Journal of Industrial and Engineering Chemistry 79 (2019) 307–313

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Application of carbon nanotube coated aluminosilicate beads as

“support on support” catalyst for hydrogenation of nitrobenzene
László Vanyoreka , Ádám Prekoba , EmÅke Sikoraa , Edina Reizera , Gábor Muránszkya ,
Ferenc Kristályb , Béla Viskolcza , Béla Fisera,c,*
a
Institute of Chemistry, University of Miskolc, Miskolc-Egyetemváros 3515, Hungary
b
Institute of Mineralogy and Geology, University of Miskolc, Miskolc-Egyetemváros 3515, Hungary
c
Ferenc Rákóczi II, Transcarpathian Hungarian Institute, Beregszász, Transcarpathia 90200, Ukraine

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

Article history: Nitrogen-doped bamboo-like carbon nanotube (N-BCNT) coating was synthesized onto the surface of
Received 21 April 2019 zeolite beads by using Catalytic Chemical Vapour Deposition (CCVD) method to develop a “support on
Received in revised form 1 July 2019 support” (SoS) system. These complex structured materials were used as supports during the preparation
Accepted 4 July 2019
of hydrogenation catalysts. Rhodium, palladium and platinum nanoparticles were deposited
Available online 12 July 2019
homogeneously onto the surface of the N-BCNTs of the SoS (final metal content 2 wt%). The catalytic
activity of these samples was compared in the hydrogenation of nitrobenzene. The Pt/N-BCNT-zeolite
Keywords:
sample was the most active (182 mol nitrobenzene after 30 min). The activity of the other two catalysts at
N-BCNT
Rhodium
20 bar was well below this value, 99.5 mol after 60 min and 96 mol after 120 min for Pd and Rh,
Palladium respectively. The aniline selectivity was different for the three catalysts and they facilitate the formation
Platinum of various by-products (e.g. N-methylaniline, cyclohexylamine). The usage of the Pd and Pt/N-
Aniline BCNT-zeolite catalysts are more convenient, as only one main by-product was formed. It was confirmed
SoS catalyst that the zeolite supported N-BCNTs are efficient catalyst supports in hydrogenation processes.
Furthermore, by using this special SoS structure to support the catalytic metals the applicability is
widened and the catalyst removal is easier.
© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Nitrobenzene has an important role in the chemical industry
including the production of dyes, drugs, and explosives as it is the
starting material of aniline synthesis. The first technology to create
aniline involves a reduction of nitrobenzene by iron in the presence
of hydrochloric acid (Béchamp process) [1]. In this case, iron oxide
was formed as a by-product, which was later used as a pigment.
There are other methods for producing aniline, for example, the
amination of phenol with ammonia in the presence of hydrogen
[2]. However, the most commonly and widely used technology is
the reduction of nitrobenzene in gas or liquid phase [3–5]. A wide
variety of catalysts can be used to promote this process, which
* Corresponding author at: Institute of Chemistry, University of Miskolc, Miskolc-
Egyetemváros 3515, Hungary.
E-mail addresses: kemvanyi@uni-miskolc.hu (L. Vanyorek),
kempadam@uni-miskolc.hu (Á. Prekob), kemsik@uni-miskolc.hu (E. Sikora),
reizeredina@gmail.com (E. Reizer), kemmug@uni-miskolc.hu (G. Muránszky),
askkf@uni-miskolc.hu (F. Kristály), bela.viskolcz@uni-miskolc.hu (B. Viskolcz),
fiser@uni-miskolc.hu (B. Fiser).
usually consists of a catalytically active metal (e.g. Ni, Pd, Pt, Cu)
and a carrier (e.g. carbon, alumina, silica, zeolites).
Carbon nanotubes (CNTs) have fascinating properties, including
extraordinary mechanical strength, good chemical stability and
large surface area, which makes them perfect catalyst carriers [6].
CNTs do not contain micropores, therefore the catalysis can be
more effective and more resistant to oxidation processes. The
characteristics of carbon nanotubes can be tuned by incorporating
heteroatoms into their structure [7]. Such incorporation can be
done by using nitrogen-containing carbon compounds as starting
materials for the synthesis of the CNTs, which will lead to the
formation of N-doped carbon nanotubes (N-CNT) [8]. Incorpo-
ration of nitrogen into the CNT structure will lead to the formation
of a bamboo-like structure (nitrogen-doped bamboo-like carbon
nanotube, N-BCNT). N-BCNTs have more defect sites than their
single- or multi-walled counterparts, and due to the incorporated
nitrogen atoms, they also have high energy adsorption sites which
are excellent spots for catalytically active metal particles [9,10].
Several studies have shown that reactions can be catalyzed
successfully by using CNT-supported metal catalysts [11].
Functionalized carbon nanotube supported Ru catalysts were used

https://doi.org/10.1016/j.jiec.2019.07.006
1226-086X/© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
308 L. Vanyorek et al. / Journal of Industrial and Engineering Chemistry 79 (2019) 307–313
in sorbitol hydrogenolysis to glycols [12], while Pd, Pt, and Ni-
containing CNT catalysts were efficiently used in nitrocyclohexene
hydrogenation [13]. N-doped CNT based catalysts were applied in
oxygen and CO2 reduction reactions [14,15]. N-BCNT supported
catalysts have also achieved remarkable results in the field of
alternative diesel production (e.g. iron-based Fischer–Tropsch
catalysts) [16].
Pd, Pt, Ru, and Rh catalysts supported on carbon (C), silica (SiO2)
or alumina (Al2O3) were tested in nitrobenzene hydrogenation
[17]. The catalytic activity changed by the employed metal (Pt
> Pd > Ru, Rh), and carriers (C > Al2O3, SiO2) [17]. Nitrobenzene
hydrogenation was also carried out by using CNT supported Pt [18],
Pd and Fex-Pd catalyst [19]. The bimetallic Pt–Fe/CNT catalysts
showed much higher activity than the Pt/CNTs due to the promoter
effect of iron [20].
The reduction of nitrobenzene (NB) to aniline, which is one of
the most important products in the chemical industry, could lead
to a wide variety of by-products and intermediates depending on
the reaction conditions. In the case of applying CNT supported
catalyst, azoxybenzene (AOB) [18] and phenylhydroxylamine
(PHA) [19] were formed as intermediates. PHA could occur by
using activated carbon as catalyst support [18]. The application of
Fex-Pd has promoted the formation of nitrosobenzene during the
hydrogenation reaction [19]. A comparable amount of aniline and
azobenzene were produced with a Pt/C catalytic system in ethanol
[21]. Hydroxylamine and azoxybenzene have been produced as
intermediates with Pd/C catalyst [22]. Carbon nanotube and
activated carbon supported Pt catalysts were compared in
nitrobenzene hydrogenation, the Pt/CNT exhibit higher activity
than the Pt/AC catalysts [23]. Oxygen-containing functional groups
on the surface of carbon nanotubes could affect the particle size of
the deposited catalytically active metals, and in some case, the
catalytic activity can be decreased [24]. Application of cobalt-
containing, oxygen and nitrogen functionalized carbon nanotubes
as a catalyst will also initiate NB hydrogenation [25].
By using According to Li et al. when Pt/CNT is applied as a
catalyst in NB hydrogenation only azoxybenzene can be detected
as intermediate, which contradicts with the results of Sun et al.
who detected nitrosobenzene (NOB) next to AOB [26,27]. Sun et al.
found, that the route from NOB to aniline is less important to the
production of aniline when Pt/CNT used [27]. During their
experiments, NOB was used as a reactant for aniline synthesis,
and mostly (95%) converted to AOB, while phenylhydroxylamine
did not form. Furthermore, increasing rection time initiated the
hydrogenation of AOB towards aniline [27].
Carbon nanotube supported catalysts are catalytically active
and can be efficiently applied in aniline synthesis. However, CNTs
can form stable dispersion in the liquid reaction media (SI Fig. 1),
thus their separation is difficult [19,26]. This difficulty can be
avoided, by using a special “support on support”, or SoS system
based on zeolite bead supported nanotube supports (SI Fig. 1).
Rhodium, palladium and platinum nanoparticles were deposited
onto nitrogen-doped bamboo-like carbon nanotube (N-BCNT)
coated zeolite beads. Thus, metal-containing SoS catalyst has been
developed. The catalytic activity of these catalysts was studied and
compared in nitrobenzene hydrogenation at various reaction
conditions.
Materials and methods
Materials
Nickel(II)-nitrate hexahydrate (Ni(NO3)2x6H2O) as a catalyst,
4A zeolite beads (2 mm diameter) as support materials, patrol as
solvent (a mixture of aliphatic alcohols, Molar Chem.) and n-
butylamine (Sigma Aldrich) as carbon source was used for N-BCNT
production. The next step was the synthesis of the catalytically
active metal particles starting from anhydrous palladium (II)-
acetate (Pd(OAc)2, Fluorochem Ltd.), rhodium (II)-acetate dimer
([Rh(OAc)2]2, Sigma Aldrich), and hexachloroplatinic acid (H2PtCl6,
Reanal). In the catalytic tests, methanol (WVR) was applied as a
solvent, nitrobenzene (WVR) and 4.5 hydrogen (Messer) was used
as reactants to produce aniline.
Synthesis of the catalysts
As catalyst support, N-BCNT coated zeolite beads were used,
which were prepared according to a previously optimized
procedure [8]. The zeolite beads (19.6 g) were added to the
aqueous solution of nickel-nitrate hexahydrate (1.98 g Ni(NO3)2

6 H2O) the nickel content was kept to 2 wt%. The water from the
beads was evaporated by rotary vacuum evaporator, thereafter the
nickel salt impregnated zeolites were dried at 120  C overnight.
The impregnated zeolite beads were used as catalysts in the
Catalytic Chemical Vapour Deposition (CCVD) method to synthe-
size N-BCNTs. In each case, 20 g catalyst was placed in a quartz
reactor and the synthesis was carried out for 60 min at 750  C. The
carbon source was butylamine, which was added by a syringe
pump (6 ml/h). The butylamine was evaporated in the front-
section of the quartz reactor, and carrier gas (nitrogen, 100 ml/min)
took it to the catalyst bed. After the CCVD method, the N-BCNT
coated zeolite beads were decorated with noble metal particles to
achieve the final SoS catalysts.
During the catalyst’s preparation, the metal precursors
(palladium-acetate, rhodium-acetate, and hexachloroplatinic acid)
were solved in distilled water. The theoretical noble metal content
was 2 wt% in each case (Table 1), which was monitored by
elemental analysis (ICP-OES) measurement. The N-BCNT coated 4A
zeolite beads were added to the solution of metal precursors.
The solvents evaporated after 30 min by using a vacuum rotary
evaporator, and thus, the Rh, Pd, and Pt were impregnated into the
N-BCNT/Zeolite beads. The impregnated beads were dried at 393 K
overnight. Then, the samples were heat-treated in a nitrogen flow
at 673 K temperature for 20 min. In the final step, the catalytically
active form of the samples was achieved by hydrogenating them
for one hour at 673 K.
Characterization of the catalysts
After the CCVD (Catalytic Chemical Vapour Deposition)
synthesis of the carbon nanotubes, the presence of the N-BCNTs
on the surface of the zeolite beads was confirmed by Hitachi S 4800
scanning electron microscope (SEM), which was equipped with
energy dispersive EDAX X-ray spectrometer. During the sample
preparation for the SEM analysis, Carbon tape rubber was used. The
catalysts were examined by SEM-EDX as well.
Netzsch Tarsus TG 209 thermo-microbalance was used to
analyze the carbon nanotube content of the CNT/zeolite through
thermogravimetric analysis (TGA). Nitrogen (4.5) and oxygen (5.0)
mixture was applied as the oxidative atmosphere in the TGA
measurements. The flow rate was set to 6 ml min1 and 14 ml
min1, for the oxygen and nitrogen, respectively. The heating rate
was 10 K min1, in the 308–1073 K temperature range. The
Table 1
Composition of the catalysts.
Catalytically active metal precursor weight (g) Weight of catalyst support (g)
Palladium (II)-acetate 0.84 19.60
Rhodium (II)-acetate dimer 0.85 19.60
Hexachloroplatinic acid 1.06 19.60
 L. Vanyorek et al. / Journal of Industrial and Engineering Chemistry 79 (2019) 307–313
presence of catalytically active noble metals was confirmed by
X-ray diffractometry (Bruker Advance D8).
The Pd/N-BCNT-zeolite SoS catalyst was measured by
Micromeritics ASAP sorptometer, and the BET surface was found
15.6 m2/g.
Catalytic tests
The catalytic hydrogenation was carried out in a Büchi Uster
Picoclave reactor, in a 200 ml stainless steel vessel with heating
jacket. An excess of hydrogen was present, and the hydrogen
pressure was 5, 10 and 20 bar and the reactions were carried at
323 K. Sampling took place after the beginning of hydrogenation at
5, 10, 15, 20, 30, 60, 120, 180, 240 min. The concentration of
nitrobenzene was 0.25 mol l1 in methanol. The total amount of
the solution was 150 ml during each test. The 2 g catalyst was used
in the reactions. Aniline 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, cyclohexylamine and n-methylaniline) were provided
by Dr. Ehrenstorfer and Sigma Aldrich. The efficiency of the
catalytic hydrogenation was compared by calculating the conver-
sion, X% of nitrobenzene based on the following equation (Eq. (1)):
consumed nnitrobenzene
X % ¼
 100
initial nnitrobenzene
The selectivity, S% of the catalysts was calculated as follows
(Eq. (2)):
naniline
S % ¼  
 100
nnitrobenzene 
where naniline and nnitrobenzene are the corresponding chemical
amounts of the compounds.
The following equation (Eq. (3)) was used to calculate the yield
(Y, mol %) of the species.:
synthetized nproduct
Y % ¼  
 100
theoritical nproduct
Results
Characterization of the N-BCNT coated zeolite beads
After the CCVD synthesis, the surface of the zeolite beads was
studied by scanning electron microscopy (SEM) in order to confirm
Fig. 1. SEM image and EDX spectrum of the 2% Rh/N-BCNT-Zeolite (a, d), 2% Pd/N-BCNT-Zeolite (b, e) and the 2% Pt/N-BCNT-zeolite (c, f) catalysts.
309
the presence of nanotubes. The SEM images verified that the
zeolite beads are abundantly coated with carbon nanotubes
(SI Fig. 2a). This observation was further studied by TGA analysis
and the carbon content was determined (SI Fig. 2b). The mass
change of the N-BCNT coated zeolite beads is related to the
oxidation of carbon in the system which is identical to the carbon
nanotube content and it was 2.6 wt%. The initial ignition
temperature of the bamboo-shaped carbon nanotubes was 669
K. There was another mass loss on the initial section of the TG
curve, which can be attributed to the elimination of adsorbed
water from the zeolite structure and from the nanotube surface.
Characterization of the Rh, Pd, and Pt-decorated N-BCNT coated
zeolite nanocomposite
The noble metal decorated SoS catalysts were examined by SEM
and EDX (Fig. 1a–f). The Rh nanoparticles are located on the N-
BCNT surface in the rhodium-containing sample and they have an
average diameter (dmean) of 6.1 nm (Fig. 1a). The size distribution of
the particles covered a relatively narrow range. The surface of
nanotubes is richly coated by Rh nanoparticles. Rhodium was also
identified on the EDX spectrum alongside with other elements
which belong to the zeolite core (Fig. 1d).
In the case of the Pd containing catalyst, the average size of the
particles was 8.3 nm (Fig. 1b). The palladium identified on the
ð1Þ X-ray spectrum and the typical peaks of the zeolite are also visible
(Fig. 1e).
The Pt catalyst has small metal particles on its surface with a
size of about 5–10 nm and the catalytically active metal is well
dispersed (Fig. 1c). The energy dispersive spectrometry demon-
ð2Þ strates the presence of platinum and other elements of the zeolite
(Fig. 1f).
The samples were examined by X-ray spectrometry (XRD) as
well. The XRD shows, that in each case the elemental rhodium,
palladium, and platinum were observable. On the diffractogram of
the 2% Rh/N-BCNT-Zeolite catalyst, the reflexion of the elemental
Rh with (111), (200) and (220) Miller indexed crystal plains can be
ð3Þ found at 40.96, 47.8 and 69.7 2Q degree, respectively (SI Fig. 3a). In
case of the 2% Pd/N-BCNT-Zeolite sample three crystal plains were
identified Pd (111), Pd (200) and Pd (220) and the corresponding
reflexion peaks are located at 40.1, 46.6 and 68.1 2Q degrees (SI
Fig. 3b). The peaks which are typical for the Pt nanoparticles (111),
(200) and (220) have been found on the diffractogram of the
platinum-containing sample at 39.7, 47.4 and 67.2 2Q degrees,
respectively (SI Fig. 3c). C (002) and C (101) crystal planes were also
found due to the presence of carbon nanotubes in the
310 L. Vanyorek et al. / Journal of Industrial and Engineering Chemistry 79 (2019) 307–313
nanocomposites and the corresponding reflexions can be seen at
26.3 and 44.4 2Q degrees in each case. In summary, the XRD results
confirmed, that the three noble metals are in catalytically active
forms, exactly in their elemental state on the surface of the
catalysts.
Results of the catalytic measurements
The developed catalyst was found to be more active during the
nitrobenzene (NB) hydrogenation. The 2% Pt/N-BCNT-zeolite
catalyst reached 99.8% conversion after 1 h at 5 bar hydrogen
pressure (Fig. 2a). The maximum conversion in the case of the
palladium-containing sample after 1 h (5 bar) was 99.7%. By
applying of rhodium nanocomposite 97.4% was reached at 5 bar
pressure, after 4 h. The Pt nanocomposite catalyst was the most
catalytically active, 180 mol (nNB) of the reactant was converted
with 1 mol of platinum, within one hour (Fig. 2d). The difference in
electron configuration and size of the metal atoms are two factors
which could be responsible for the different activity of the
catalysts. The strength of the interaction between the nitrogen of
aniline and the noble metals are highly influenced by the above-
mentioned factors and could be the reason behind the outstanding
activity of Pt.
By increasing hydrogen pressure up to 10 bar, the conversion
rate increased in case of all catalysts (Fig. 2b). The Pt-containing
catalyst resulted in 99.8% NB conversion after 30 min, so 182 mol
nitrobenzene converted by 1 mol Pt, within 30 min hydrogenation
(Fig. 2e). The nitrobenzene conversion was lower with the same
amount of rhodium in a similar system.
By further increasing the pressure up to 20 bar, the conversion
also increased and within 15 min it has reached 95.6% in case of the
platinum catalyst (Fig. 2c). The conversion on the Rh/N-BCNT-
zeolite was increased from 60% to 95%, after 80 min. In the case of
the Pd/N-BCNT-zeolite catalyst, 20 min shorter reaction time was
enough to compare to lower pressure to achieve maximum
nitrobenzene transformation. In the case of the Pd and Rh catalysts,
99.5 mol (after one hour) and 96 mol (after two hours) nitroben-
zene were converted by 1 mol catalytically active metal. For the Pt
Fig. 2. Nitrobenzene conversion and converted moles of nitrobenzene on the surface of 1 mol catalytic metal of the nanocomposite at 5 bar (a and d), 10 bar (b and e) and
20 bar (c and f). Blue square — 2% Pd/N-BCNT-zeolite; white circle — 2% Pt/N-BCNT-zeolite; red triangle — 2% Rh/N-BCNT-zeolite. (For interpretation of the references to colour
in this figure legend, the reader is referred to the web version of this article.)
catalyst, this parameter was almost the same as in the case of 10
bar hydrogen pressure (Fig. 2f).
In terms of selectivity 84% aniline was reached with the 2% Pd/
N-BCNT-zeolite catalyst at 5 bar after 80 min hydrogenation, and it
did not change when 10 or 20 bar pressure was applied (Fig. 3a–c).
The aniline selectivity was higher (98.1%) with the Rh containing
samples at 5 bar, but the reaction time was longer (4 h). However,
the pressure increase was counterproductive and at 10 and 20 bar,
the achieved selectivity is only 88% and 53%, even after running the
reaction for four hours. The aniline selectivity at 5 and 10 bar
pressure was reached the maximum (99.2% and 98.9%) after 80 and
20 min in case of the 2% Pt/N-BCNT-zeolite, at 20 bar this was
achieved after 60 min. The concentration of the synthesized aniline
was decreased by in pressure, and reaction time. This can be
explained by aniline polymerization, which was also confirmed by
the mass-spectra of the species. On the mass spectra obtained from
the UPLC-MS chromatogram the following m/z ratios belong to the
polyaniline structure [C6H4NH]n: 183.3 (n = 2), 274.2 (n = 3), 365.3
(n = 4), 456.3 (n = 5), 547.5 (n = 6) (SI Fig. 4). Thus, 5 bar is optimal
for the aniline synthesis, because increasing pressure and reaction
time facilitates polyaniline formation.
Several intermediates/by-products such as N-methylaniline
(NMA), azoxybenzene (AOB), cyclohexylamine (CHA), dicyclohex-
ylamine (DCHA), o-toluidine (OTD) and nitrosobenzene (NOB)
were formed during the hydrogenations in different concentra-
tions (Figs. 4a–i and 5 ).
In the case of the 2% Pd/N-BCNT-zeolite catalyst, during aniline
production, one intermediate and one by-product, nitrosobenzene
and N-methylaniline (11.7 mmol/dm3) were formed at 5 bar
(Fig. 4a). The same Pd catalyst at 10 bar converted nitrobenzene
into aniline and NMA (11.4 mmol/dm3) (Fig. 4d). By increasing the
pressure to 20 bar NMA was still formed (10.2 mmol/dm3) and its
concentration did not change significantly, while the NOB was
eliminated after 120 min hydrogenation.
The Pt-containing catalyst was less selective towards aniline,
and several other components were detected next to the main-
product (Fig. 4b, e, h). At 5 bar CHA, AOB, OTD, and NOB were
formed (Fig. 4b). CHA, AOB and NOB were intermediates, which
 L. Vanyorek et al. / Journal of Industrial and Engineering Chemistry 79 (2019) 307–313 311

Fig. 3. Aniline selectivity of the catalysts by applying 5 bar (a), 10 bar (b) and 20 bar (c) hydrogen pressure. Blue square — 2% Pd/N-BCNT-zeolite; white circle — 2% Pt/N-BCNT-
zeolite; red triangle — 2% Rh/N-BCNT-zeolite. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. Concentration of the intermediates and by-products at different hydrogen pressure produced by using the prepared catalysts: 2% Pd/N-BCNT-zeolite at 5 bar (a), 10 bar
(d) and 20 bar (g); 2% Pt/N-BCNT-zeolite at 5 bar (b), 10 bar (e) and 20 bar (h); 2% Rh/N-BCNT-zeolite at 5 bar (c), 10 bar (f) and 20 bar (i).

reacted forward to produce aniline at the end of the hydrogenation.
By increasing the pressure to 10 bar AOB and NOB were formed
again as intermediates, but they have converted to aniline within
less than an hour, while CHA did not form (Fig. 4e). At 10 and 20 bar
pressure, NMA was not detected unlike in the case of the Pd/N-
BCNT-zeolite catalyst but, new by-product such as o-toluidine
appeared (6.4 and 5.9 mmol/dm3) (Fig. 4e, h). The transformation
rate of the two intermediates increased with the pressure (Fig. 4h),
but the OTD content did not change significantly.
In the case of the 2% Rh/N-BCNT-zeolite catalyst 5 intermediates
and by-products, AOB, NOB, NMA, CHA, and DCHA has been
detected (Fig. 4c, f, i). The NOB (10.3 mmol/dm3) and the AOB
(71 mmol/dm3) have not converted into aniline at 5 bar, and
instead of that, NMA (9.6 mmol/dm3) other aromatic compounds
(CHA and DCHA, 32 and 4 mmol/dm3, respectively) which were not
detected in cases of the Pd and Pt catalyst appeared in the reaction
mixture after 120 min (Fig. 4c). This suggests, that the Rh catalyst
opens new reaction pathways. By increasing the pressure to 10 bar,
312 L. Vanyorek et al. / Journal of Industrial and Engineering Chemistry 79 (2019) 307–313
Fig. 5. Proposed mechanism of nitrobenzene hydrogenation including the detected structures for all three studied SoS catalysts (Pd — green frame, Pt — black-dashed frame,
Rh — grey). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
NOB and AOB converted to aniline, but the amount of the other by-
products only slightly has changed. The concentration of NMA and
CHA decreased to 7.9 and 22.5 mmol/dm3, while the DCHA
increased up to 5 mmol/dm3. (Fig. 4f and i). Further, an increase
in the pressure to 20 bar caused a significant increase in the yield of
CHA and DCHA up to 66 and 9.6 mmol/dm3, respectively. However,
the other components were eliminated after 180 min. All in all, we
can conclude that the Pd/N-BCNT-zeolite catalyst was the most
selective as it facilitates the formation of only aniline and one by-
product (NMA).
The process of nitrobenzene hydrogenation to aniline was first
described by Haber [28] and later it was modified and new
proposals were developed [29]. These proposals are not complete-
ly applicable in this case. Thus, based on the results of the catalytic
measurements, a reaction mechanism was envisaged which
includes all the structures detected during the nitrobenzene
hydrogenation (Fig. 5). This complex reaction mechanism starts
with nitrobenzene (NB). After two hydrogen additions and one
water elimination in the third step, the formation of nitro-
sobenzene (NOB) can be achieved, which was detected in the
presence of each catalyst. The reaction continues with another H
addition, which is followed by a water elimination resulting in this
way the indirect formation of azoxy–azobenzene (AOB). With the
help of an additional water molecule, the reaction route goes on
with the split of azoxy–azobenzene, reaching in this way the main
product of this study, aniline (AN). However, aniline can be formed
also indirectly from azoxy–azobenzene, resulting in orto-toluidine
(OTD) as well, which was a by-product in case of the Pt catalyst
(black-dotted line). Since, at the ends of nanotubes, numerous
highly reactive carbenes could be found, orto-toluidine (OTD), as
well as N-methylaniline (NMA), can be formed directly from
aniline with the addition of a carbene. The reaction which gives N-
methylaniline can occur by applying both Pd and Rh catalysts. In
previous studies, NMA was not detected when carbon supported
Pd was applied [29,30,31]. Cyclohexilamine (CHA) was detected by
applying Rh catalyst, and can be formed by the further
hydrogenation of aniline. By applying Rh another molecule
appeared, dyciclohexylamine (DCHA) which can be reached from
aniline through a four-step reaction. CHA and DCHA were reached
previously by using nickel and palladium-containing catalysts
(Pd/Al2O3 and Ni/Al2O3) [32–35].
Conclusion
In our work, special “support on support” (SoS) catalysts have
been developed which include nitrogen-doped bamboo-like
carbon nanotube (N-BCNT) coated zeolite beads as catalyst
supports for rhodium, palladium and platinum nanoparticles.
The surface of the zeolite beads was abundantly covered by N-
BCNTs. On the surface of the zeolite supported N-BCNTs noble
metal nanoparticles were deposited by using a hydrogenation
procedure. The SEM images confirmed that the distribution of
nanoparticles on the surface of the three catalysts was homoge-
nous. The catalytic activity of the three samples was compared at
different pressures (5, 10 and 20 bar) at 323 K by using the
nitrobenzene (NB)/niline (AN) hydrogenation reaction. The Pt/N-
BCNT-zeolite sample was the most active catalytically (182 mol
nitrobenzene after 30 min). The activity of the other two catalysts
at 20 bar was well below this, 99.5 mol after 60 min and 96 mol
after 120 min for the 2% Pd/N-BCNT-zeolite and 2% Rh/N-BCNT-
zeolite, respectively. Although the catalytic activity is lower, the Pd
containing catalyst can be a convenient choice for the NB/AN
hydrogenation, as only one main by-product was formed
(N-methylaniline). The selectivity of the Rh catalyst is unsuitable
to produce aniline, because several side-reaction pathways
appeared, which led to various by-products, such as cyclohexyl-
amine, dicyclohexylamine, N-methylaniline, and polyaniline deri-
vates as well. Reaction pathways are proposed which describe the
formation of all detected structures for all three studied SoS
catalysts. All in all, the SoS system is more convenient to use
 L. Vanyorek et al. / Journal of Industrial and Engineering Chemistry 79 (2019) 307–313
compared to other catalysts, because it is easy to treat and remove
from the reaction medium and the formation of a stable dispersion
of the carbon nanotubes can be avoided.
Conflict of interest
On behalf of all authors, the corresponding author states that
there is no conflict of interest.
Acknowledgements
This research was supported by the European Union and the
Hungarian State, co-financed by the European Regional Develop-
ment Fund in the framework of the GINOP-2.3.4-15-2016-00004
project, aimed to promote the cooperation between the higher
education and the industry.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jiec.2019.07.006.
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