Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 2846−2856 pubs.acs.org/IECR

Acquiring Clean and Highly Dispersed Nickel Particles (ca. 2.8 nm)
by Growing Nickel-Based Nanosheets on Al2O3 as Efficient and
Stable Catalysts for Harvesting Cyclohexane Carboxylic Acid from
the Hydrogenation of Benzoic Acid
Weijie Lian,† Bo Chen,† Bingyu Xu, Song Zhang, Zhe Wan, Dan Zhao,* Ning Zhang,
and Chao Chen*
Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, College of Chemistry, Nanchang University, Nanchang,
Jiangxi 330031, China
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ABSTRACT: By growing nickel-based nanosheets on Al2O3, a

nickel catalyst present as clean uniform nickel particles ca. 2.8
nm in size was feasibly produced from the two-dimensional
(2D) nanoprecursor predispersing strategy, and investigated
for the hydrogenation of benzoic acid to cyclohexane
carboxylic acid. A 98% yield of cyclohexane carboxylic acid
and a 15−40-fold enhanced turnover frequency (TOF) value
(31.4 s−1) were achieved with the catalyst. These values were
superior to those achieved (yield = 28%−40%, time of flight
TOF = 0.8−2.0 s−1) for traditional catalysts with larger nickel
particles (ca. 5.2−6.8 nm); interestingly, the superior activity
was re-examined, because of the well-maintained size of the
catalyst after continuous catalytic recycling. The kinetic
measurements further illuminated that the reaction activation energy could be clearly decreased by employing smaller nickel
particles, which could be responsible for the dramatic TOF enhancements. These results also suggest that the hydrogenation
with a nickel-based catalyst could be a structure-sensitive catalytic process.

1. INTRODUCTION application.22,23 Ni−Zr−B and Ni−Zr−B/γ-Al2O3 could

Direct hydrogenation of the benzene ring in a benzoic
aromatic molecule was believed to be the most efficient way
to synthesize cyclohexane derivatives,1,2 which has attracted
considerable interest from both the pharmaceutical and
petrochemical industries, such as a safe drug intermediate
synthesis and diesel fuel production.3−6 In this field, the
synthesis of cyclohexane carboxylic acid (CCA) from the
hydrogenation of benzoic acid (BA) is significant, since CCA is
a vital organic intermediate for important pharmaceuticals,
such as praziquantel, caprolactam, and ansatrienin.7−9
However, the application of this promising synthesis was
suspended by the absence of proper hydrogenation catalysts
for the reaction.10,11
Some precious metal catalysts, such as Pd/C,12 Pd/CN,13,14
Pd/MCN,15 Ir/γ-Al2O3,16 Ru/MC,17 Rh/CN,18 Rh/TiO2,19 Pt
nanowire,20 and RuPd/CN21 have been widely studied for the
chemical transformation. However, the high cost of these
catalysts excludes their industrial potentials. As an alternative
route, recently, inexpensive metal catalysts, mostly focused on
nickel-based catalysts, have been studied because of the
considerable activity of nickel exhibited for the reaction.
Early on, Raney nickel was used for the reaction and showed
superior performance. However, the pyrophoric and environ-
mentally unfriendly nature of the catalyst limited its
show ∼100% selectivity for CCA at 93% BA conversion, but
the performance was not reproducible in the subsequent
reaction recycles, suggesting the poor stability of amorphous
nickel-based alloy catalysts for the reaction.24,25 To solve the
problem, some researchers were interested in controllable
synthesis of nickel crystalline catalysts from some new
preparation procedures. Bai et al.26 successfully prepared
highly dispersed nickel nanoparticles with an average size of ca.
2.8 nm on SiO2; this unconventional preparation was believed
to be responsible for the excellent activity and stability
observed for their catalysts. Xia et al.27 also produced active
and stable Ni/CSC catalysts from microwave treatment
procedures for the hydrogenation of BA to CCA. However,
relatively harsher reaction conditions were required, because of
the larger (ca. 9.4 nm) nickel particles employed in the work of
these researchers. These reports suggested that supported
nickel particles could be a competitive candidate catalyst for
the efficient hydrogenation of benzoic acid, especially when the
size of the nickel particles is well-controlled.
Received: December 5, 2018
Revised: February 2, 2019
Accepted: February 7, 2019
Published: February 7, 2019

© 2019 American Chemical Society 2846 DOI: 10.1021/acs.iecr.8b06037

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Industrial & Engineering Chemistry Research
The conventional methods to prepare supported metal
catalysts, such as incipient-wetness impregnation or deposi-
tion−precipitation,28,29 were not efficient to manipulate the
size of the supported particles. The steps involved in these
preparations, such as assembling the metal precursors and the
combination of metal precursors with supports, were largerly
unordered or uncontrollable processes, leading to the
difficulties in obtaining small uniform particles. Prereduction
of metal precursors with the assistance of surfactants (as
protection to prevent the excessive aggregation of metal atoms
present from reduction) before access of the support became a
mainstream technique for the controllable synthesis of metal
particle catalysts.30−32 Although the strategy was highly
efficient to synthesize highly dispersed small metal nano-
particles, the surfactant protector adhered to the surface of
small metal particles, which, in turn, would create difficulties in
the subsequent process of loading metal particles onto the
support. This adhesion could also prevent the access of
reactants to the metal surface, leading to the confined metal
loading or depressed catalytic efficiency of the catalysts.33,34
We noticed that two-dimensional (2D) nanomaterials were
more feasible and exhibited unique features for modulating
structural characteristics and electronic properties, and these
materials have been regarded as effcient catalyst precursors,
such LDH and LMH nanosheets.35−38 Considering that 2D
nanomaterials could be more able to control the exposed active
sites than conventional preparation systems, in this work, a
new preparation of supported nickel nanoparticles was
designed by predispersing nickel precursors as 2D nanosheets
grown on Al2O3 for the catalytic hydrogenation of BA to CCA.
The main interesting feature of the 2D nanoprecursor
predispersing control was that the clean, highly dispersed
nickel particles with a typical size of ca. 2.8 nm could be
feasibly obtained. These materials even endured a severe
thermal-reduction treatment under surfactant-free conditions,
subsequently leading to the attractive catalytic activity and
stability upon the more prominent interaction between the
size-controlled small nickel particles and Al2O3 support, in
comparison with samples prepared by traditional methods.
These findings could provide an attractive reference to
synthesize efficient metal catalysts for catalytic hydrogenation
applications.
2. EXPERIMENTAL SECTION
2.1. Materials. All reagents of analytical purity, including
dodecane (Aldrich), γ-Al2O3, benzoic acid, ethanol, nickel
nitrate (Ni(NO3)2·6H2O), urea, NaOH, NaBH4, and cyclo-
hexane were purchased and used without further purification.
2.2. Preparation Procedures of Catalysts. Al2O3-
supported nickel catalysts were prepared for the catalytic
hydrogenation of benzoic acid (BA) to cyclohexane carboxylic
acid (CCA) in this work. The goal catalyst was prepared from
a 2D nanoprecursor predispersing control by growing nickel-
based nanosheets on Al2O3; details are given in the following
description. 7.3 g of commercial γ-Al2O3 support calcined by
pseudo-boehmite (550 °C, 4 h) was immersed in an aqueous
solution of nickel nitrate (3.6 g in 5 mL of deionized water)
and dispersed under ultrasound for 30 min. The mixture was
heated at 120 °C for 12 h and changed to a green paste. The
paste was moved into an ice bath and reduced by adding 25
mL of NaBH4/NaOH aqueous solution (containing 1.9 g of
NaBH4 and 0.2 g of NaOH) dropwise under vigorous stirring
for 2 h. The precipitate then was filtered and washed
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alternately, in turn, with deionized water and ethanol until
the filtrate pH was neutral. The precipitate was redispersed in
ethanol under stirring for 12 h, then was filtered and dried at
60 °C in air for 12 h to obtain the precursor powder of nickel-
based nanosheets (NS) on Al2O3. Notably, although reductant
NaBH4 was employed in the above preparation of NS
precursor, in a report of Zhang et al., it was found that the
reduced nickel could suffer from an amorphous boron-
mediated oxidation process in aqueous solution with the
prolonged period, to result in the continuous and deep
oxidation of nickel.38 In our case, the phenomenon would
appear to be similar to the observation from the literature,
given that a long period (2 h) was required to allow growth of
the nanosheet. In order to obtain the supported nickel catalysts
in metallic state as much as possible, the precursor powder was
further reduced in 50 mL/min hydrogen flow at 400 °C for 3
h; the obtained catalyst was denoted as Ni/Al2O3-NS. Notably,
to avoid excessive oxidation of nickel metal in a catalyst in air,
the characterizations and catalytic measurements of the catalyst
should be performed as soon as possible after producing the
catalyst through the thermal reduction treatments.
For reference, two other Ni/Al2O3 catalysts were also
prepared from traditional incipient-wetness impregnation
(IWI) and deposition precipitation (DP) procedures. The
amount of γ-Al2O3 support and nickel nitrate was the same as
those in the above preparation of Ni/Al2O3-NS, and the last
reduction step with hydrogen and the corresponding
conditions to obtain the catalysts also were the same. The
two catalysts were denoted as Ni/Al2O3-IWI and Ni/Al2O3-
DP, respectively. Briefly, the mixture of calcinated γ-Al2O3 and
nickel nitrate solution was dried at 120 °C for 12 h. After
washing with deionized water and ethanol, the powder was
dried at 60 °C for 12 h to obtain the precursor of Ni/Al2O3-
IWI. For Ni/Al2O3-DP, 3.6 g of nickel nitrate and 7.3 g of the
Al2O3 support were mixed in 250 mL of deionized water. Then
7.4 g of urea was added to the solution, and the suspension was
stirred at 80 °C for 16 h to complete the deposition−
precipitation process. The precipitate was filtered and washed
with deionized water and ethanol. The obtained paste then was
dried at 60 °C for 12 h to obtain the precursor.
2.3. Characterizations. The actual nickel loading in the
catalyst was quantified by an inductively coupled plasma−
optical emission spectrometry (ICP-OES) system (Agilent
Technologies, Model 5100 ICP-OES).
X-ray diffraction (XRD) data of the sample powder were
collected at ambient temperature on a Puxi DX-3 diffrac-
tometer operated at 40 kV, 40 mA for Cu Kα (λ = 1.5418 Å),
with a scan speed of 0.125°/min and a step size of 0.02° in the
2θ range of 10°−80°.
Transmission electron microscopy (TEM) was performed
using a Model JEM-2100 TEM microscope (JEOL Co., Japan)
operating at 200 kV to observe the morphology and size
distribution of samples.
The surface chemical property of the catalysts was further
analyzed by X-ray photoelectron spectroscopy (XPS). The
spectra were obtained at ambient temperature under ultrahigh
vacuum on an Axis Ultra DLD electron spectrometer. During
data processing, the binding energy was calibrated with
reference to the C 1s peak of the contaminant carbon at
284.6 eV.
The H2 temperature-programmed reduction (H2-TPR)
measurements were performed in a quartz U-tube reactor.
Prior to these measurements, all the catalyst samples were
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pretreated with an argon flow (30 mL/min, 1 h, 200 °C). The
TPR profiles were obtained by passing carrier gas (10% H2 in
Ar) through the catalyst samples (30 mL/min, ramping from
50 °C to 800 °C at 10 °C/min) from a Micromeritics Auto
Chem II 2920 chemisorption analyzer.
Temperature-programmed desorption of H2 (H2-TPD) of
the catalyst was conducted in a quartz tube reactor
(Micromeritics AutoChem II 2920) that was equipped with
a thermal conductivity detection (TCD) system. Typically, 50
mg of sample was sealed in the reactor, pretreated with an
argon flow (30 mL/min, 1 h, 150 °C). The sample was
reduced at 400 °C for 3 h in 50 mL/min H2 flow and cooled to
room temperature in H2 flow. After H2 chemisorption at 30 °C
for 1 h, by removing the free adsorbate with an argon stream at
the rate of 30 mL/min for 30 min, the program was performed
in the temperature range of 30−500 °C with a heating rate of
10 °C/min to record the TCD signal.
2.4. Catalytic Measurements. All experiments were
perfomed in a Teflon reactor with 50 mL capacity contained
in a stainless-steel autoclave equipped with a mechanical
engineering stirrer and an electric heating system. BA (61 mg),
catalyst (50 mg) and cyclohexane (10 mL) were added into
the reactor. The reaction system was filled with H2 five times
then by evacuation to exclude air, and followed by increasing
the pressure to 1.0 MPa. The typical reaction was allowed at
150 °C under the stirring rate of 400 rpm for 2.5 h. The
mixture after reaction was cooled to ambient temperature and
filtered out of the catalyst; the filtrate was measured by gas
chromatography (GC) (Agilent, Model GC-7820A) and the
product were further ascertained by gas chromatography−mass
spectroscopy (GC-MS) (Agilent, Model 7890B-5077MS).
3. RESULTS AND DISCUSSION
3.1. Physiochemical Properties of Catalysts. Nickel
loadings in three catalysts, Ni/Al2O3-IWI, Ni/Al2O3−DP, and
Ni/Al2O3-NS, were ascertained by ICP-OES analysis as 10.0,
10.6, and 10.3 wt %, respectively, indicating comparable nickel
content among three catalysts. The entire structures of three
catalysts were studied with the Al2O3 support as reference by
XRD measurements, and the corresponding diffraction
patterns are given in Figure 1. All samples exhibited similar
peak at 2θ values of 19.5°, 37.6°, 45.8°, and 66.8°; these peaks
matched well with the crystalline planes (111), (311), (400),
and (440) of γ-Al2O3 (Powder Diffraction File (PDF) No. 29-
Figure 1. X-ray diffractions of catalysts: o, Al2O3; a, Ni/Al2O3-IWI; b,
Ni/Al2O3-DP; and c, Ni/Al2O3-NS.
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0063), respectively. In addition to the phase feature of Al2O3
support, two weak peaks could also be observed on the Ni/
Al2O3-IWI and Ni/Al2O3-DP samples, at ∼51.8° and ∼76.4°,
which could be attributed to the features of the metallic nickel
phase.39 In contrast, these Ni diffractions peaks could not be
resolved on the Ni/Al2O3-NS catalyst even in the local area, as
shown by the enlarged illustration inset in Figure 1, suggesting
that the nickel entities in Ni/Al2O3-NS catalyst could be
present as small particles (<ca.5.0 nm) or an amorphous form.
Because the highest Ni diffraction intensity was shown for the
Ni/Al2O3-IWI catalyst, the size order of nickel entities for the
three catalysts could be approximately estimated as Ni/Al2O3−
IWI > Ni/Al2O3-DP > Ni/Al2O3-NS.
To confirm the estimation, TEM images for the three
catalysts were collected, as shown in Figure 2. For comparison,
the morphologies of the precursors of the three catalysts were
collected in the first row in Figure 2. In comparison with the
blocklike images of precursors for the Ni/Al2O3-IWI and Ni/
Al2O3-DP catalysts, the precursor of the Ni/Al2O3-NS catalyst
exhibited a unique flower edge around a block powder with a
deep color; in fact, such a flower-edge appearance was initially
present on nickel-based nanosheets prepared without the
presence of Al2O3 (shown by the illustration in Figure 2c-1),
indicating that the precursor of Ni/Al2O3-NS catalyst was
composed of the nickel-based nanosheets grown on Al2O3.
Although such morphological differences disappeared after the
thermal-reduction procedure for producing catalysts, the
gradually enlarged images of catalysts disclosed the size
difference of nickel particles among the samples. As shown,
the d-space values of typical particle from the three catalysts
exhibited by the HRTEM images all matched well with the
0.203 nm value for crystalline Ni(111),40 indicating the
formation of metallic nickel particles after the thermal-
reduction treatment. The size distributions of particles
among the Ni/Al2O3-IWI, Ni/Al2O3-DP, and Ni/Al2O3-NS
catalysts were further determined as be 6.8 ± 1.5, 5.2 ± 1.2,
and 2.8 ± 0.5 nm, respectively, which verified the size order
estimation from XRD analysis.
In addition, the size order also indicated that growing nickel-
based nanosheets on Al2O3 as a precursor could be more
beneficial to obtaining small nickel nanoparticles, in compar-
ison with the two traditional methods, especially when a
considerable nickel loading (∼10.0 wt % for three catalysts)
was achieved. Notably, in most preparations to produce metal
nanoparticles smaller than ca. 5.0 nm, the protecting
surfactants were always employed to prevent the aggregation
of reduced metal to bigger particles; the performance of the
obtained metal particles would inevitably suffer from the
influence of adhered surfactants on the metal surface. In
contrast, there no surfactants were used in our preparations,
especially for the preparation of ca. 2.8 nm nickel particles
from the 2D nanoprecursor predispersing strategy. Thus, the
properties of metal catalysts on the relatively clean metal
surface could be better to be recognized from the character-
izations.
The redox states of catalysts were measured by XPS and H2-
TPR spectra, as given in Figure 3. Two main peaks located at
∼851.8 and 855.4 eV with a shakeup peak at 861.4 eV were
resolved in the Ni 2p3/2 spectra (Figure 3A) for the three
catalysts, indicating the co-occurrence of Ni(0) and Ni(II)
distributions on the surface of the three catalysts.41−43 The
distributions were further resolved as the atomic ratio values of
Ni(0)/Ni(II), which were collected in Table 1. As shown, with
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Figure 2. TEM data of samples: (a) Ni/Al2O3-IWI, (b) Ni/Al2O3-DP, and (c) Ni/Al2O3-NS. Using the labeling format of X = a, b, or c, the
following images are shown: X-1, images of precursors; X-2, images of catalysts; X-3, local images of catalysts; and X-4, HRTEM images of particles
in catalysts. Size distributions of particles in catalysts are shown in panels X-5 (where X = a, b, or c).

Figure 3. (A) XPS (Ni 2p3/2) spectra and (B) H2-TPR profiles of catalysts: a, Ni/Al2O3-IWI; b, Ni/Al2O3-DP; and c, Ni/Al2O3-NS.

Table 1. Physicochemical Parameter of Catalysts

nickel contenta particle sizeb metal dispersiond H desorption amountd TOF activation energy, Eae
catalyst (wt %) (nm) Ni(0)/Ni(II)c (%) (μmol gcat−1) (s −1) (kJ mol−1)
Ni/Al2O3-IWI 10.0 6.8 ± 1.5 0.09 6.9 113.9 0.8 56.9
Ni/Al2O3-DP 10.6 5.2 ± 1.2 0.11 6.6 116.1 2.0 52.7
Ni/Al2O3-NS 10.3 2.8 ± 0.5 0.05 12.2 201.0 31.4 41.9
a
Based on ICP-OES measurements. bStatistic results derived from TEM tests. cSurface atomic ratio determined by XPS measurements. dMeasured
from H2-TPD characterizations. eCalculated from kinetic measurements.

the decreasing order of size among the three catalysts, the
Ni(0)/Ni(II) ratio also decreased, which could be observed
because the smaller the nickel particle size was, the higher the
surface energy or more active the particle surface was,
facilitating the surface oxidation of particles.44 To eliminate
the surface oxidation influence on catalytic performance,
before catalytic measurements, all catalysts were freshly made
with the thermal reduction treatment. In addition, more
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obvious peak shifts toward higher binding energy occurred
with the decrease in particle size among catalysts, suggesting a
stronger interaction between the Al2O3 support and nickel
particles would occur when smaller nickel particles adhered to
the oxide support.45,46 The trend was further estimated with
H2-TPR profiles from Figure 3B. Two main reduction peaks
occurred for the three catalysts, which could be roughly
distinguished according to the reduction temperature. One set
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of peaks appearing below 300 °C could be attributed to the
reduction of nickel particles; the other set initiated from 350
°C correlated with nickel species on the Ni/Al2O3 inter-
face.42,47,48 Interestingly, the two sets of peaks showed different
change trends in temperature shift with particle size differences
on the three catalysts. The lowest temperature of ∼140 °C for
the reduction of nickel particles was observed for the Ni/
Al2O3-NS catalyst with the smallest nickel particles (ca. 2.8
nm), which could be attributed to the higher reactivity of
smaller nickel particles with H2.49,50 However, the highest
temperature of ∼512 °C for the reduction of interfacial nickel
species was also observed for the catalyst, suggesting a stronger
oxidation influence from Al2O3 on smaller nickel particles.51−54
Therefore, both XPS and H2-TPR characterizations implied
that a more prominent Ni−Al2O3 interaction occurred for the
Ni/Al2O3-NS catalyst, in comparison with other two catalysts
with bigger nickel particles.
Before catalytic hydrogenation measurements, the H2-
adsorption−desorption features of freshly prepared catalysts
were determined by H2-TPD profiles, as shown in Figure 4.
Figure 4. H2-TPD profiles of catalysts: a, Ni/Al2O3-IWI; b, Ni/Al2O3-
DP; and c, Ni/Al2O3-NS.
Similar H2-desorptions exhibiting a main single peak at
approximately 100 °C were observed for the three catalysts,
indicating almost identical H2 activation feature among the
three catalysts. Thus, the area resolved from the desorption
peak could be used to estimate and compare the number of Ni
active sites among three catalysts. According to a standard
estimation method with known Pt/Al2O3 catalyst, as described
in ref 55, H desorption (or active site) numbers were
determined and are collected in Table 1. The H-desorption
number on Ni/Al2O3-NS was approximately twice the values
for the Ni/Al2O3-IWI and Ni/Al2O3-DP catalysts, suggesting
that the active surface area value or active site number on Ni/
Al2O3-NS could be twice as high as those on the other two
catalysts. This finding was reasonable, since the Ni dispersion
on Ni/Al2O3-NS was almost two times higher than that on the
other two catalysts because the size ratio of nickel particles was
∼50% between Ni/Al2O3-NS and the other two catalysts.
3.2. Catalytic Performance of Catalysts. The catalytic
performance values for the hydrogenation of benzoic acid to
cyclohexane carboxylic acid for the three catalysts are collected
in Figure 5. Figure 5A shows the dependence of benzoic acid
conversion on reaction time for the catalysts. With the
insignificant benzoic acid conversion observed for the reaction
system containing bare Al2O3 as the blank reference (curve o),
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all three catalysts (curves a, b, and c) showed obvious
conversion and high selectivity (>98%) for cyclohexane
carboxylic acid (CCA). In comparison with the low conversion
(26%−40%) on Ni/Al2O3-IWI and Ni/Al2O3-DP, benzoic acid
could be almost completely converted to CCA with a yield of
98% on Ni/Al2O3-NS within 2.5 h. In addition, the initial
benzoic acid conversion within 0.5 h on Ni/Al2O3-NS was
clearly faster than that with the other two catalysts. A control
experiment involving filtering Ni/Al2O3-NS out of reaction
solutions after 1 h was also performed, as shown by the dotted
curve in Figure 5A. The reaction stopped once the catalyst was
removed, indicating that the supported nickel particles were
responsible for the efficient conversion of benzoic acid. Here,
note that 0.24 wt % of Na residue was found on the Ni/Al2O3-
NS catalyst, because of the Na-contained reagent used in the
preparation of the catalyst, but Na was not detected in Ni/
Al2O3-IWI or Ni/Al2O3-DP. Researchers have noted that Na+
could play an important role in the catalytic performance of
nickel-based catalysts.56 To evaluate this influence, Ni/Al2O3-
IWI and Ni/Al2O3-DP samples with deliberately introduced
Na+ at contents of 0.26 and 0.28 wt %, respectively, together
with a Ni/Al2O3-NS sample with 0.56 wt % of Na residue were
also employed for the reaction. Their catalytic performance
curves are labeled as a′, b′, and c′ in Figure 5A. The curves of
the three catalysts with additional introduced Na almost
overlapped with the curves of their respective counterpart with
low Na loadings; these results indicated that the content of
Na+ present in Ni/Al2O3 catalysts was not a governing factor
for their catalytic performance in the hydrogenation of benzoic
acid to CCA.
To estimate the catalytic stability of the catalysts, the recycle
uses of the catalysts for the reaction are compared in Figures
5B−D. As shown, the yield of cyclohexane carboxylic acid
significantly decreased over repeated used of Ni/Al2O3-IWI
and Ni/Al2O3-DP catalysts, demonstrated by their lowered
yield (from ∼30% to ∼12%); In contrast, a slight yield
decrease from 98% to 91% after five catalytic cycles was
observed for Ni/Al2O3-NS; the trend was parallel with the
benzoic acid conversion change during catalytic cycles, which
could be attributed to the gradual weight loss from the catalyst-
solution separation process between the different catalytic
cycles. The above comparison indicated that the Ni/Al2O3-NS
catalyst with smaller nickel particles was more active and stable
than the other two catalysts with bigger nickel particles.
Because the reactant benzoic acid was a type of acid, such a
feature could play an important role in the stability of nickel
catalysts, the reaction solutions from catalytic recycling
processes for the three catalysts were all carefully collected
and analyzed by ICP-OES. There was no evident amount of
metal species (including nickel and aluminum) found in any of
the solutions. In addition, we also measured the nickel loading
on recycled catalysts; the nickel loading deviations were
estimated within 0.4 wt %, according to the basic nickel loading
of ∼10.0 wt % for the three used catalysts. These results
suggested that the leakage of metal ions from the particles was
not obvious for the catalysts studied in this work.
To illuminate the possible change of catalysts during
catalytic recycles, three catalysts were reobserved by TEM
measurements after repeat uses, as shown in Figure 6. In
comparison with the original size of the fresh samples, the
nickel particles on Ni/Al2O3-IWI and Ni/Al2O3-DP catalysts
all increased in size by a factor of ∼3, on average, after five
catalytic cycles. In contrast, a slight size increase for nickel
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Figure 5. (A): Dependence of benzoic acid conversion on reaction time over catalysts: o, Al2O3; a, Ni/Al2O3-IWI; b, Ni/Al2O3-DP; c, Ni/Al2O3-
NS (the control experiment on the catalyst was also performed); a′, 0.26%Na−Ni/Al2O3-IWI; b′, 0.28%Na−Ni/Al2O3-DP; and c′, 0.56% Na−Ni/
Al2O3-NS. (B−D) Variations of yield of cyclohexane carboxylic acid during catalytic recycles over different catalysts, (B) for Ni/Al2O3-IWI (panel
(B)), for Ni/Al2O3-DP (panel (C)), and for Ni/Al2O3-NS (panel (D)).
particles from ca. 2.8 nm to ca. 4.2 nm was exhibited by Ni/
Al2O3-NS.
In accordance with the observations, the XRD patterns of
the used catalysts in Figure 7 showed more distinct Ni
crystalline diffractions, particularly on Ni/Al2O3-IWI and Ni/
Al2O3-DP catalysts. These results clearly demonstrate that the
small nickel particles derived from the predispersed nickel-
based nanosheets could adhere more tightly on the Al2O3
surface than the larger nickel particles obtained from
traditional incipient-wetness impregnation (IWI) and deposi-
tion precipitation (DP) procedures, i.e., the precursor-2D-
dispersing strategy not only controlled the nickel particles to
produce smaller sizes, but also induced a stronger interaction
between the nickel particles and Al2O3 support, in comparison
with traditional preparations. The synthetic effect could
efficiently prevent the movement, aggregation, and growth of
metal particles during thermal catalytic reactions and was
responsible for the superior activity and stability observed for
the Ni/Al2O3-NS catalyst. This deduction was also supported
by the previous XPS and H2-TPR measurements, in which the
stronger interaction between nickel particles and the Al2O3
support in Ni/Al2O3-NS, compared to the other two catalysts,
has been illuminated. Furthermore, the above results indicated
that the well-controlled nickel particles with small size such as
3.0−4.0 nm, were a key factor in accelerating the hydro-
genation of the benzene ring of benzoic acid.
In this study, one may argue that the smaller nickel particles
would possess more active sites, as described from H2-TPD
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measurements, which could be an important factor to
accelerate the reaction. To illuminate the influence among
the catalysts, the initial reaction rate (within 20 min) was
normalized to the active sites to obtain the turnover frequency
(TOF) for each individual catalyst; the TOF values are listed
in Table 1. Interestingly, a dramatic enhancement in TOF (an
increase of ∼15-fold to 40-fold) on Ni/Al2O3-NS (31.4 s−1),
compared to Ni/Al2O3-IWI (0.8 s−1) and Ni/Al2O3-DP (2.0
s−1), was observed. The active site number on Ni/Al2O3-NS
was just two times that of the other two catalysts (denoted by
the Ni dispersion in Table 1), indicating that the Ni sites on
smaller particles of the Ni/Al2O3-NS catalyst were much more
efficient than those on the Ni/Al2O3-IWI and Ni/Al2O3-DP
catalysts. This result also suggested that the kinetic factor for
the entire reaction system should be further considered. Thus,
in Figure 8, the relationships between ln Ct and reaction time t
at three temperatures (120, 140, and 150 °C (or 393, 413, and
423 K, respectively) are given. The relationships approach
linear dependences on the three catalysts (Figure 8A−C),
suggesting that the conversions of benzoic acid all followed
pseudo-first-order kinetics for the three catalysts. With these
plots, the dependences of ln k (where k represents the reaction
rate constant) on the reciprocal of reaction temperature (T−1)
are given in Figure 8D; the reaction activation energy (Ea) for
Ni/Al2O3-IWI, Ni/Al2O3-DP, and Ni/Al2O3-NS were esti-
mated as 56.9, 52.7, and 41.9 kJ mol−1, respectively. With the
Ea values (listed in the last column of Table 1), according to
the Arrhenius equation, the influence of Ea on reaction rate (r)
DOI: 10.1021/acs.iecr.8b06037
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Industrial & Engineering Chemistry Research Article

Figure 6. TEM images of catalysts (X-1) and particle size distribution in catalysts (X-2) after catalytic recycles (X = a, b, or c): a, Ni/Al2O3-IWI; b,
Ni/Al2O3-DP; and c, Ni/Al2O3-NS.

and TOF was determined for the catalysts, in which R is the 12, respectively. Correspondingly, the experimental ratios with
universal gas constant (R = 8.314 J mol−1 K−1), N is active site the TOF values listed in Table 1 were determined as
number of catalyst (which is roughly estimated by the TOF(NS)/TOF(IWI) = 42 and TOF(NS)/TOF(DP) = 16,
desorption amount H, listed in Table 1), and T is temperature respectively. The experimental ratios matched well with the

ij k yz
(chosen to be 423 K). theoretical ratios resolved from Ea, which indicated that the

lnjjj 1 zzz = a2
kinetic for the hydrogenation of benzoic acid to cyclohexane
jk z
E − Ea1
k 2{
carboxylic acid with Al2O3-supported nickel catalysts would be
RT (1) intensively accelerated by lowering the reaction activation
energy as a result of employing smaller nickel particles, i.e., the
r1 k reaction could present structure-sensitive catalytic behavior on
= 1
r2 k2 (2) oxide-supported nickel catalysts, since the reaction activity was
dependent directly on the size of the nickel particles.57 In fact,
TOF1 kN such an influence of metal particle size on its catalytic activity
= 1 2 has long been a hot topic for heterogeneous catalysis systems.
TOF2 k 2N1 (3)
Baranova et al. found that smaller platinum particles loaded on
Based on eqs 1−3, the TOF ratio between Ni/Al2O3-NS and zirconium-based supports would be more favorable for the
other two reference catalysts would be theoretically calculated catalytic oxidation of ethylene and CO due to the lowered
as TOF(NS)/TOF(IWI) = 40 and TOF(NS)/TOF(DP) = activation energies, compared to larger particles.58 In an earlier
2852 DOI: 10.1021/acs.iecr.8b06037
Ind. Eng. Chem. Res. 2019, 58, 2846−2856
Industrial & Engineering Chemistry Research
Figure 7. X-ray diffraction (XRD) spectra of catalysts after catalytic
recycles: o, Al2O3; a, Ni/Al2O3-IWI; b, Ni/Al2O3-DP; and c, Ni/
Al2O3-NS.
report, such enhanced catalytic activity by using smaller metal
particles was believed to be correlated with the enlarged
metal−support interface, since more-active species could form
along the interface, to accelerate the reaction.59 Besides the
metal−support interaction, the feature change of the metal
particle itself with size could also play an important role in
governing its catalytic performance. Generally, the effects could
Figure 8. Kinetic measurements. (A−C) Relation lines between ln Ct and reaction time (t) over different catalysts: for Ni/Al2O3-IWI (panel (A)),
for Ni/Al2O3-DP (panel (B)), and for Ni/Al2O3-NS (panel (C)). (D) Dependences of ln k on the reciprocal of reaction temperature (T−1) over
catalysts: a, Ni/Al2O3-IWI; b, Ni/Al2O3-DP; and c, Ni/Al2O3-NS.
2853
Article
be differentiated as geometrical and electronic factors. In view
of the geometrical factor, the exposed atoms on the corner or
edge of a metal particle would be more active than those on
the flat surface, because of the more unsaturated coordination
state of corner or edge atoms. The smaller the size of a metal
particle, the higher the percentage of such more highly active
sites, which leads to the activity enhancement.60,61 Considering
the electronic aspect, metal nanoparticles with smaller size
would show enhanced electron density near the Fermi level
(EF), narrowed d-band, and higher-lying d-band center.62
These electronic features would be more favorable to facilitate
the interaction of the metal with reactant to accelerate the
reaction. Therefore, for supported metal catalysts, particularly
those with small metal nanoparticles, the influence from the
metal/support interface and the nature of the metal particle
could conjunctively govern their catalytic activity. In our case,
these factors could coexist for the structure-sensitive catalytic
behavior observed for the Ni/Al2O3 catalysts in the catalytic
hydrogenation of benzoic acid to cyclohexane carboxylic acid.
Beyond all doubt, more-detailed investigations or more
contrast experiments were required to clearly clarify the
concrete contribution of these factors; given the topic of the
current work, such investigations could be expected in the
future.
Generally, it can be concluded that the 2D-nanoprecursor-
predispersing strategy (growing 2D nickel-based nanosheets on
Al2O3 as a catalyst precursor) employed for designing Ni/
DOI: 10.1021/acs.iecr.8b06037
Ind. Eng. Chem. Res. 2019, 58, 2846−2856
Industrial & Engineering Chemistry Research
Al2O3-NS catalyst was advanced not only in controlling
supported nickel as clean and small nanoparticles, but also in
offering a positive metal−support interaction, which, in turn,
leads to dramatic enhancements in both activity and stability,
compared to the catalysts prepared from traditional methods.
4. CONCLUSIONS
Clean, small nickel nanoparticles with a uniform average size of
ca. 2.8 nm indicated on Al2O3 were feasibly obtained by
growing nickel-based nanosheets on Al2O3 as a precursor. The
2D nanoprecursor predispersing strategy was notable for not
only achieving control of the production of small nanoparticles,
but also inducing a more positive interaction between the
metal and support, compared to traditional methods, which, in
turn, resulted in favorable catalytic activity and stability for the
hydrogenation of benzoic acid to cyclohexane carboxylic acid
with the derived catalyst. The feasibility and the feature of the
strategy to produce active metal catalyst with high dispersion
under conditions such as the absence of surfactant,
considerable metal loading, and thermal endurance made the
method a promising system to synthesize efficient supported
transition-metal catalysts for advanced heterogeneous catalysis,
such as scaled-up catalytic hydrogenation applications.
■
AUTHOR INFORMATION
Corresponding Authors
*Tel.: +86-15879176996. E-mail: zhaodan@ncu.edu.cn (D.
Zhao).
*Tel.: +86-15179167359. E-mail: chaochen@ncu.edu.cn (C.
Chen).
ORCID
Dan Zhao: 0000-0001-5618-9795
Chao Chen: 0000-0002-0913-0544
Author Contributions
† state synthesis of Ru−MC with highly dispersed semi-embedded
These authors contributed equally.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (NSFC) (Nos. 21003071 and
21563018) and Doctoral Fund of Ministry of Education of
China (No. 20093601120007).
■
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