Accepted Manuscript

Palladium nanoparticles supported on carbon nanoglobules as

efficient catalysts for obtaining benzocaine via selective
hydrogenation of ethyl 4-nitrobenzoate

Roman M. Mironenko, Olga B. Belskaya, Tatiana I. Gulyaeva,

Mikhail V. Trenikhin, Vladimir A. Likholobov

PII: S1566-7367(18)30212-7
DOI: doi:10.1016/j.catcom.2018.06.002
Reference: CATCOM 5417
To appear in: Catalysis Communications
Received date: 27 April 2018
Revised date: 26 May 2018
Accepted date: 1 June 2018

Please cite this article as: Roman M. Mironenko, Olga B. Belskaya, Tatiana I. Gulyaeva,
Mikhail V. Trenikhin, Vladimir A. Likholobov , Palladium nanoparticles supported on
carbon nanoglobules as efficient catalysts for obtaining benzocaine via selective
hydrogenation of ethyl 4-nitrobenzoate. Catcom (2018), doi:10.1016/
j.catcom.2018.06.002

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 ACCEPTED MANUSCRIPT

Palladium nanoparticles supported on carbon nanoglobules as efficient

catalysts for obtaining benzocaine via selective hydrogenation of ethyl

4-nitrobenzoate

Roman M. Mironenkoa,b,* , Olga B. Belskayaa,c, Tatiana I. Gulyaevaa, Mikhail V.

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Trenikhina,c, Vladimir A. Likholobova,d

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a
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of

Sciences, 54 Neftezavodskaya st., 644040, Omsk, Russia

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b
Dostoevsky Omsk State University, 55a Mira ave., 644077, Omsk, Russia
c
Omsk State Technical University, 11 Mira ave., 644050, Omsk, Russia
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d
Omsk Scientific Center, Siberian Branch of the Russian Academy of Sciences, 15

Karla Marksa ave., 644024, Omsk, Russia

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* Corresponding author: Roman M. Mironenko

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E-mail: mironenko@ihcp.ru

Phone: +7 (3812) 670 474, Fax: +7 (3812) 646 156

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Abstract

The palladium catalysts prepared using carbon nanoglobules (CNGs) as the support and

containing no more than 2 wt.% Pd were shown to be highly effective for the liquid-

phase hydrogenation of ethyl 4-nitrobenzoate under mild conditions. Regardless of the

kind of CNGs and the catalyst preparation method, the most of the Pd/CNGs catalysts

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allow achieving a complete conversion of substrate giving benzocaine in a 100% yield.

The Pd/CNGs catalyst is easily recycled many times without loss of its catalytic

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performance. The results obtained may be useful for the development of effective Pd/C

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catalysts for chemoselective hydrogenation of various nitroarenes.
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Keywords: catalytic hydrogenation, carbon nanoglobules, palladium catalysts, ethyl 4-
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nitrobenzoate, benzocaine
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1. Introduction

Local anesthetics of the aminoester series, such as novocaine, tetracaine, and

benzocaine, are currently considered as important best-selling drugs and commercially

synthesized by the reduction of 4-nitrobenzoic acid derivatives [1‒3]. For instance,

benzocaine (i.e., ethyl 4-aminobenzoate, EAB) can be prepared in one step from ethyl

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4-nitrobenzoate (ENB) either by reduction with iron in acidic medium or by

hydrogenation over Raney Ni [1, 3‒5]. However, these methods have drawbacks,

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namely non-recyclable wastes, significant amount of by-products, pyrophoricity of

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Raney Ni.

Recently, chemoselective hydrogenation of aromatic nitro compounds to

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corresponding anilines over supported metal nanoparticles (NPs) is of remarkable
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interest [6‒8]. In particular, the development of highly active supported catalysts for

selective hydrogenation of ENB to EAB is a topical task [3, 9]. By now, various
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supported catalysts containing Pd [3, 9‒14], Pt [15, 16], Ni [17‒19] have been proposed

for this reaction. Nevertheless, the proposed catalysts often contain a considerable
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amount of precious metal, do not always provide a full conversion of the substrate or
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require severe reaction conditions to achieve a high yield of EAB. Besides, the
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preparation of some of the catalysts consists of several steps and requires expensive
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reagents and materials.

Carbon nanoglobules (CNGs) are the nanostructured carbon material produced

commercially on a large scale as carbon black [20, 21]. Like other porous carbon

materials, CNGs have some advantages for application as support of metal catalysts for

liquid-phase reactions: a developed pore space that ensures a transfer of reactants and

reaction products, controllable structure and chemical properties of the surface,

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chemical inertness [21, 22]. Moreover, CNGs are one of the cheapest and most available

carbon materials. The CNGs-supported catalysts have industrial application for

hydrogenation of 2,4-dinitrotoluene to 2,4-toluenediamine [21]. Recently [23], it has

been found that Pd/CNGs catalysts may be superior in hydrogenation activity to

analogous palladium catalysts based on activated carbon or carbon nanotubes (CNTs). It

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is important to note that current reviews on the application of carbon nanomaterials in

catalysis [22, 24, 25] pay little attention to CNGs or indicate that this material has very

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limited catalytic application.

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In the present study, it was shown that CNGs-based catalysts containing no more

than 2% palladium are highly active in the liquid-phase hydrogenation of ENB to EAB
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under mild conditions and allow attaining a 100% selectivity of the target product at a
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complete conversion of the substrate. The Pd/CNGs catalysts were prepared by simple

and widespread methods and using the CNGs supports with different morphology,
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porosity and surface chemistry. The supports as well as the catalysts based on them

were characterized by a set of methods.

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2. Experimental
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2.1. Catalysts preparation

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Different kinds of CNGs used as the supports were obtained at the Department

of Experimental Technologies, Institute of Hydrocarbons Processing (Omsk, Russia).

The support samples denoted as CNGs-1 and CNGs-2 were prepared by oxidative

pyrolysis of mixed hydrocarbon feedstocks of different composition at different contact

time, whereas the CNGs-3 support was obtained by non-oxidative pyrolysis of natural
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gas. Besides, commercial CNTs (Baytubes C 150 HP, Bayer MaterialScience AG) were

also used as the support for comparison.

The palladium catalysts containing 1 or 2 wt.% Pd were synthesized by the two

techniques described previously [26, 27]: (i) incipient wetness impregnation of a carbon

support with solutions of palladium chloride complexes (CC), followed by drying in air

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at room temperature and reduction in flowing hydrogen at 573 K for 2 h (Pd-CC/CNGs

catalysts); (ii) hydrolytic precipitation of polynuclear hydroxy complexes (PHC) of Pd

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on a carbon support and subsequent reduction with a solution of sodium formate at 363

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K for 0.5 h (Pd-PHC/CNGs catalysts). NU
2.2. Characterization of the CNGs supports and Pd/CNGs catalysts
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The structure of CNGs supports was characterized using powder X-ray

diffraction (XRD) on a D8 Advance (Bruker) diffractometer with CuK radiation at a

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step width of 0.05o . Pore structure parameters of the supports were measured using

nitrogen adsorption–desorption at 77 K on an ASAP-2020 (Micromeritics) porosity

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analyzer. The composition of surface functional groups of the supports was analyzed
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using Fourier transform infrared (FTIR) spectroscopy on an IRPrestige-21 (Shimadzu)

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instrument. Raman spectra of the CNGs supports were recorded on a DXR Smart
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Raman (Thermo Fisher Scientific) spectrometer with a 633 nm laser source.

Transmission electron microscopy (TEM) images of the supports and reduced catalysts

were taken by a JEM-2100 (JEOL) microscope using an accelerating voltage of 200 kV.

The energy dispersive X-ray (EDX) analysis was performed with an INCA 250 (Oxford

Instruments) spectrometer. The processes of hydrogen consumption/evolution were

investigated on an AutoChem II 2920 (Micromeritics) chemisorption analyzer. The

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palladium dispersion in reduced catalysts was determined by pulse chemisorption of CO

molecules at room temperature using an AutoChem II 2920 analyzer. Palladium content

in the catalysts was estimated by atomic absorption spectrometry (AAS) on an AA-6300

(Shimadzu) spectrometer.

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2.3. Catalytic measurements

The hydrogenation of ENB with hydrogen gas in the presence of palladium

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catalysts was performed in a Miniclave drive (Büchi AG) periodic reactor at a

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temperature of 323 K and pressure of 0.5 MPa for 1 h in ethanol. The reaction mixture

was magnetically stirred at 1000 rpm. The progress of the reaction was monitored by
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measuring the volume of consumed hydrogen. The reaction products were identified by
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gas chromatography–mass spectrometry (GC-MS). The quantitative composition of the

reaction solutions was determined by GC.

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See Supplementary Materials for more experimental details on the preparation

and characterization of the catalysts as well as the procedure of catalytic reaction.

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3. Results and discussion

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3.1. Characterization of the CNGs supports

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According to XRD data (Fig. S8, Table S2), all of the CNGs samples exhibit a

hexagonal graphite-like structure having a turbostratic stacking of graphene layers. At

the same time, the samples differ little among themselves in structural parameters,

which correspond to those for carbon black [22]. The results of Raman spectroscopy

(Fig. S9) indicate that CNGs have a disordered structure since the intensity of D band

(related to amorphous carbon or disordered graphite) is larger than that of G band [28].
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From the TEM images, it can be clearly seen that the CNGs supports consist of

aggregates of globules (Fig. S10). The mean sizes of globules and their aggregates

depend on the conditions of CNGs synthesis and, therefore, are different for each

sample (Table S2). So, the CNGs-3 material obtained by non-oxidative pyrolysis of

natural gas exhibits the largest globules and aggregates. This is typical for carbon blacks

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which are produced by the thermal black process [20, 21].

The investigation of the pore structure of CNGs showed that the CNGs-3

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support has the lowest specific surface area and total pore volume compared to the

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CNGs-1 and CNGs-2 samples (Table S3). The difference between CNGs-1 and CNGs-2

involves the lower specific surface area of the CNGs-1 sample along with a large
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average pore size.
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According to FTIR spectroscopy (Fig. S11), the CNGs samples differ in the

intensity of the absorption bands attributed to С–О stretching vibrations in ether,

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lactone, alcohol and phenol groups, as well as C=O stretching vibration in quinones.

Thus, CNGs-2 is characterized by an increased intensity of absorption bands

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corresponding to acidic alcohol and phenol groups. This may be due to the fact that the
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formation of CNGs-2 proceeds in the oxidative pyrolysis of hydrocarbon feedstock at

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elevated contact time with oxidant. It is important that oxygen groups on the carbon
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surface increase the interaction of the palladium precursor with the support [29] that can

change the composition of deposited palladium species.

3.2. Characterization of the Pd/CNGs catalysts

According to H2 -TPR, the reduction profiles of the 1% Pd-CC/CNGs catalysts

display a single hydrogen consumption peak, which is attributed to the reduction of

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supported palladium precursor (Fig. S12). The 1.0% Pd-CC/CNGs-3 catalyst is reduced

at lowest temperature within a very narrow range below 425 K, while the hydrogen

consumption peaks for the samples based on CNGs-1 and CNGs-2 are broad and shifted

to the high-temperature region. The observed difference in the reduction conditions may

be due to distinctions in the composition of supported Pd CC which, in turn, is

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determined by the composition of surface functional coverage of the CNGs supports.

Moreover, results from CO chemisorption and TEM measurements (Table 1, Figs. S14,

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S16, S18) revealed that the size of Pd NPs formed upon reduction of Pd CC essentially

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depends on the kind of CNGs. Thus, the Pd CC supported on CNGs-3 are quite

homogeneous in composition and their reduction leads to highly dispersed Pd NPs with
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a rather narrow size distribution. In contrast, the catalysts based on the CNGs-1 and
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CNGs-2 supports enriched with oxygen groups are reduced in a much wider

temperature range giving large Pd NPs with a relatively broad size distribution. Despite
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these differences, all catalysts prepared using Pd CC exhibit a rather uniform

distribution of Pd NPs over the carbon supports (see EDX maps in the Supplementary
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Materials).
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During the synthesis of Pd-PHC/CNGs catalysts, the reduction of precursor to

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metallic palladium by sodium formate is assumed to be complete since no hydrogen

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consumption was observed under H2 -TPR conditions (Fig. S13). The negative signals at

a temperature range of 320‒370 K correspond to the release of hydrogen as a result of

the decomposition of palladium -hydride [27, 30], which is formed upon the

interaction between palladium and hydrogen already at room temperature. According to

CO chemisorption and TEM data (Table 1, Fig. 1; see also Figs. S15, S17, S19), the

dispersion of supported palladium in the 1% Pd-PHC/CNGs catalysts does not

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substantially depend on the kind of CNGs. The samples exhibit close values of the

average size of Pd NPs with a distribution predominantly within the size range of 2‒6

nm. The EDX maps show an uneven distribution of Pd NPs formed from Pd PHC over

the carbon supports, especially for the 1.0% Pd-PHC/CNGs-3 sample. Unlike the

catalysts prepared using Pd CC, the Pd-PHC-type catalysts contain clusters of up to

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several dozen Pd NPs. These clusters are localized mainly in defective areas of the

carbon surface, as well as the contact points of globules.

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3.3. Catalytic hydrogenation of ENB

The Pd-CC/CNGs and Pd-PHC/CNGs catalysts containing 1 wt.% Pd were

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studied in the hydrogenation of ENB in ethanol medium at a temperature of 323 K and
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hydrogen pressure of 0.5 MPa. As can be seen from Table 1 (see also Fig. S20a), the

catalysts based on CNGs-3 are very active in the reaction under study and allow to
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reach a complete conversion of substrate and 100% selectivity for EAB. At the same

time, the activity of the catalysts supported on CNGs-1 and CNGs-2 depends on the
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conditions of the catalyst preparation. So, the hydrogenation over the catalysts
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synthesized using Pd PHC always proceeds with a high turnover frequency (TOF), leads
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to full conversion of substrate and gives EAB in 100% yield. The catalysts prepared by
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impregnation of CNGs-1 and CNGs-2 with solutions of Pd CC are less active and the

selectivity does not reach 100%. In the case of least active 1.0% Pd-CC/CNGs-2

catalyst, such by-products as ethyl 4-(hydroxyamino)benzoate (EHAB), diethyl 4,4'-

azoxydibenzoate (DAD) and diethyl 4,4'-azobenzenedicarboxylate (DABD) were

detected in the reaction mixture. Based on the results obtained (see also Fig. S21), it can
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be assumed that the hydrogenation of ENB proceeds in accordance with the mechanism

proposed by Haber [6‒8] as depicted in Scheme 1.

O O O O
H2 H2 H2
O CH3 O CH3 O CH3 O CH3
-H2O HO -H2O
O2N ON N H2N
H
ethyl 4-nitrobenzoate ethyl 4-nitrosobenzoate ethyl 4-(hydroxyamino)benzoate ethyl 4-aminobenzoate
(ENB) (undetected) (EHAB) (EAB)

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-H2O H2

O O

O CH3 O CH3

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N H2 N
N N
H3C O O -H2O H3C O

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O O
diethyl 4,4’-azoxydibenzoate diethyl 4,4’-azobenzenedicarboxylate
(DAD) (DABD)
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Scheme 1. Proposed reaction network for ENB hydrogenation over Pd/CNGs catalysts.
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For comparison, the hydrogenation of ENB in the presence of a catalyst based

on commercial CNTs was also carried out. This catalyst containing 1 wt.% Pd was
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prepared in the same way as the catalysts of Pd-CC/CNGs series. As can be seen (Table

1), the most of 1% Pd/CNGs catalysts are not inferior to 1% Pd/CNTs in yield of EAB,
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but superior in the TOF values.

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The CNGs-based catalysts containing 2 wt.% Pd proved to be even more active

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in the hydrogenation of ENB compared to the one-percent samples (Table S4, Fig.
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S20b). Under the same reaction conditions, a 99‒100% selectivity for target EAB

(except the 2.1% Pd-CC/CNGs-2 catalyst) is achieved at a complete conversion of

ENB.

In the industrial process, the catalyst reusability is essentially important.

Therefore, the recyclability of Pd/CNGs catalytic system for selective hydrogenation of

ENB to EAB was investigated. For this purpose, one of the most active samples namely
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1.0% Pd-PHC/CNGs-3 was applied. The reusability test for this catalyst was performed

under the same reaction conditions as indicated above but on an enlarged scale. After

each cycle, the catalyst was separated from the reaction mixture, washed, dried and

applied for the next run. As can be seen from Fig. 2, the catalyst shows an excellent

reusability and can be used for six times without loss of the activity (100% conversion

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of ENB). Moreover, the yield of EAB remains at the high level of 100% for all cycles

that opens the possibility of the application of CNGs-based catalyst for the EAB

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synthesis on a large scale.

4. Conclusions
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Thus, it was found that CNGs-supported catalysts containing less than 2 wt.%
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Pd are very effective in the liquid-phase hydrogenation of ENB under mild conditions

(323 K, 0.5 MPa). The dispersion state of supported Pd NPs and their catalytic activity
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(TOF) depend in some degree on the kind of CNGs (morphology, porosity and surface

chemistry) as well as the catalyst preparation method. Nevertheless, despite this, the
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most of the Pd/CNGs catalysts allow attaining a complete conversion of substrate

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giving benzocaine in a 100% yield. The Pd/CNGs catalyst is easily recycled many times
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without loss of its catalytic performance. The results obtained are useful for the
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development of effective Pd/CNGs catalysts for selective hydrogenation of various

nitroarenes. For this purpose, commercially available carbon blacks differing in

morphology, porosity and surface chemistry may be successfully applied.

In the near future, we plan to study the performance of CNGs-based catalysts

containing 0.5% Pd in the hydrogenation of ENB and other nitroarenes. This is

important primarily in terms of reducing the loading of expensive palladium.

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Acknowledgements

The authors thank O.V. Maevskaya, T.V. Kireeva, R.R. Izmailov, I.V.

Muromtsev, A.B. Arbuzov, E.N. Kudrya, V.P. Talsi, S.N. Evdokimov for their help

with experiments. Besides, the authors are grateful to A.V. Romanenko (Boreskov

Institute of Catalysis, Novosibirsk) for the supply of ENB sample. Characterization of

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catalysts and identification of reaction products were performed using equipment of the

Omsk Regional Center of Collective Usage, Siberian Branch of the Russian Academy

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of Sciences.

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This work was supported by the Russian Foundation for Basic Research (grant

no. 16-29-10742).
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Table captions

Table 1. Catalytic properties of the 1% Pd/CNGs samples in the hydrogenation of ENB.

Figure captions

Fig. 1. TEM images of the 1.0% Pd-PHC/CNGs-1 (a), 1.1% Pd-PHC/CNGs-2 (b), 1.0%

Pd-PHC/CNGs-3 (c) catalysts and the corresponding histograms of the Pd NPs diameter

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distribution.

Fig. 2. Recyclability test of the 1.0% Pd-PHC/CNGs-3 catalyst in the hydrogenation of

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ENB. Reaction conditions: temperature of 323 K, pressure of 0.5 MPa, 1 h, 100 mL of

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ethanol, 5.000 g of ENB, 500 mg of catalyst; the ENB/catalyst ratio was kept the same

in all cycles.
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Table 1. Catalytic properties of the 1% Pd/CNGs samples in the hydrogenation of

ENBa.

TOF (mol S (%)f

d d vs H2 ∙ mol X
Catalyst vs,CO
(nm)b (nm)c Pds-1 ∙ min- (%)e EAB EHAB
1 d DAD DABD
)
1.1% Pd- very slow,
3.3 4.3 100 96.2 1.2 1.6 1.0
CC/CNGs-1 undefined
1.0% Pd-

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PHC/CNGs- 4.6 3.5 153 (115) 100 100 0 0 0
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1.0% Pd- very slow,
3.3 2.9 96.1 86.4 5.4 1.6 6.6

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CC/CNGs-2 undefined
1.1% Pd-

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PHC/CNGs- 5.0 3.8 328 (249) 100 100 0 0 0
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1.0% Pd-
2.8 2.5 253 (230) 100 100 0 0 0
CC/CNGs-3
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1.0% Pd-
PHC/CNGs- 4.3 3.7 398 (345) 100 100 0 0 0
3
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1.0% Pd-
1.9 undefined 92 100 100 0 0 0
CC/CNTs
a
Reaction conditions: temperature of 323 K, pressure of 0.5 MPa, 1 h, 50 mL of
ethanol, 500 mg of ENB, 50 mg of catalyst.
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b
The mean volume-surface diameter of Pd NPs calculated from CO chemisorption data,
see Eq. (8) in Supplementary Materials.
c
The mean volume-surface diameter of Pd NPs calculated from TEM data, see Eq. (6)
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in Supplementary Materials.
d
TOF values were calculated using dispersion values derived from CO chemisorption
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data or from TEM data (in parentheses), see Eq. (9) in Supplementary Materials.
e
Conversion of ENB after 1 h of the reaction according to GC, see Eq. (10) in
Supplementary Materials.
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f
Selectivity for the products according to GC, see Eq. (11) in Supplementary Materials.
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Fig. 1

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Fig. 2
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Graphical abstract

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Highlights
 Pd/CNGs is a promising catalyst for hydrogenation of ethyl 4-nitrobenzoate.
 Pd/CNGs allow obtaining benzocaine in a 100% yield.
 CNGs kind affects the reducibility and dispersion state of supported Pd.
 Pd/CNGs can be a practical catalyst for synthesis of benzocaine and other anilines.

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