Accepted Manuscript

Hydrogenation of nitrobenzene to aniline catalyzed by

C60-stabilized Ni

Yingmin Qu, Hao Yang, Songlin Wang, Tong Chen, Gongying

Wang

PII: S1566-7367(17)30164-4
DOI: doi: 10.1016/j.catcom.2017.04.029
Reference: CATCOM 5014
To appear in: Catalysis Communications
Received date: 8 January 2017
Revised date: 10 April 2017
Accepted date: 15 April 2017

Please cite this article as: Yingmin Qu, Hao Yang, Songlin Wang, Tong Chen, Gongying
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 ACCEPTED MANUSCRIPT

Hydrogenation of nitrobenzene to aniline catalyzed by

C60-stabilized Ni
Yingmin Qua, b , Hao Yang a,b
, Songlin Wang c, Tong Chen a* , Gongying Wang a
a
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041,

PR China;

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b
University of Chinese Academy of Sciences, Beijing 100049, P R China;
c
School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology,

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Xinxiang 453003, PR China

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*Corresponding author. Tel.: +86 028 85250005; fax: +86 028 85220713.

E–mail: chentongw@cioc.ac.cn (Tong Chen)

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Abstract

The C60 -stabilized Ni catalyst, denoted as Ni/C60 , was prepared by regular impregnation

following the chemical reduction and employed to catalyze hydrogenation of nitrobenzene. The

characterizations suggested that reductants, NaBH4 amount and nickel precursor influenced

metallic Ni concentration on surface of catalyst, and C60 improved the dispersion of Ni and

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reduced the electron density of metallic Ni. The nitrobenzene conversion and the aniline

selectivity both reached above 99.9% over Ni/C60 , within 40 min under 90 ℃ and 2 MPa of H2 .

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C60 improved the aniline selectivity and enhanced the stability of Ni/C60 ascribed to its

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hydrophobicity.

Keywords: C60 , Ni, hydrogenation, nitrobenzene, aniline

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1. Introduction

Catalytic hydrogenation of aromatic nitro compounds is an important process for the

synthesis of aromatic amine compounds which were valuable compounds for the plastic, rubber

processing, herbicide, dyes and pharmaceutical industries [1-4]. The liquid phase hydrogenation of

nitrobenzene proceeds consecutively in several steps and is employed to the production of aniline，

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which is usually catalyzed by supported noble metals or Ni-based catalysts [5-9]. Ni-based

catalysts were widely reported for their higher activity and lower price. However, this reaction

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over Ni-based catalysts must be performance at higher temperature, higher H2 pressure, and longer

time in order to reach a satisfied selectivity of aniline [10]. It suggested that the nickel precursor

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affected the crystallite size and degree of dispersion of metallic Ni, which influenced significantly

the catalytic activity of Ni-based catalyst [8]. So, it is important to improve the contention and
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dispersion of metallic Ni on the surface of catalyst to obtained excellent catalytic activity of

hydrogenation. According to researches, higher nitrobenzene conversions have been reported

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when carbon was used as support than alumina or silica. Moreover, carbon is rather chemically

inert, allowing condensation reactions to be avoided compared with oxide supports [11]. Mahata et
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al. [12] reported that nickel nanoparticles stabilized by filamentous carbon with approximately 99%

aniline yield were better than Raney Ni in terms of activity and aniline selectivity. The oxide
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layers together with filamentous carbon protected nickel particles from bulk oxidation of Ni by air.
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Qiu et al. [13] prepared magnetically recoverable Ni/C catalysts to catalyze selective

hydrogenation of nitroarenes with high-stability.

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Fullerene (C60 ), a zero-dimension carbon nanomaterial, has superb ability to accommodate

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electrons and hold and release electrons, and used to catalyze some reaction with unique catalytic

performances [14-21]. Furthermore, C60 is the only form of carbon which potentially can be

chemically hydrogenated and dehydrogenated reversibly, due to its unique molecular structure,

making such structure as a high-capacity hydrogen-storage material and employing to catalyze

hydrogenation reactions with special catalytic activity [22-25]. In addition, C60 molecules limited

the growth of Ni and protected the metallic Ni from oxidation in air [26, 27]. Furthermore,

Vijayakrishnan et al. reported that Ni interacted stronger with C 60 than with graphite [28].

Therefore, it would be exhibited interesting catalytic performance for C60-stabilized Ni catalysts in

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the hydrogenation of nitrobenzene to aniline.

In the present work, C60 -stabilized Ni catalysts, denoted as Ni/C60 , were prepared and

employed to catalyze the hydrogenation of nitrobenzene to aniline. The effects of nickel precursor

and reductants on the catalytic activity of Ni/C60 were investigated.

2. Experimental section

2.1. Catalyst preparation

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The C60 (95%) was bought from Suzhou Dade Carbon Nanotechnology (China), and treated

with concentrated HCl before use. Other chemicals were analytical grade and used without further

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treatment.

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For preparation of Ni/C60 , an appropriate amount of Ni precursor was added into 3 g/L C60 of

ethanol solution. The mixture was sonicated for 30 min, stirred at 60 ℃ under N2 atmosphere for
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12 h, and then evaporated. The results were dried at 80 ℃. The loading of Ni was 30 wt%

otherwise specified. The obtained catalysts were denoted as Ni/C60 -x, in which x was Ni precursor
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and represent Ac, NI or Cl shorted for Ni(OAc) 2 , Ni(NO3 )2 and NiCl2 , respectively. Ni/C60 -x was

reduced before use by N2 H4 ·H2 O or NaBH4 . Generally, 0.1 g precursor, 12 mL 12.5 mol/L NaOH

and 2.0 mL 80% N2 H4 ·H2 O was mixed in 20 mL ethanol and heated to 80 ℃ under N2
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atmosphere for 12 h. The resulting mixture was centrifuged and washed with water until the pH of

the supernatant was about 7, and kept in ethanol. Or, a certain amount NaBH4 was added to
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ethanol solution containing precursor of Ni/C60 at 0 ℃, and stirred. The mixture was centrifuged
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and washed with ethanol and soaked in ethanol. The obtained catalysts with the molar ratio of B to
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Ni of 2:1, 4:1, 6:1 and 8:1 were denoted as Ni/C60 -x-B-2, Ni/C60 -x-B-4, Ni/C60 -x-B-6 and
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Ni/C60 -x-B-8, respectively. Ni-B-4 was prepared employing Ni(OAc) 2 according to the same

procedure without the addition of C60 .

2.2. Catalyst characterization

Powder X-ray diffraction (XRD) pattern was conducted on Philip X’Pert PRO MPD

diffractometer. The X-ray photoelectron spectroscopy (XPS) measurements were obtained on a

XSAM 800 apparatus with an Al Ka=1.486.6 eV exciting source (12 kV, 12 mA). The TEM was

done on a JEM-2100F transmission electron microscope. The SEM of samples was detected using

a field emission scanning electron microscope (JSM-6700F). The Ni content was determined by
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inductively coupled plasma-atomic emission spectrometry (ICP-AES) using an IRIS 1000

instrument (Thermo Electron, USA).

2.3. Hydrogenation of nitrobenzene

The catalytic hydrogenations were carried out in a 100 mL stainless steel reactor equipped

with a magnetic stirred. Typically, 2.0 g nitrobenzene, 8 mL ethanol and an appropriate amount of

catalyst were charged into the reactor. The reactor was flushed three times with 2 MPa N 2 and 2

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MPa H2 successively, and introduced the desired pressure of H2 afterwards. Then, it was heated to

the desired temperature in an oil bath and stirred vigorously for a certain time. After reaction, the

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reactor was cooled to room temperature and then slowly depressurized. The resulting products

were centrifuged to separate the catalyst washed by ethanol, and then were analyzed by gas

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chromatography (Agilent Technologies 7820A) using toluene as internal standard. The amount of

catalyst employed was express by the amount of catalyst precursor.

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3. Results and discussion

3.1 Characterization
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The XRD patterns of Ni/C60 -Ac with different reductants and varied molar ratio of B to Ni

were shown in Fig. 1. It could be seen that only diffraction peaks of C60 for Ni/C60 -Ac reduced by
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NaBH4 were appeared, indicating the high dispersion of metallic Ni. In contrast, the peaks

assigned to Ni(OH) 2 and metallic Ni were presented in the XRD patterns of Ni/C60 -Ac reduced by
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N2 H4 ·H2 O, meaning metallic Ni particle size was much larger than that of Ni/C60 -Ac reduced by
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NaBH4 . While, a broad diffraction peak attributed to metallic Ni appeared after Ni/C60 -Ac-B-4

used, implying Ni particle size became larger during hydrogenation of nitrobenzene.

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The XRD patterns of Ni/C60 with different nickel precursors and Ni/C60 -Ac-B-4 with varied
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Ni contents were shown in Fig. A.1. No peaks assigned to metallic Ni were appeared in the XRD

patterns of all samples, suggesting that metallic Ni were highly dispersed in Ni/C60 reduced by

NaBH4 . Fig. A.2 displayed the XRD patterns of fresh Raney Ni and used Raney Ni. It was

observed that the phase of Al0.9 Ni4.22 partially transformed into Ni2 Al3 in used Raney Ni.

The XPS spectra of Ni2p of Ni/C60 -Ac-B-4 was shown in Fig. 2. The XPS spectra of Ni2p of

other Ni/C60 catalysts prepared were displayed in Fig. A.3. In addition, the XPS spectra of B1s of

the samples were shown in Fig. A.4. The binding energy (BE) of 853.0±0.2 ev and the BE of

188.6±0.2 ev were assigned to Ni 2p3/2 of a metallic nickel and B 1s of elementary boron,

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respectively. Metallic Ni and oxidized Ni existed for all samples except for Ni/C60 -Ac-B-2. The

content of metallic Ni and B specie on the surface of catalysts calculated were displayed in Table 1.

It could be seen that the metallic Ni content of Ni/C60 -Ac-B first increased and then decreased

with increased molar ratio of B to Ni. The metallic Ni content reached highest on Ni/C60 -Ac-B-4

with B undetectable. Furthermore, the oxidized B content (about 191.0 ev) increased with molar

ratio of B to Ni increasing from 6:1 to 8:1. The XPS results illustrated that the NaBH4 amount viz.

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the molar ratio of B to Ni influenced the metallic Ni concentration, the B content, and excess

NaBH4 was oxidized easily to oxidized boron which cover metallic Ni leading to decreased

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metallic Ni content. It could be observed that the metallic Ni content for Ni/C60 -N-B-4,

Ni/C60 -Cl-B-4 and Ni-B-4 were much lower than that for Ni/C60 -Ac-B-4, indicating that the nickel

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precursors influenced the metallic Ni content on the surface of catalyst and C60 could promote the

dispersion of nickel resulting in high metallic Ni content. The metallic Ni content of 10.0%
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Ni/C60 -Ac-B-4 was lower than that of Ni/C60 -Ac-B-4 due to low Ni loading. In comparison with

the BE of Ni 2p3/2 of Ni-B-4, the BE of metallic Ni present in the Ni/C60 -Ac-B-4 positively shifted
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by 0.3 eV, which implied that partial electron transferred from metallic Ni to C60 , making Ni

electron-deficient. Moreover, the metallic Ni content of Ni/C60 -Ac-B-4 increased from 2.21% to
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7.17% after seven times use resulting from the enrichment of metallic Ni on the surface, which

was consistent with the results of XRD. The metallic Ni content of Raney Ni after reused was
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0.89%, and the oxidized Ni content was 3.23%, indicating metallic Ni of Raney Ni was oxidized
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during the hydrogenation reaction.

The SEM images and TEM images of samples were displayed in Fig. A.5 and Fig. A.6,
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respectively. It could be observed that C60 was cluster which was irregular assemblies. From the
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SEM images, it was found that the spherical particle size of Ni-B-4 with an average size of ca. 330

nm was much larger than that of Ni/C60 -Ac-B4 of ca. 64 nm, indicating C60 promoted the

dispersion of nickel species. Compared with the Ni/C60 -Ac-B4, the particles of used Ni/C60 -Ac-B4

became larger due to the agglomeration, which was in good accord with the XRD data in Fig. 1. In

Fig. A.6, it could be seen that Ni/C60 -Ac-B4 was spherical particle of an average particle size of 13

nm with the average Ni particle size of 6 nm. The difference of particle sizes between TEM

images and SEM images was ascribed to the treatment of samples.

3.2 Effect of Ni content on catalytic performance of Ni/C60 -Ac-B-4

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The catalytic activities of Ni/C60 -Ac-B-4 with varied Ni content were displayed in Table 2.

The nitrobenzene conversion and the aniline selectivity increased remarkably from 79.6% to

above 99.9% and from 65.2% to above 99.9%, respectively, with Ni content increasing from 1.0

wt % to 30.0 wt %. The low nitrobenzene conversion at low Ni content was ascribed to the less

amount of metallic Ni. It observed that the nitrobenzene conversion was 98.1% over Ni-B-4 with

83.4% of aniline selectivity, which indicated that C60 in 30 wt% Ni/C60 -Ac-B-4 significantly

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increased the aniline selectivity originating from the high metallic Ni content, high dispersion of

Ni and the interaction between C60 and metallic Ni making Ni electron-deficient. The nitrobenzene

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conversion and the aniline selectivity were 98.6% and 99.4%, respectively, over 30.0wt%

Ni/C60 -Ac using N2 H4 ·H2 O as reductant, and lower than those using NaBH4 as reductant due to

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the bigger metallic Ni particles. The byproducts were nitrosobenzene and azoxybenzene.

3.3 Effect of nickel precursor on the catalytic activities of Ni/C60 -x-B-4

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Table A.1 revealed the effect of nickel precursor on the catalytic performances of

Ni/C60 -x-B-4. It clearly suggested that Ni/C60 prepared using Ni(CH3 COO)2 exhibited the best
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catalytic activity. The nitrobenzene conversion and the aniline selectivity both reached above 99.9%

within 10 min at 110 ℃ over Ni/C60 -Ac-B-4. The excellent catalytic performance of
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Ni/C60 -Ac-B-4 was due to the high metallic Ni content. The aniline selectivity over Ni/C60 -Cl-B-4

was lowest, ascribed to the highest oxidized boron concentration favoring the formation of
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byproducts or inhibiting the formation of aniline.

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The effect of temperature and H2 pressure on hydrogenation of nitrobenzene over

Ni/C60 -Ac-B-4 was shown in Table A.2. The nitrobenzene conversion of 98.9% and the aniline
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selectivity of above 99.9% were reached within 60 min at 80 ℃ and 1 MPa of H2 , which was
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better than those with other supported nickel catalysts [29, 30]. Moreover, the nitrobenzene

conversion and the aniline selectivity both reached above 99.9% within 40 min under 90℃ and 2

MPa of H2 . The nitrobenzene consumption rates for Ni-based catalysts reported were displayed in

Table 3. It suggested that Ni/C60 -Ac-B-4 had higher nitrobenzene consumption rates even under

mild conditions than that for other Ni-based catalysts reported.

3.4 Effect of the NaBH4 amount on catalytic activity of Ni/C60 -Ac-B

The effect of the NaBH4 amount on activity of Ni/C60 -Ac-B was shown in Table 4. The

nitrobenzene conversion and the aniline selectivity over Ni/C60 -Ac-B first increased and then
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decreased with increased molar ratio of B to Ni. The nitrobenzene conversion and the aniline

selectivity both reached above 99.9% over Ni/C60 -Ac-B-4. So the optimal molar ratio of B to Ni

was 4:1.

Combining with Table 1, the above results illustrated that the catalytic activity of

Ni/C60 -Ac-B increased with increasing metallic Ni concentration on the surface of catalyst,

implying the surface metallic Ni content significantly affected the catalytic activity of catalyst.

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Furthermore, it could be speculated that excess oxidized boron on the surface of the catalyst might

inhibit hydrogenation of nitrobenzene to aniline and favor the formation of byproducts.

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3.5 Reusability of Ni/C60 -Ac-B-4

The effect of Ni/C60 -Ac-B-4 amount on hydrogenation of nitrobenzene was shown in Table

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A.3. The optimum amount was 0.1 g with the nitrobenzene conversion and the aniline selectivity

both above 99.9%.

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The reusability of Ni/C60 -Ac-B-4 was performed and the results were displayed in Fig. 3. The

nitrobenzene conversion kept above 99.0% and the aniline selectiv ity remained above 94.0% over
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Ni/C60 -Ac-B-4 after seven times, which was more stable than that of other Ni-based catalyst and

Raney Ni (Table A.4) [30, 33]. Table A.5 showed the cycling test with moderated nitrobenzene
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conversion, suggesting that the nitrobenzene conversion and the aniline selectivity slightly

reduced after seven times, illustrating the outstanding stability of Ni/C60 -Ac-B-4. The better
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stability of Ni/C60 -Ac-B-4 might partial because of the high dispersion of metallic Ni by C60 , the
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attracting electron effect of C60 and the hydrophobicity of C60 preventing metallic Ni from

deactivation due to reaction of metallic Ni with water produced to oxidized Ni during

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hydrogenation [34]. The reduced aniline selectivity was ascribed to the agglomeration of Ni
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particles and the decreased activity of Raney Ni might be ascribed to the phase transformation and

the oxidation of Ni.

4. Conclusions
The C60 -stabilized Ni catalyst was an excellent catalyst with high catalytic performance under

mild conditions and outstanding stability. The reductants, NaBH4 amount and nickel precursor

affected the surface concentration and particle size of metallic Ni of Ni/C60 which directly

determined the catalytic activity of Ni-based catalyst. The nitrobenzene conversion and the aniline

selectivity over Ni/C60 -Ac-B-4 both reached above 99.9% within 40 min at 90 ℃ and 2 MPa of
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H2 with higher nitrobenzene consumption rate of 30.0 g NB/(g cat•h) than that with other

Ni-based catalysts reported. The nitrobenzene conversion kept above 99.0% and the aniline

selectivity remained above 94.0% after seven times use. C60, as a promoter, improved the

dispersion of metallic Ni and reduced electron density of metallic Ni leading to excellent aniline

selectivity, and prevented metallic Ni from reacting with water leading to enhanced stability.

Acknowledgements

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Financial support for this work from the National High Technology Research and

Development Program of China (863 program, No. 2013AA031703), the Science and Technology

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Support Program of Sichuan Province (No. 2013GZX0135) and the Science and Technology

Innovation Program for Youth Team of Sichuan Province (No. 2013TD0010) are greatly

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acknowledged.

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Fig.1 XRD patterns of (a) Ni/C60 -Ac-B-8, (b) Ni/C60 -Ac-B-4 used, (c) Ni/C60 -Ac-B-4 and (d)

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Ni/C60 -Ac reduced by N2 H4 ·H2 O

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Fig. 2 XPS spectra of Ni2p of Ni/C60 -Ac-B-4

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Fig 3. The reusability of Ni/C60 -Ac-B-4

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reaction conditions: 90 ℃, 2.0 MPa H2 , catalyst 0.1 g, nitrobenzene 2.0 g, ethanol 8.0 g, 40 min

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Table 1 Molar content of Ni and B on the surface of Ni/C60 -B calculated according to the

XPS spectra

catalysts Metallic Ni % Elementary B % Total B %

Ni/C60 -Ac-B-2 0 0 0

Ni/C60 -Ac-B-4 2.21 0 0

Ni/C60 -Ac-B-6 0.23 0.23 1.14

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Ni/C60 -Ac-B-8 0.06 0 1.83

used Ni/C60 -Ac-B-4 7.17 0 0

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Ni/C60 -N-B-4 0.17 0 0.91

Ni/C60 -Cl-B-4 0.23 0 1.94

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Ni-B-4 1.63 NU 0 0

10.0% Ni/C60 -Ac-B-4 0.11 0 0.62

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Table 2 Effect of Ni content on catalytic performance of Ni/C60 -Ac-B-4

a b
wt Ni % wt Ni % Xnitrobenzene% Yaniline% Saniline%

1.0 0.8 79.6 51.9 65.2

10.0 8.1 99.3 86.9 87.5

30.0 24.3 ＞99.9 ＞99.9 ＞99.9

*
30.0 24.3 98.6 97.9 99.4

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reaction conditions: 110 ℃, 2.0 MPa H2 , catalyst 0.1 g, nitrobenzene 2.0 g, ethanol 8.0 g, 5 h
a
theoretical loading of Ni

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Ni loading determined by ICP

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* N2 H4 ·H2 O as reductant
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Table 3 Nitrobenzene consumption rate for Ni-based catalysts reported

nitrobenzene
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Catalyst Xnitrobenzene% Saniline% consumption rates Ref.
(℃) (MPa)
(g NB/(g cat·h))

30.0 wt % 80 1 98.9 ＞99.9 19.8

This work
Ni/C60 -Ac-B-4 90 2 ＞99.9 ＞99.9 30.0

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Co-Ni 120 3 ～90 ～100 6 [31]

Ni-53-EN 110 2 100 96.8 6 [30]

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NiO/MWCNTs 140 1.2 100 100 2.5 [32]

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Ni-B-SiO2 100 1.8 99.9 99.8 5.0 [33]
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Table 4 Influence of the NaBH4 amount on activities of Ni/C60 -Ac-B

catalyst Xnitrobenzene% Yaniline% Saniline%

Ni/C60 -Ac-B-2 27.0 27.0 ＞99.9

Ni/C60 -Ac-B-4 ＞99.9 ＞99.9 ＞99.9

Ni/C60 -Ac-B-6 98.4 96.1 97.7

Ni/C60 -Ac-B-8 66.4 43.6 65.7

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reaction conditions: 90 ℃，2.0 MPa H2 , catalyst 0.1 g, nitrobenzene 2.0 g, ethanol 8.0 g, 40 min

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Graphical abstract
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Highlights

 C60 improved the metallic Ni content on the surface of catalyst.

 C60 reduce electron density of metallic Ni.

 C60 improved the aniline selectivity and enhanced the stability of Ni/C60 .

 The nitrobenzene consumption rate of 30.0 g NB/(g cat•h) over Ni/C60 -Ac-B-4 was

higher.

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The NaBH4 amount significantly affected the catalytic performance of Ni/C60 .

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