Catalysis Letters

https://doi.org/10.1007/s10562-018-2351-2

Solvent-Controlled Reactivity of Au/CeO2 Towards Hydrogenation of p-

Chloronitrobenzene
Zhun Hu1   · Shunquan Tan1 · Rongli Mi1 · Xiang Li1 · Dan Li1 · Bolun Yang1

Received: 4 September 2017 / Accepted: 23 February 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
The solvent effect on catalyst activity and selectivity for the hydrogenation of para-Chloronitrobenzene (p-CNB) over Au/
CeO2 catalyst was investigated. Reaction over Au/CeO2 generated p-chloroaniline as the sole product, whereas the p-CNB
hydrogenation rate extremely hinged on solvent via modification of apparent activation energy (­ Ea) and pre-exponential
factor (A). The apparent activation energy and the pre-exponential factor in different solvents followed the order: etha-
nol > i-butanol > s-butanol > t-butanol > t-pentanol, which linearly correlated with the hydrogen bond donation ability of
solvents. Moreover, the constable plot was firstly found in the solvent effect on supported gold catalyst. From the ATR-FTIR
analysis, N–O bond in p-CNB was strongly affected by the solvents via hydrogen bond compared with the benzene ring
and C–Cl bond, thereby weaken the adsorption of the p-CNB on Au catalyst, inducing the increment of activity of p-CNB
hydrogenation. These findings could provide a criterion to compare the performance of various catalysts in different solvents
and a guideline to designate an appropriate solvent.
Graphical Abstract

ROH HBD Ea (kJ/mol) 100 (F)

Apprant activation energy (kJ/mol)

ethanol 86 94.6 80

60
i-butanol 79 91.7
40
s-butanol 69 73.7
Au 20
t-butanol 42 52.8
0
CeO2 t-pentanol 28 24.9
0 20 40 60 80
Hydrogen bond donation
100

Keywords  Solvent effect · Hydrogenation reaction · Para-chloronitrobenzene · Au catalyst · Constable plot

Electronic supplementary material  The online version of this

1 Introduction
article (https​://doi.org/10.1007/s1056​2-018-2351-2) contains
supplementary material, which is available to authorized users. The multitude of applications of halogenated anilines, which
are extensively used as an intermediate in the synthesis a
* Zhun Hu
diversity of fine chemicals, e.g., pharmaceuticals, dyes, pig-
huzhun@mail.xjtu.edu.cn
ments, herbicides and agrochemicals, results in a growing
* Bolun Yang
interest in the process of their manufacture. The most com-
blunyang@mail.xjtu.edu.cn
mon method for the synthesis of halogenated anilines is a
1
Institute of Industrial Catalysis, School of Chemical selective reduction of halogenated nitroaromatic compounds,
Engineering and Technology, Xi’an Jiaotong University, which could be reduced by chemical, electrochemical and
Xi’an 710049, Shaanxi, China

13
Vol.:(0123456789)

catalytic methods. Among all these methods, the selective
catalytic reduction over heterogeneous catalysts is regarded
as the most effective method, due to feasible separation and
purification of final haloaniline [1].
The most frequently used catalysts for the selective cata-
lytic hydrogenation of halogenated nitroaromatic with H ­ 2 are
supported noble metal catalysts, e.g. Pt [2], Pd [3], Rh [4]
catalysts, etc. The problem with the occurrence of dechlo-
rination could be still existed, although many efforts have
been made to modify the selectivity via either tailoring the
particle size of metal nanoparticles/the support or addition
of organic or inorganic modifiers. High selectivity in the
catalytic conversion of substituted nitroarenes to the target
amine remains challenging, especially at high conversions.
Recently the greatest breakthrough in the area of hydrogena-
tion of haloaromatic nitro compounds was the discovery of
remarkable high chemoselective hydrogenation of gold cata-
lyst [5–10]. Supported gold catalysts appeared to be capable
of hydrogenation of nitro group in functionalized nitroben-
zenes with 100% selectivity at the complete conversion.
With respect to the hydrogenation of p-chloronitrobenzene
(p-CNB) to p-chaloroaniline (p-CAN) over gold catalysts,
current researchers primarily focus on the metal size [11,
12], addition of other precious metal as promoter [13–15],
metal-support interaction [16], type of support [17–19] etc,
but give little attention to the effects of solvents on the reac-
tion. The solvents in the liquid-phase heterogeneous catalysis
reaction not only provide reaction environment to dissolve
solid reactants and transform heat during catalytic process,
but also influence the catalyst activity and selectivity. The
careful selection of an appropriate solvent for a liquid-phase
heterogeneous reaction is vital for chemists to begin their
chemical reaction. Some investigations have been reported
about the solvent effect on hydrogenation reaction over other
metal catalysts. Cheng et al. [20] studied the effect of water
on the hydrogenation of o-CNB over Pd/C and Pt/C catalysts
in ethanol, n-heptane and compressed carbon dioxide. They
found that o-chloronitrobenzene (o-CNB) hydrogenation rate
decreased in ethanol, but increased in n-heptane and com-
pressed carbon dioxide with the addition of water. Hence they
drew a conclusion that the role of water was not only to acti-
vate the functional group of ­NO2 through the interactions via
a hydrogen bonding, but also to affect the solubility of hydro-
gen in ethanol and n-heptane. The o-CNB hydrogenation rate
hinged on the positive effect of water-reactants interaction and
negative effect of hydrogen solubility. Ren et al. [21] studied
catalytic hydrogenation of 2,4-DNEB to 2,4-DAEB over Ni/
HY catalysts in various solvents. They found that the reac-
tion exhibited the best activity in protic solvents, which was
ascribed to the stronger hydrogen-bond interaction between the
protic solvents with the reactant, intermediates and product,
which facilitates the desorption of intermediates and products
from the catalysts and helps to polarize the N=O bonds of the
13
Z. Hu et al.
reactant and intermediates adsorbed on the catalysts. Bertero
et al. [22] investigated the solvent effect on catalytic activ-
ity and selectivity for the hydrogenation of acetophenone to
1-phenylethanol. A reasonable correlation between the catalyst
activity and some solvatochromic parameters was found only
when solvents with similar nature were compared. The high
activity in protic solvents was ascribed to extra active hydrogen
via dissociative absorption of solvent on metal nickel surface.
However, the past studies focusing on the p-CNB hydro-
genation over Au catalyst usually disregarded the solvent
effect, inducing the difficulty to compare other factors accu-
rately. In heterogeneous catalysis system, the solvent effects
on catalyst performance usually focused on the general
classic parameters of solvent (polarity, dielectric constant,
etc) or extra active hydrogen resource. On the contrary, in
homogenous catalysis system, the solvent was usually in
view of a molecular-microscopic level on the hydrogena-
tion reaction, which could provide more specific knowledge
to understand the solvent effects on the catalyst performance.
Hydrogen bond donation ability was known to have a sig-
nificant effect on the homogeneous hydrogenation reaction,
which could affect catalyst activity and selectivity with elec-
tron transfer though solute/solvent or solvent/intermediate
interactions. However, less attention was paid to this effect
in the heterogeneous catalysis. In order to understand the
effect of hydrogen bond donation of diversity solvents on
the p-CNB hydrogenation reaction, some specific solvents
were chosen with varied hydrogen bond donation (HBD)
ability and similar other nature (hydrogen bond acceptance,
polarity/polarizablilty, polarity) [23, 24].
In this paper, liquid-phase hydrogenation of p-CNB
over Au/CeO2 with varied solvents was investigated sol-
vent effect from the perspective of hydrogen bond donation
ability. The solvents were chosen at varied hydrogen bond
donation (HBD, α) ability with similar other solvent nature,
i.e. ethanol, i-butanol, s-butanol, t-butanol, t-pentanol. The
results demonstrated that apparent activation energy and pre-
exponential factor of p-CNB reaction over Au/CeO2 catalyst
was linear relationship with hydrogen bond donation ability.
From a specific term analysis, the solvent influence on the
catalytic activity was comprehensive proposed on the basis
of the solvent properties. The reactant-solvent interaction
was studied through analyzing the p-CNB in various sol-
vents by ATR-FTIR.
2 Experimental
2.1 Reagents
Ethanol and ­C eO 2 were purchased from Tianjin Fuyu
Huagong Co., Ltd (China). i-butanol, s-butanol, t-butanol,
t-pentanol were from Tianjin Kermel Chemical Reagent
Solvent-Controlled Reactivity of Au/CeO2 Towards Hydrogenation of p-Chloronitrobenzene

(China). ­HAuCl4 was from Alfa Aesar. p-CNB was from the H2 consumption in the hydrogenation of p-CNB
H2 conversion =
Macklin Reagent Company. the initial molar quantity of H2

2.2 Catalyst Preparation
3 Results and Discussion
Au/CeO2 catalyst was prepared using H ­ AuCl4 as the gold
precursor by deposition–precipitation with urea onto the
3.1 Parameter of Varied Solvents
­CeO2, as previously reported [6]. The precipitate was iso-
lated and washed thoroughly with deionize water with
The solvents used in this work for the p-CNB hydrogena-
several times until it was free from chloride ion. Then the
tion have been classified (Table 1), according to the values
resultant sample was dried at 110 °C for 12 h and calcined
of hydrogen bond donation capability (HBD, α), hydrogen
at 400 °C for 5 h in flowing air (100 mL/min). The Au load-
bond acceptance capability (HBA, β), polarity/polarizability
ing was determined to be ca. 1.0 wt%, by X-Ray fluores-
π*, ­ET(30) representing polarity parameter. The values of
cence spectrometer (XRF) analysis. The structure of catalyst
various parameters were obtained from the reference [23].
(XRD and TEM in Figure S2) was provided in supporting
All of the solvents have a good solubility to p-CNB and
information.
o-xylene (internal standard). It should be noted that the sol-
vents were chosen based on the varied α with similar β, π*
2.3 Characterization
and ­ET(30).
Attenuated total reflection Fourier transformed infrared
3.2 Catalyst Activity
spectroscopy (ATR-FTIR) was conducted in a Nicolet iS50
FTIR spectrometer (Thermo Fisher Scientific Inc., Madison,
Hydrogenation of p-CNB over Au/CeO2 catalyst (60–80
USA). Spectra were recorded from 4000 to 525 cm− 1, with
mesh, Table  S1) was conducted at vigorously string at
a resolution of about 0.2 cm− 1 and 32 scans. In addition,
900 rpm to eliminate diffusion limitation and the conver-
p-CNB in various solvents spectra were obtained after the
sions under all the conditions were controlled lower than
corresponding solvents as the background spectra. In order
25%. Table 2 shows catalytic results of the selective hydro-
to obtain the accurate data, each spectruma was repeated
genation of p-CNB over Au/CeO2 catalyst at 150 °C for 1 h.
six times.
The TOF (shown in Table 2) for the overall p-CNB conver-
sion against the degree of Au dispersion, which is here esti-
2.4 Hydrogenation Reaction
mated by an approximate conversion as the dispersion = 0.9/
diameter (in nm). The TOF of Au catalyst was similar with
Hydrogenation of p-CNB was carried out in the liquid phase,
the previously reported [16]. In all the investigated sol-
at 1–5 MPa pressure and 383–453 K, using a 25 mL stain-
vents, Au/CeO2 exhibited 100% selective hydrogenation of
less steel autoclave equipped with a magnetic stirrer. The
p-CNB to p-CAN with no undesirable dechlorination prod-
solvents used were: ethanol, i-butanol, s-butanol, t-butanol,
ucts, which was coincided with previous report [6]. When
t-pentanol. Typically, 1 mmol p-CNB in 5.0 mL solvent
using ethanol as solvent, p-CNB conversion over Au/CeO2
and 25.0 mg of catalyst were first charged into the auto-
was 22.9%. While, replacement the solvents from ethanol to
clave reactor; the overall molar p-CNB/Au ratio was 800.
i-butanol, s-butanol, t-butanol and t-pentanol, p-CNB con-
The reactor was sealed, flushed six times with 5 MPa H ­ 2
version decreased from 22.9 to 19.0, 15.6, 9.1 and 3.5%,
to exclude air before it was pressurized to the desired ­H2
respectively. It should be noted the mass specific activity
pressure, and then placed in a furnace at the desired reac-
was linear correlation with hydrogen bond donation, which
tion temperature. The temperature was electronically con-
trolled by K-type thermocouple at outer reactor wall. In
order to ensure the reaction liquid to reach the desired tem-
perature, the system was stirred vigorously (900 rpm) after Table 1  The property parameters of organic solvents HBD ability α,
the temperature equilibrated at the set point (c.a. 5 min). HBA ability β, polarity/polarizability π*, polarity E
­ T(30) [23]
After the reaction, the reactor was cooled down in an ice- Solvent α β π* ET(30)
water bath. The reaction products were filtrated through a
Ethanol 86 75 54 51.9
0.45 µm syringe filter to obtain a clear solution. The sam-
i-Butanol 79 84 40 48.6
ples were analyzed by GC with a KB-5 capillary column
s-Butanol 69 80 40 48.6
(30 m × 0.32 mm × 0.25 µm) and an FID as detector, using
t-Butanol 42 93 41 43.7
o-xylene as an internal standard.
t-Pentanol 28 93 40 41.1
The ­H2 conversion was calculated as follows:

13
 Z. Hu et al.

Table 2  Catalytic results of the Solvent Conv. (%) Product sel. (%) TOF ­(h−1) MSA
selective hydrogenation of p- (mmol h− 1 gAu−1)
CNB over Au/CeO2 catalyst p-CAN AN NB

Ethanol 22.9 100 0 0 542 917.42

i-Butanol 19.0 100 0 0 448 758.26
s-Butanol 15.6 100 0 0 368 662.38
t-Butanol 9.1 100 0 0 216 365.69
t-Pentanol 3.5 100 0 0 85 143.32

Reaction conditions: 25.0  mg catalyst, 1.0  mmol p-CNB, 1  mmol o-xylene in 5  mL solvent, 150  °C,
2.0 MPa ­H2, 1 h, stirring speed: 900 rpm

1000 to correlate the reaction in the hydrogenation reaction. Then

R² = 0.99 the systematic investigation on the solvents was then needed
to standardized understanding on the intrinsic activity of Au
800
catalyst, including the kinetic parameters (apparent activa-
tion energy and pre-exponential factor).
MSA (mmol/h/g-Au)

600 In order to recognize the solvent effects on the catalyst

activity, various solvent parameters were selected to analyze
the solvent interactions with the reactants in the heteroge-
400 neous system, i.e. ­H2-solvent, CNB-solvent interactions.
Meanwhile solvent parameters will be analyzed separately,
200 explaining its key term on the catalytic activity.

3.3 Catalyst Activity and ­H2 Solubility

0
20 40 60 80
Hydrogen bond donation
Fig. 1  Relationship between mass specific activity over Au catalyst
and hydrogen bond donation of solvents
was first reported (as shown in Fig. 1) in the hydrogenation
reaction over Au catalysts in heterogeneous catalysis.
In previous reports, Au catalyst was considered as a
superior selective hydrogenation p-CNB to p-CAN, more
attention was paid to the influencing factors of activity
enhancement. The addition of other precious metal (e.g.
Pt, Pd) to Au catalyst was aimed to enhance the activated
ability to hydrogen, thereby improving the activity of Au
catalysts [13–15]. Other strategies were concentrated on
studying the electronic state or synergistic effect on the Au
catalyst through changing the Au particle size, the supports
and promoters. However, the intercomparison on the various
researchers was difficult due to different organic solvents
such as alcohols, acetone, benzene, ethyl acetate. The sol-
vent nature affecting the catalyst activity and selectivity were
reported in other reactions [20, 21, 25–27]. In general, the
classical solvent polarity parameters (i.e., dipolar moment or
dielectric constant) were correlated with the reaction rates.
Most of these studies were qualitative analysis and lack of
quantitative understand. However, in homogenous catalysis,
hydrogen bond donation was often used as a key parameter
100
It has been reported that alcohols could be as an extra active
hydrogen source on the hydrogenation reaction via hydro-
gen transfer reaction [22]. In order to verify this hypothesis,
experiments of catalytic hydrogenation of p-CNB were car-
ried out with the same conditions except under ­N2 replace-
ment of ­H2. The results showed that after 16  h, p-CNB
exhibited a negligible conversion in ethanol, indicating that
transfer hydrogenation reaction between alcohol and p-CNB
did not play a significant role in this reaction.
In some hydrogenation reactions, ­H2 solubility in differ-
ent solvents was the crucial factor on the catalytic activ-
ity in the liquid phase. For the sake of better understanding
­H2 solubility under varied solvents on the hydrogenation
reaction, we performed the experiments in ethanol at varied
hydrogen pressures (1.0–5.0 MPa). Ethanol was chosen as
the research object because of its maximum p-CNB hydro-
genation rate. Figure 2 shows p-CNB conversion over Au/
CeO2 catalyst with varied hydrogen pressures at 150 °C 1 h.
The p-CNB conversion remained invariable at all the hydro-
gen pressures, indicating ­H2 solubility and dissolution rate
were not rate-determining step of the hydrogenation reaction
under our investigated reaction conditions.
As previously reported, Hinkle et al. [28] investigated the
solubility of ­H2 in n-alcohols, and they found the solubility
of hydrogen ­H2 linearly increased with increment of carbon
number of n-alcohols. It is surprising that p-CNB hydrogen-
ation rate decreased with increment of H ­ 2 solubility when

13
Solvent-Controlled Reactivity of Au/CeO2 Towards Hydrogenation of p-Chloronitrobenzene
Fig. 2  p-CNB conversion over Au/CeO2 catalyst with varied hydro-
gen presures
increasing carbon number with n-alcohols in our investi-
gated conditions. The H ­ 2 solubility is smaller in ethanol than
that in pentanol, but hydrogenation rate in ethanol is five
times higher than that in pentanol. It should be noted that
­H2 solubility could not be distinguished among i-butanol,
s-butanol and t-butanol. However, the hydrogenation rate in
i-butanol was almost twice as that in t-butanol. These results
illustrated that no correlation could be established between
p-CNB hydrogenation rate and ­H2 solubility. The possible
explanation was that the hydrogen solubility and dissolution
rate, which was greatly exceeds the activation p-CNB hydro-
genation rate over Au catalysts. Even at 1 MPa as the lowest
hydrogen pressure in this work, hydrogen molar amount was
10 mmol, which is ten times as that of p-CNB. The p-CNB
conversion was 22%, the corresponding ­H2 conversion was
only 2.2% when ­H2 pressure is 1 MPa. Above all of these
reasons render that the p-CNB hydrogenation rate over Au/
CeO2 was less relationship with ­H2 pressure. Therefore, we
further investigated some other factors to be acquainted with
the crucial factor to affecting hydrogenation rate when using
different solvents, such as solvent-reactant interactions.
3.4 Solvent‑Reactant Interactions
For the purpose of understanding solvent-CNB interaction,
attenuated total reflection Fourier transformed infrared
spectroscopy (ATR-FTIR) was conducted to characterize
the vibration of the functional group in the p-CNB. All the
IR spectra were obtained at the condition of the correspond-
ing solvent as the background, which could minimise solvent
interference. Figure 3 shows the spectra of p-CNB in various
solvents within the corresponding solvent as background.
The regions from 1570 to 1590 cm− 1 and from 1595 to
1615 cm− 1 in Fig. 3a were attributed to the breathing vibra-
tion of aromatic ring in p-CNB. While the region from
1510 to 1540 cm− 1 was ascribed to antisymmetric stretch-
ing vibration of nitro-group in p-CNB. Figure 3b shows the
stretching vibration of C–Cl in p-CNB. It should be noted
that the peak at nitro-group (region from 1510 to 1540 cm− 1)
increased gradually from 1524 cm− 1 to 1527 cm− 1, when the
replacement solvent from ethanol to i-butanol, s-butanol,
t-butanol and t-pentanol. This red shift in the nitro-group
could be assigned to the interaction between solvent and
nitro-group. Moreover, the increment order of red shift was
in accordance with the hydrogen bond donation of solvent,
suggesting the interaction type in the formation of hydro-
gen bond. These hydrogen bonds could modify the reactant
adsorption energy over Au catalyst, thereby influencing the
hydrogen reaction rate.
3.5 Solvent Effect on the Kinetics Parameters
Since the various solvents have different influence on the
functional group of p-CNB, these promotions probably
modified the kinetics parameters on p-CNB hydrogenation
reaction. In order to obtain credible apparent activation
energies ­(Ea), the p-CNB conversions over Au/CeO2 were
equivalent at different reaction temperature via altering the
reaction time. Figure 4(a–e) show the arrhenius plot of reac-
tion rate versus temperature for p-CNB hydrogenation over
Au/CeO2 catalyst in ethanol(A), i-butanol(B), s-butanol(C),
t-butanol(D), t-butanol(E) at temperatures ranging from 383
to 423 K. The E ­ a (as shown in Table 3) decreased from 94.6
to 91.7, 73.7, 52.8 and 24.9 kJ/mol, when the solvent was
shifted from ethanol to i-butanol, s-butanol, t-butanol and
t-pentanol, respectively. It was surprising that the ­Ea as simi-
lar as MSA, was linear relationship with hydrogen donation
ability (as shown in Fig. 4F). As said above in Table 2, p-
CNB conversion on the ethanol used as solvent exhibited
more superior activity than other solvents. Nevertheless, the
highest estimates for E ­ a was obtained when using ethanol as
solvent. Ea and MSA in heterogeneous catalysis normally
exhibited contradictory orderliness, high MSA was routinely
coincided with low E ­ a. Since the reaction rate constant was
manipulated by the ­Ea and pre-exponential factor (A), more
details concerned with the pre-exponential factor were fur-
ther investigated. The pre-exponential factor was estimated
at the hypothesis of pseudo first-order reaction, as previous
reported [29].
Table 3 shows the pre-exponential factor (A) on the p-
CNB hydrogenation over Au/CeO2 catalyst in the varied
solvents. The A decreased from 9.28  h− 1 to 7.67, 6.26,
3.66 h− 1 and 1.42 h− 1, when the solvent was switched from
ethanol to i-butanol, s-butanol, t-butanol and t-pentanol,
respectively. The higher MSA witnessed in ethanol than in
13
 Z. Hu et al.

1527 A 742 B
0.005 0.005

e e

Absorbance (a.u.)
Absorbance (a.u.)

d d

c c

1524 b
b

a
a

1620 1580 1540 1500 770 750 730 710

Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 3  ATR-FTIR spectra of p-CNB in various solvents. a Ethanol, b i-butanol, c s-butanol, d t-butanol, e t-pentanol within the corresponding
solvent as background

other solvents might be then explained essentially by con-
sidering the higher in the pre-exponential. All these results
demonstrated that the solvent influence the catalytic activity
not only via the apparent activation energy ­(Ea), but also
the pre-exponential factor (A). Moreover, the ­Ea affected by
solvent was not constantly congruent with A on the impact
on the catalytic activity.
An acceptable linear relationship between ln(A) and E ­a
was obtained (Fig. 5), i.e., constable plot was observed in
this system [29]. The highest estimates for A and ­Ea were
obtained when using ethanol as solvent. In the realm of
kinetics, the reaction rate hinged on the activation energy
barrier and pre-exponential factor. It should be noted that the
largest reaction rate and the biggest activation energy barrier
were obtained in ethanol as solvent, since these two facets
were regarded as controversial. The pre-exponential factor
and activation energy barrier exhibit a linear relationship
lnA and E ­ a (Constable Plot), which was reported by Conner
[30]. As a consequence of increasing the activation energy
gives rise to an increasing entropy of transition. This incre-
ment of entropy could enhance the pre-exponential factor of
the reaction, inducing the increment of reaction rate. These
results were first to present the solvent effect through the
kinetic fundamental parameters (active energy and pre-expo-
nential factor), not only on the reaction rate. This constable
plot in various solvents motivated us to comprehensive to
predict the effect of solvent on p-CNB hydrogenation over
Au catalysts.
3.6 Origin of Solvent Effect
The reaction mechanism for the selective hydrogenation of
p-CNB over metal-based catalysts was considered as Lang-
muir–Hinshelwood mechanism [31]: hydrogen dissocia-
tive adsorption on the metal surface and generates active H
atoms, and p-CNB also adsorbed on the neighboring active
site, then H atom reacted with –NO2 or C–Cl group of the
adsorbed reactant molecule. The reaction pathways mainly
hinged on the adsorption forms of H ­ 2 and the organic reac-
tants on the metal surface, which are often affected by the
used solvent in the heterogeneous reaction system. As shown
in Fig. 3, the red shift of nitro group in p-CNB detected
by ATR-IR demonstrated electron-rich of nitro group in the
order of the ability of hydrogen bond donation in various
solvents. This electron-rich group would weaken the adsorp-
tion of p-CNB on Au catalyst via promoting the genera-
tion of feedback π bond between reactant and Au catalyst,
thus enhancing the reaction reactivity of hydrogenation of
p-CNB. Furthermore, the fascinating linear correlation was
probably result that they favored the polarization and activa-
tion of N=O bond of para-chloronitrosobenzene via hydro-
gen bond generation. These results were first to present the

13
Solvent-Controlled Reactivity of Au/CeO2 Towards Hydrogenation of p-Chloronitrobenzene

8 8
(A) Ethanol (B) i-Butanol
7 7

6 Ea = 94.6 kJ/mol Ea = 91.7 kJ/mol

6
ln (r)

ln (r)
5 5

4 4

3 3
2.3 2.4 2.5 2.6 2.3 2.4 2.5 2.6
1/T (10-3K-1) 1/T (10-3K-1)
8 8
(C) s-Butanol (D) t-Butanol
7 7

Ea = 73.7 kJ/mol Ea = 52.8 kJ/mol

6 6
ln (r)

ln (r)
5 5

4 4

3 3
2.3 2.4 2.5 2.6 2.3 2.4 2.5 2.6 2.7
1/T (10-3K-1) 1/T (10-3K-1)
8
Apprant activation energy (kJ/mol)

(E) t-Pentanol 100 (F)

7
80
6
60
ln (r)

Ea = 24.9 kJ/mol
5
40

4 20

3 0
2.3 2.4 2.5 2.6 2.7 0 20 40 60 80 100
1/T (10-3K-1) Hydrogen bond donation

Fig. 4  Arrhenius plot of reaction rate versus temperature for p-CNB 383 to 423  K. f Represents relationship between apparent active
hydrogenation over Au/CeO2 catalyst in ethanol(a), i-butanol(b), energy and hydrogen bond donation of solvents
s-butanol(c), t-butanol(d), t-butanol(e) at temperatures ranging from

solvent effect through the linear relationship between kinetic 4 Conclusions

fundamental parameters (reaction rate, active energy and
pre-exponential factor) and solvent’s hydrogen bond dona-
tion. These linear relationships in various solvents motivated
us to comprehensive to predict the effect of solvent on p-
CNB hydrogenation over Au catalysts.
The catalytic activity of p-CNB hydrogenation solvent was
rest on the solvent chemical nature, but the selectivity to
p-CAN did not impact in various solvents. The solvent
mainly modified the nitro group of p-CNB via hydrogen

13
 Z. Hu et al.

Table 3  The apparent activation energy ­(Ea) and pre-exponential fac- References

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1.0
0.5
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0 20 40 60 80
Ea (kJ/mol)
Fig. 5  Constable plot in the p-CNB hydrogenation over Au/CeO2 cat-
alysts with various solvents
bond as the evidence of red shift in ATR-IR spectra. More-
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Acknowledgements  We acknowledge the financial support from the
Fundamental Research Funds for the Central Universities (xjj2016113),
the China Postdoctoral Science Foundation (2017M613143), the Natu-
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and the National Natural Science Foundation of China (U1662117).
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