗t
Fig. 1 XRD pattern of the maghemite (blue line) and Pd/maghemite catalyst (red line) (a) HRTEM
image and size distribution of maghemite (b) and Pd/maghemite (c)
111
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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
are smaller than 8nm (the average size is 4.5nm) (Fig.1c). The formation of palla-
dium nanoparticles can be explained by the reduction effect of the appearing .CH2R
radicals. These reactive species generated by the ultrasonic treatment through the
reaction of .OH radicals and ethanol [37, 38].
Catalytic activity ofthemagnetic Pd catalyst
The prepared magnetic Pd catalyst was tested in nitrobenzene hydrogenation. The
maximum conversions were reached after 80min at 293K and 303K (Fig.2a). At
283K the reaction is slower, but the total amount of nitrobenzene was transformed
to aniline. The aniline selectivity was high, 97% and 96.7% at 293K and 303K,
respectively (Fig.2b). The catalytic activity was tested through five cycles at 303K
and 20bar hydrogen pressure, while the reaction time was 80min. The catalyst was
not regenerated between the cycles, only washed with methanol. The activity started
to decrease from the third cycle, which indicates that the regeneration of the catalyst
is necessary (Fig.2c).
The selectivity was lower, only 73.8%, at 283K which can be explained by the
low reaction rate, and the persistence of the intermediates which are not converted
to aniline (Fig.3a). At 283K, azoxybenzene and nitrosobenzene have been detected
during the reactions, which indicates that, the hydrogenation process follows the
Haber mechanism [38–42]. At higher temperatures the intermediates transformed
to aniline (Fig.3b and c). The catalyst was very selective towards the formation of
aniline, by-products have not been detected. All in all, the prepared maghemite sup-
ported palladium catalyst at 303K reaction temperature and 20bar hydrogen pres-
sure can be applied effectively for aniline synthesis.
The reaction rate constants (k) at different temperatures were calculated based
on the measured nitrobenzene concentrations by using non-linear regression [43]
(Fig.4; Table1).
Fig. 2 Conversion of nitrobenzene vs time of hydrogenation (a) and aniline selectivity (b) at various
temperatures (283, 293 and 303K). Aniline yield vs number of cycles at 20bar pressure and 303K, after
80min of hydrogenation
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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
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Conclusion
Maghemite supported palladium catalyst was prepared. The maghemite catalyst
support was made by a newly developed combined technique, where sonochemical
Fig. 3 Concentration of the intermediates vs time of hydrogenation, at 283 K (a), 293 K (b) and
303K(c) at 20bar pressure
Fig. 4 Concentration of nitrobenzene vs time of hydrogenation
Table 1 Reaction rate constants
of nitrobenzene hydrogenation Temperature (K) 283 293 303
Reaction rate constant (s−1)1.73 × 10–2 4.09 × 10–2 5.10 × 10–2
SD 7.76 × 10–4 2.99 × 10–3 3.83 × 10–3
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Reaction Kinetics, Mechanisms and Catalysis (2020) 129:107–116
treatment and combustion have been used. This procedure leads to nanoparticles
with smaller crystalline size (21.8nm) and high adsorption capability. The catalyst
is in an active form immediately after the production of the Pd/maghemite nano-
composite, as the sonochemical treatment initiated the involvement of the disper-
sion media in the reduction of palladium ions to elemental palladium particles (Pd0).
In this sense, the catalyst does not require further post-treatments, and it does not
need to be reduced under a hydrogen atmosphere, therefore the catalyst preparation
method is simplified. The synthesized magnetic catalyst was efficiently applied in
nitrobenzene hydrogenation at 293K and 303K and the conversion was more than
99% in both case. The catalyst was selective towards aniline, and the selectivity was
97.0% and 96.7% at 293K and 303K, respectively. By-products were not detected
during the reaction. All in all, a simple method has been designed for magnetic cata-
lyst production. The achieved catalytic system is easily separable from the reaction
media, thanks to its magnetic property and successfully applicable in nitrobenzene
hydrogenation.
Acknowledgements Open access funding provided by University of Miskolc (ME). This research was
supported by the European Union and the Hungarian State, co-financed by the European Regional Devel-
opment Fund in the framework of the GINOP-2.3.4–15-2016–00004 project, aimed to promote the coop-
eration between the higher education and the industry. The EFOP-3.6.1-16-2016-00014 project is also
gratefully acknowledged due to support our work.
Compliance with ethical standards
Conict of interest On behalf of all authors, the corresponding author states that there is no conflict of
interest.
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License,
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ses/by/4.0/.
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Aliations
ViktóriaHajdu1· ÁdámPrekob1· GáborMuránszky1· IstvánKocserha2·
ZoltánKónya3· BélaFiser1,4· BélaViskolcz1· LászlóVanyorek1
Viktória Hajdu
kemviki@uni-miskolc.hu
Ádám Prekob
kempadam@uni-miskolc.hu
Gábor Muránszky
kemmug@uni-miskolc.hu
István Kocserha
istvan.kocserha@uni-miskolc.hu
Zoltán Kónya
konya@chem.u-szeged.hu
Béla Fiser
kemfiser@uni-miskolc.hu
Béla Viskolcz
bela.viskolcz@uni-miskolc.hu
1 Institute ofChemistry, University ofMiskolc, 3515Miskolc-Egyetemváros, Hungary
2 Institute ofCermics andPolymer Engineering, University ofMiskolc,
3515Miskolc-Egyetemváros, Hungary
3 Department ofApplied andEnvironmental Chemistry, University ofSzeged, Rerrich Béla sq. 1,
6720Szeged, Hungary
4 Ferenc Rákóczi II. Transcarpathian Hungarian Institute, Beregszász, Transcarpathia90200,
Ukraine