energies

Article
Selective Hydrogenation of Phenol to Cyclohexanol
over Ni/CNT in the Absence of External Hydrogen
Changzhou Chen 1,2 , Peng Liu 1,2 , Minghao Zhou 1,2,3, *, Brajendra K. Sharma 3, * and
Jianchun Jiang 1,2, *
1 Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass
Energy and Material, Jiangsu Province, National Engineering Laboratory for Biomass Chemical Utilization,
Key and Open Laboratory on Forest Chemical Engineering, SFA, Nanjing 210042, China;
changzhou_chen@163.com (C.C.); liupengnl@163.com (P.L.)
2 Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry
University, Nanjing 210037, China
3 Illinois Sustainable Technology Center, Prairie Research Institute, one Hazelwood Dr., Champaign,
University of Illinois at Urbana-Champaign, Champaign, IL 61820, USA
* Correspondence: zmhzyk19871120@163.com (M.Z.); bksharma@illinois.edu (B.K.S.); jiangjc@icifp.cn (J.J.)




Received: 7 January 2020; Accepted: 11 February 2020; Published: 14 February 2020


Abstract: Transfer hydrogenation is a novel and efficient method to realize the hydrogenation in
different chemical reactions and exploring a simple heterogeneous catalyst with high activity is
crucial. Ni/CNT was synthesized through a traditional impregnation method, and the detailed
physicochemical properties were performed by means of XRD, TEM, XPS, BET, and ICP analysis.
Through the screening of loading amounts, solvents, reaction temperature, and reaction time,
20% Ni/CNT achieves an almost complete conversion of phenol after 60 min at 220 ◦ C in the absence of
external hydrogen. Furthermore, the catalytic system is carried out on a variety of phenol derivatives
for the generation of corresponding cyclohexanols with good to excellent results. The mechanism
suggests that the hydrogenation of phenol to cyclohexanone is the first step, while the hydrogenation
of cyclohexanone for the generation of cyclohexanol takes place in a successive step. Moreover,
Ni/CNT catalyst can be magnetically recovered and reused in the next test for succeeding four times.

Keywords: phenol; hydrogenation; Ni/CNT; cyclohexanol; transfer hydrogenation

1. Introduction
Cyclohexanol is an important chemical raw materials, for example, it could be used as the
main intermediate for the production of adipic acid, hexamethylene diamine, cyclohexanone, and
caprolactam, or as an excellent solvent for rubber, resin, nitro fiber, and metal soap [1–5]. Except for this,
its downstream product, cyclohexane, can also be converted into various useful chemicals [6–8]. Hence,
the production of cyclohexanol has attracted increasing attention, both in industry and in the laboratory,
recently. In the past several years, tremendous efforts have been devoted to the hydrogenation of
phenol for the generation of cyclohexanol. The main pathways can be classified into two groups,
gaseous [9] and liquid phase [10]. In the gaseous phase, a variety of supported noble metals, such as
Pd [11,12], Pt [13,14], Ru [15,16], Rh [17,18], have been reported to be effective in the hydrogenation
system. For example, Wang et al. reported a hierarchically porous ZSM-5 zeolite with micropore and
b-axis-aligned mesopore-supported Ru nanoparticles (Ru/HZSM-5-OM), which were highly effective for
the hydrogenation of both phenol and its derivatives to the corresponding cyclohexane [15]. However,
elevated temperature and high pressure of hydrogen (150 ◦ C, 4 MPa) were required, and carbonaceous
deposits in the process would result in the deactivation of catalyst. In the liquid phase, although

Energies 2020, 13, 846; doi:10.3390/en13040846 www.mdpi.com/journal/energies

Energies 2020, 13, 846 2 of 12

the hydrogenation process could be performed under a relatively lower temperature [19], the main
shortcoming of recent hydrogenation systems is that they could not avoid the presence of hydrogen [20].
For instance, Li et al. developed a series of Pd@FDU-N catalysts for the hydrogenation of phenol in
the presence of 0.1 MPa H2 [21]. Therefore, the exploration of a cheap and effective catalyst for the
hydrogenation of phenol in the absence of hydrogen is essential. Catalytic transfer hydrogenation (CTH)
has been regarded as a good alternative to avoid the application of high-pressure hydrogen [22–25].
Galkin et al. reported that Pd/C could catalyze transfer hydrogenolysis of β-O-4 model compound in
lignin employing formic acid as a hydrogen-donor for the generation of acetophenone and phenol
derivatives [22]. Paone et al. reported the transfer hydrogenolysis of α-O-4 model compound in
lignin conducted on Pd/Fe3 O4 under 240 ◦ C [23]. Wu et al. found that Ru/C could efficiently catalyze
the cleavage of the 4-O-5 aromatic ether bond in a variety of lignin-derived compounds through the
transfer hydrogenolytic pathway using isopropanol as the hydrogen-donor solvent [24]. Despite those
achievements for the transfer hydrogenolytic transformation of biomass to value-added chemicals,
the catalytic hydrogenation without the use of external hydrogen remains a great challenge [25,26].
Carbon nanotubes (CNT) are interesting materials for carrying out chemical reactions in confined
spaces, and several organic reactions have been carried out [27–29] inside the nanotubes. In this work,
CNT supported nickel catalyst was introduced into the hydrogenation of phenol for the generation of
cyclohexanol via a transfer hydrogenolytic route. Through the screening of loading amounts, solvents,
temperature and time, herein we reported a mild reaction condition (20% Ni/CNT, iPrOH, 220 ◦ C
and 60 min) for the hydrogenation of phenol to cyclohexanol. A variety of phenol derivatives were
also conducted to verify the high efficiency of this catalytic reaction system. The possible reaction
mechanism was finally investigated as well. The detailed physicochemical properties were investigated
by means of XRD, TEM, XPS, BET, and ICP analysis.

2. Experimental
Materials: CNT was purchased from Aladdin Industrial Inc. Shanghai, China and pre-treated in
HNO3 before use [27,28]. Ni(NO3 )2 .6H2 O was provided by Aladdin Industrial Inc. Shanghai, China.
Phenol and other derivatives were obtained from tansoole.com. All chemicals were obtained from
commercial sources and used without further purification.
General procedure for Ni/CNT catalyzed phenol: In one typical catalytic reaction process, 500
mg of phenol and other derivatives, 50 mg of Ni/CNT catalyst, and 10 mL isopropanol were placed
in a 25 mL stainless steel reactor. After being sealed, the catalytic reaction was stirred at desired
temperature for desired time. The reactor was naturally cooled to room temperature after the reaction.
The mixture solution was filtered to collect the catalyst and the filtrate was analyzed by the Gas
Chromatograph/Mass Spectrometer (GC/MS, Agilent 7890) utilizing n-dodecane as an internal standard.
The collected catalyst was washed with isopropanol three times and dried at 105 ◦ C for the next test
under the optimal reaction conditions. The conversion and product yields in the liquid phase were
calculated according to the following formula, respectively:

mole o f reacted substrate

Conversion = × 100%
total mole o f substrate f eed

mole o f cyclohexanone
Yield o f cyclohexanone = × 100%
total mole o f substrate f eed
mole o f cyclohexanol
Yield o f cyclohexanol = × 100%
total mole o f substrate f eed
Catalyst preparation: Ni/CNT was prepared by an impregnation method. In one typical
process of 20% Ni/CNT catalyst, Ni(NO3 )2 .6H2 O (0.2 g) was dissolved in 30 mL of deionized water.
Then, CNT (2.0 g) was added to the above solution and stirred for 24 h until a uniform dispersion.
The obtained suspension was dried for 12 h at 105 ◦ C in the oven. Subsequently, the obtained black
Energies 2020, 13, 846 3 of 12
Energies 2020, 13, 846 3 of 13

hydrogen atmosphere at 500 °C for 2 h. The preparation of Fe/CNT, Co/CNT, Mo/CNT was the same
solid was calcined at 500 ◦ C for 2 h in the muffle furnace, and finally reduced in a tube furnace under
as Ni/CNT.
hydrogen atmosphere at 500 ◦ C for 2 h. The preparation of Fe/CNT, Co/CNT, Mo/CNT was the same
Catalyst characterization: Powder X-ray diffraction (XRD) was examined on a Bruker D8
as Ni/CNT.
Advance X-ray powder diffractometer. Transmission electron microscopy (TEM) images were tested
Catalyst characterization: Powder X-ray diffraction (XRD) was examined on a Bruker D8 Advance
using a TEM Tecnai G2 20. The X-ray photoelectron spectroscopy (XPS) was carried out on an
X-ray powder diffractometer. Transmission electron microscopy (TEM) images were tested using a
ESCALAB-250 (Thermo-VG Scientific, USA) spectrometer with Al Kα (1486.6 eV) irradiation source.
TEM Tecnai G2 20. The X-ray photoelectron spectroscopy (XPS) was carried out on an ESCALAB-250
The textural properties of the Ni/CNT catalyst were tested by N2 adsorption–desorption isotherms
(Thermo-VG Scientific, USA) spectrometer with Al Kα (1486.6 eV) irradiation source. The textural
using a COULTER SA 3100 analyzer, and the Brunauer–Emmett–Teller (BET) surface area was
properties of the Ni/CNT catalyst were tested by N2 adsorption–desorption isotherms using a COULTER
evaluated by the N 2 adsorption–desorption isotherms.
SA 3100 analyzer, and the Brunauer–Emmett–Teller (BET) surface area was evaluated by the N 2
adsorption–desorption isotherms.
2.1. Catalyst Characterization
2.1. Catalyst
FigureCharacterization
1 shows the XRD patterns of two different samples, including solo CNT, and the optimal
catalyst in the system
Figure 1 shows for the
the XRD hydrogenation
patterns of phenol.
of two different The peak
samples, at 26.5°
including solocould
CNT,beandassigned to the
the optimal
diffraction peaks of the (002) planes of the graphite-like tube-wall of the CNT [30–32].
catalyst in the system for the hydrogenation of phenol. The peak at 26.5◦ could be assigned to the Apart from the
CNT feature,
diffraction peaksthe
of presence
the (002) of metallic
planes Nigraphite-like
of the in the reduced 20% Ni/CNT
tube-wall catalyst
of the CNT was clearly
[30–32]. revealed.
Apart from the
As could be clearly seen from the XRD results, only one kind of Ni-based phase
CNT feature, the presence of metallic Ni in the reduced 20% Ni/CNT catalyst was clearly revealed. was observed for
AsNi/CNT
could becatalyst.
clearlyPeaks
seen at 44.5°,
from the51.9°,
XRDand 76.4°only
results, couldonebe assigned to the diffraction
kind of Ni-based phase wasof the (111), (200),
observed for
Ni/CNT catalyst. Peaks at 44.5 , 51.9 , and 76.4 could be assigned to the diffraction of the (111), (200),in
and (220) planes of metallic ◦ Ni [27],
◦ indicating
◦ that only metallic nickel species were observed
Ni/CNT
and (220) catalyst.
planes of metallic Ni [27], indicating that only metallic nickel species were observed in
Ni/CNT catalyst.

Figure 1. 1.Characterization
Figure Characterizationofofthe
the20%
20%Ni/CNT
Ni/CNTcatalyst.
catalyst.(a)
(a)XRD
XRDpattern
patternofofCNT,
CNT,(b)(b)XRD
XRDpattern
patternofof
20% Ni/CNT.
20% Ni/CNT.

XPS
XPS detection waswas
detection carried out toout
carried analyze the composition
to analyze of prepared
the composition of 20% Ni/CNT.
prepared 20%TheNi/CNT.
absorption The
peaks were identified for C, O, and Ni. As for the presence of oxygen element in Figure
absorption peaks were identified for C, O, and Ni. As for the presence of oxygen element in Figure 2b, perhaps it
was
2b,due to theitpresence
perhaps was dueoftooxygen-containing groups of CNT during
the presence of oxygen-containing the of
groups HNOCNT3 pre-processing
during the HNO [30,31].
3 pre-
Inprocessing
addition, the oxidation of Ni/CNT catalyst before or during the XPS examination
[30,31]. In addition, the oxidation of Ni/CNT catalyst before or during the XPS could also lead to
the presence ofcould
examination oxygen element.
also lead to The binding energies
the presence of oxygen at 852.9
element.andThe
856.3 eV were
binding observed
energies for 20%
at 852.9 and
Ni/CNT (Figure 2a), which corresponded to Ni 0 (2p 3/2) and Ni2+ (2p3/2), respectively. The binding
856.3 eV were observed for 20% Ni/CNT (Figure 2a), which0 corresponded 2+ to Ni (2p 3/2) and
0
energies at 872.3
Ni2+(2p3/2), and 874.8 eV
respectively. The corresponded to theatmain
binding energies lines
872.3 andof874.8
Ni (2p
eV 1/2) and Ni (2p
corresponded 1/2).main
to the It could
lines
beoffound
Ni (2p 1/2) and Ni (2p 1/2). It could be found that part of metallic Ni was oxidized beforetoor
0 that part of metallic
2+ Ni was oxidized before or during the XPS testing, which contributed
the understanding of Ni2+which
during the XPS testing, detection in the XPS
contributed spectra.
to the understanding of Ni2+ detection in the XPS spectra.
 Energies 2020, 13, 846 4 of 13

Energies 2020, 13, 846 4 of 12

Energies 2020, 13, 846 4 of 13

Figure 2. Characterization of the 20% Ni/CNT catalyst. (a) XPS of Ni 2p, (b) XPS pattern of 20%
Ni/CNT.
Figure 2.2.Characterization
Figure Characterizationofof
thethe
20%20% Ni/CNT
Ni/CNT catalyst.
catalyst. (a) of
(a) XPS XPSNi of
2p,Ni
(b)2p,
XPS(b) XPS of
pattern pattern of 20%
20% Ni/CNT.
As can be seen in Figure 3, most of Ni particles displayed outside the CNT uniformly. However,
Ni/CNT.
the As
Ni can
particle sizeinand
be seen its distribution
Figure 3, most of Ni varied fromdisplayed
particles each other mainly
outside owing
the CNT to the loading
uniformly. amount
However,
of Ni
the Ni on the
Asparticle surface
can be size
seenand of CNT. We selected
its distribution
in Figure 20%
3, most of varied Ni/CNT catalyst
from displayed
Ni particles as
each otheroutsidean example.
mainly the
owing The histogram
CNTtouniformly.
the loading of 20%
amount
However,
ofNi/CNT
theNi in surface
the given
Nionparticle sizein ofFigure
and CNT. 3a,
We in which
selected
its distribution the mean
20%
varied fromsize
Ni/CNT was 14.0
catalyst
each other as nm. Taken
owingtogether,
an example.
mainly The
to nanoparticle
thehistogram
loading of 20%
amount Ni
on
Ni/CNTthe
of Ni on insurface
thegiven of CNT
in Figure
surface of CNT.performed
3a,We an excellent
in selected
which the20%mean activity
size was
Ni/CNT in the
14.0as
catalyst hydrogenation
nm.anTaken of
together,
example. phenol under
nanoparticle
The histogram our
Ni
of 20%
onreaction
Ni/CNT insystem.
the surface of in
given CNT performed
Figure an excellent
3a, in which the mean activity in 14.0
size was the hydrogenation of phenol
nm. Taken together, under our
nanoparticle Ni
reaction system.of CNT performed an excellent activity in the hydrogenation of phenol under our
on the surface
reaction system.

Figure 3. Characterization of the 20% Ni/CNT catalyst. (a) TEM image of 20% Ni/CNT, (b) Distribution
Figure 3. Characterization of the 20% Ni/CNT catalyst. (a) TEM image of 20% Ni/CNT, (b)
of Ni particles.
Distribution of Ni particles.
Table
Figure1 3.show the chemicalofand
Characterization thephysical
20% Ni/CNT properties
catalyst.for (a)
the TEM
different
image ratios of Ni/CNT
of 20% Ni/CNT,catalysts,
(b)
Table 1 show the chemical and physical properties for the different ratios of Ni/CNT catalysts,
including the Ni loading
Distribution amounts, BET surface area, and average Ni-particle size. The ICP results prove
of Ni particles.
including the Ni loading amounts, BET surface area, and average Ni-particle size. The ICP results
that the metal loading amounts were in great accordance with the theoretical calculating value with the
prove that1the
Table metal
show theloading
chemical amounts were inproperties
great accordance with the ratios
theoretical calculating value
preparation of the catalysts. Theand
BETphysical
surface area for the different
of 5% Ni/CNT catalyst was much of Ni/CNT catalysts,
larger than 25%
with the preparation
including the Ni loading of the catalysts.
amounts,
2 /g BET The BET surface area of 5% Ni/CNT catalyst was ICP
much larger
Ni/CNT (range from 149.3 m to 120.5 m2surface area, and
/g), suggesting thataverage Ni-particle
Ni particles could be size. The
better results
dispersed on
than 25%
prove that Ni/CNT
the metal (range
loading from 149.3 were
amounts m2/g to in 120.5
great m2/g), suggesting
accordance with that
the Ni particles
theoretical could bevalue
calculating better
the surface of CNT. Owing to the different loading amounts of Ni on the CNT, the average particle size
dispersed
with on the surface
the preparation of the of CNT. Owing
catalysts. The BETto the different
surface area loading amounts of Niwas on much
the CNT, the
of Ni/CNT with different metal amounts ranged from 12.1 to of
15.65%nmNi/CNT
(estimatedcatalyst
from XRD larger
in Table 1).
average
than particle
25% that
Ni/CNT size of
(range Ni/CNT
fromloadingwith
149.3 m different metal amounts ranged from 12.1 to 15.6 nm (estimated
It proved excessive metal on/gCNT
2 to 120.5
could minevitably
2 /g), suggesting
lead tothat
metalNi agglomeration,
particles could resulting
be better
from XRDoninthe Table 1). It of
proved that excessive metal loading on CNT could of inevitably lead to metal
in an increase of the metal particle size [32]. The TEM also gave the same results on the distributionthe
dispersed surface CNT. Owing to the different loading amounts Ni on the CNT, of
agglomeration,
average particle resulting
size in anwith
increase of the metal particleranged
size [32]. The TEM alsonm
gave the same
Ni particles (Table 1). of Ni/CNT
Hence, different
these changes metal
in catalyst amounts
properties wouldfrom 12.1
directly to 15.6
influence (estimated
the catalytic
results
from XRDonin the distribution
Table of Ni that
1). It proved particles (Table
excessive 1). Hence,
metal loading these changes
oninCNT in catalyst properties would
activity in the hydrogenation of phenol, which will be discussed detailcould
in theinevitably
followinglead to metal
experiments.
agglomeration, resulting in an increase of the metal particle size [32]. The TEM also gave the same
results on the distribution of Ni particles (Table 1). Hence, these changes in catalyst properties would
 Table 1. Chemical and physical properties of CNT-supported Ni catalysts.

Composition (wt.%) a SBET b Average Metal Average Metal

Catalysts
Energies 2020, 13, 846 Ni (m2/g) Size c (nm) Size d (nm)5 of 12
CNT / 180.6 / /
5% Ni/CNT 4.32 149.3 12.1 12.8
10% Table 1. Chemical and physical properties of CNT-supported Ni catalysts.
10.55 145.6 12.6 13.1
Ni/CNT Composition (wt.%) a b
SBET Average Metal Average Metal
15%Catalysts
14.66Ni (m2 /g)
135.8
c (nm)
Size12.8 Size d (nm)
13.5
Ni/CNT
20%CNT / 180.6 / /
5% Ni/CNT 19.68
4.32 132.4
149.3 13.1
12.1 12.814.0
Ni/CNT
10% Ni/CNT 10.55 145.6 12.6 13.1
25%
15% Ni/CNT 14.66 135.8 12.8 13.516.5
24.09 120.5 15.6
Ni/CNT
20% Ni/CNT 19.68 132.4 13.1 14.0
a25% Ni/CNTby ICP analysis,
—measured 24.09
b—evaluated from 120.5 15.6
N2 adsorption-desorption 16.5
isotherms, c—estimated
a —measuredby ICP analysis, b
by XRD, d-measured by TEM.—evaluated from N2 adsorption-desorption isotherms, c —estimated by XRD,
d —measured by TEM.

2.2. Activity of Various Catalysts for the Hydrogenation of Phenol

2.2. Activity of Various Catalysts for the Hydrogenation of Phenol
First of all, hydrogenation of phenol was chosen as a typical model reaction to explore the
Firstperformance
catalytic of all, hydrogenation
over a variety of phenol was (Table
of catalysts chosen2).asWhen
a typical model
carried reactionany
out without to explore
catalyststhe in
the hydrogenolytic system, the reaction failed to transform phenol to cyclohexanol (Table 2, catalysts
catalytic performance over a variety of catalysts (Table 2). When carried out without any entry 1).
in the hydrogenolytic
Meanwhile, solo CNTsystem, the reaction
also showed a poorfailed to transform
activity under ourphenol
reaction to condition
cyclohexanol (Table
(Table 2, entry
2, entry 2),
1). Meanwhile, solo CNT also showed a poor activity under our reaction condition
indicating that CNT only served as a support, and showed no catalytic effect in the catalytic process. (Table 2, entry 2),
indicating that CNT only served as a support, and showed no catalytic effect
Then, we tried different catalysts for the transformation of phenol, including 10% Fe/CNT, 10% in the catalytic process.
Then, we tried
Co/CNT, 10% different
Mo/CNTcatalysts
and 10% forNi/CNT
the transformation of phenol,
(Table 2, entries 3–5including
and entry10% 7). Fe/CNT, 10% Co/CNT,
It was surprising to
10% Mo/CNT and 10% Ni/CNT (Table 2, entries 3–5 and entry 7). It was surprising
discover that the supported Ni catalyst exhibited good performance in the hydrogenation of phenol to discover that
thegenerate
to supported Ni catalystindicating
cyclohexanol, exhibited thatgoodthe performance in theadsorbed
substrate phenol hydrogenationon the of phenol
metal to generate
surface prior to
cyclohexanol, indicating that the substrate phenol adsorbed on the metal surface
the reaction decreased the activation barrier of hydrogenation reaction [33]. The catalytic activity prior to the reaction
decreased
could the activation
be sorted barrier
as follows: of hydrogenation
10% Ni/CNT > 10% Co/CNTreaction [33].Mo/CNT
> 10% The catalytic
> 10%activity
Fe/CNT. could be sorted
However, the
as follows: 10% Ni/CNT > 10% Co/CNT > 10% Mo/CNT > 10% Fe/CNT. However,
loading amount of Ni on the surface of CNT could also affect the efficiency of the hydrogenolytic the loading amount
of Ni on It
process. the surface
could of CNTseen
be clearly couldinalso
Table affect thethe
2 that efficiency of the
conversion hydrogenolytic
increased with theprocess.
increased It could
loadingbe
clearly seen in Table 2 that the conversion increased with the increased loading
amount of Ni (from 5% to 25%), and the trend of the cyclohexanol yield showed the same result. amount of Ni (from 5%
to 25%), andwe
Meanwhile, thefound
trendthat
of the
thecyclohexanol yield showed
yield of cyclohexanol the 95%
reached samewhenresult.
20% Meanwhile,
Ni/CNT was weused
found in that
our
the yield of cyclohexanol reached 95% when 20% Ni/CNT was used in our
hydrogenolytic system (Table 2, entries 6–10). On the base of the results above, 20% Ni/CNT was hydrogenolytic system
(Table 2,asentries
chosen the most6–10). On the
suitable base offor
catalyst the
theresults above, exploration.
subsequent 20% Ni/CNT was chosen as the most suitable
catalyst for the subsequent exploration.
Table 2. Optimization of catalysts for the hydrogenation of phenol. a.
Table 2. Optimization of catalysts for the hydrogenation of phenol a .

T.(◦ C)/ Yieldb (%) b

Entry Catalyst T.(° C)/ Con. (%) Yield (%)
Entry Catalyst t.(h) Con. (%)
t.(h) 2a 2a 3a 3a
1 1 none
none 180/4
180/4 00 0 0 0 0
2 2 CNT
CNT 180/4
180/4 00 0 0
3 10% Fe/CNT 180/4 8 2 0
3 10% Fe/CNT 180/4 8 2 0
4 10% Co/CNT 180/4 48 5 5
5 4 10% Co/CNT
10% Mo/CNT 180/4
180/4 48
27 5 4 5 22
6 5% Ni/CNT 180/4 73 3 66
7 10% Ni/CNT 180/4 81 4 68
8 15% Ni/CNT 180/4 95 3 88
9 20% Ni/CNT 180/4 100 2 95
10 25% Ni/CNT 180/4 100 2 94
aReaction conditions: 1a (500 mg), catalyst (50 mg), Isopropanol (10 mL). b The conversion and yield were
determined by GC/MS with n-dodecane as the internal standard.
 aReaction conditions: 1a (500 mg), catalyst (50 mg), Isopropanol (10 mL). b The conversion and yield
were determined by GC/MS with n-dodecane as the internal standard.

2.3. Influence of Hydrogen-Donor Solvents

Energies 2020, 13, 846 6 of 12
Alcohol, as an excellent hydrogen-donor solvent, plays an important role in the catalytic transfer
hydrogenolytic process.
2.3. Influence Therefore,Solvents
of Hydrogen-Donor we selected three most common alcohols in our catalytic system.
Unfortunately, methanol and ethanol failed the transformation of phenol to cyclohexanol (Table 3,
Alcohol, as an excellent hydrogen-donor solvent, plays an important role in the catalytic transfer
entries 2–3). H2O wasprocess.
hydrogenolytic considered as we
Therefore, a green
selectedand
threeenvironmentally
most common alcoholsfriendly solvent,
in our catalytic and always
system.
applied in various chemical
Unfortunately, methanol reactions.
and ethanol However,
failed the 20% Ni/CNT of
transformation catalyst
phenol showed a poor(Table
to cyclohexanol activity
3, in the
hydrogenation of phenol
entries 2–3). in aqueous
H2 O was considered media (Table
as a green and3,environmentally
entry 4). Whenfriendly
isopropanol
solvent,was
and utilized
always in our
catalytic system, a satisfactory result was achieved that cyclohexanol was obtained in theinyield
applied in various chemical reactions. However, 20% Ni/CNT catalyst showed a poor activity the of 95%
(Table 3,hydrogenation of phenol in aqueous media (Table 3, entry 4). When isopropanol was utilized in our
entry 1). Therefore, isopropanol was the most efficient hydrogen-donor solvent for the
catalytic system, a satisfactory result was achieved that cyclohexanol was obtained in the yield of
transformation
95% (Tableof 3,
phenol
entry 1).toTherefore,
cyclohexanol.
isopropanol was the most efficient hydrogen-donor solvent for the
transformation of phenol to cyclohexanol.
Table 3. Optimization of solvents for the hydrogenation of phenol. a.
Table 3. Optimization of solvents for the hydrogenation of phenol a .

T.(◦ C)/ Yield (%) b

Entry Solvent T.(°
t.(h)
C)/ Con. (%) Yield (%) b
Entry Solvent Con. (%) 2a 3a
t.(h) 2a 3a
1 isopropanol 180/4 100 2 95
21 isopropanol
methanol 180/4
180/4 100
15 23 95 6
32 ethanol
methanol 180/4
180/4 13
15 32 6 5
4 H2 O 180/4 5 0 0
3 ethanol 180/4 13 2 5
a Reaction conditions: 1a (500 mg), 20% Ni/CNT (50 mg), Solvent (10 mL). b The conversion and yield were
4 H2O 180/4
determined by GC/MS with n-dodecane as the internal standard.
5 0 0
aReaction conditions: 1a (500 mg), 20% Ni/CNT (50 mg), Solvent (10 mL). b The conversion and yield
were2.4.
determined
Influence ofby GC/MS
Reaction with n-dodecane
Temperature as Time
and Reaction the internal standard.
In addition, reaction temperature and reaction time were important key factors for the
2.4. Influence of Reaction
transformation of Temperature
phenol (Figureand Reaction
4). As Time
shown in Figure 4a, the conversion of phenol progressively
increased when the reaction temperature increased from 160 to 220 ◦ C, and phenol could almost
In addition, reaction temperature and reaction time were important key factors for the
totally transfer to cyclohexanol at 220 ◦ C with a reaction time of 60 min. In the catalytic process, the
transformation
dominantofproducts
phenolwere
(Figure 4). As shown
cyclohexanol, in Figure
with a small amount4a, the conversion
of cyclohexanone of phenol
detected progressively
in the GC/MS.
increasedAswhen the reaction
the temperature temperature
continued increased
to rise, the yield from 160
of cyclohexanol to 22095%.
kept around °C, Subsequently,
and phenolitcould
could almost
be foundto
totally transfer that the conversionat
cyclohexanol of220
phenol
°C increased with the prolonging
with a reaction time of 60ofmin. the reaction
In thetime (Figureprocess,
catalytic 4b), the
and the phenol was completely consumed in only 60 min at 220 ◦ C. With the prolonged reaction time,
dominant products were cyclohexanol, with a small amount of cyclohexanone detected in the
the yield of cyclohexanol increased when the reaction time increased from 20 to 60 min. When the
GC/MS. reaction
As thetime temperature continued to rise, the yield of cyclohexanol kept around 95%.
exceeded 60 min, the conversion of phenol achieved 100%, and the yield of cyclohexanol
Subsequently,
kept at it
thecould
highestbepoint.
found that the
Through theconversion of phenol increased
screening of temperature and time ofwith the prolonging
the hydrogenation of of the
reaction phenol,
time (Figure 4b),temperature
the optimal and the phenol
and time was completely
could consumed
be summarized as 220 ◦ Cin only
and 60 min
60 min, at 220 °C. With
respectively.
the prolonged reaction time, the yield of cyclohexanol increased when the reaction time increased
from 20 to 60 min. When the reaction time exceeded 60 min, the conversion of phenol achieved 100%,
and the yield of cyclohexanol kept at the highest point. Through the screening of temperature and
time of the hydrogenation of phenol, the optimal temperature and time could be summarized as 220
°C and 60 min, respectively.
Energies 2020, 13, 846 7 of 12
Energies 2020, 13, 846 7 of 13

Figure4.4.Influence
Figure Influenceof
ofreaction
reactiontemperature
temperature(a)
(a)and
andtime
time(b)
(b)on
onthe
thehydrogenation
hydrogenationofofphenol.
phenol.Reaction
Reaction
conditions:
conditions: Phenol (500 mg), 20% Ni/CNT (50 mg), isopropanol (10 mL); reaction time,60
Phenol (500 mg), 20% Ni/CNT (50 mg), isopropanol (10 mL); reaction time, 60min
min(for
(fora);
a);
reaction temperature, 220 ◦ C (for b).
reaction temperature, 220 °C (for b).
2.5. Scope of the Substrates
2.5. Scope of the Substrates
Encouraged by the perfect performance of the efficient hydrogenation of phenol, a variety of phenol
Encouraged by the perfect performance of the efficient hydrogenation of phenol, a variety of
derivatives were tested on 20% Ni/CNT. As shown in Table 4, phenol could be completely transformed
phenol derivatives were tested on 20% Ni/CNT. As shown in Table 4, phenol could be completely
to afford the corresponding cyclohexanol in a yield of 95% without additional hydrogen under the
transformed to afford the corresponding cyclohexanol in a yield of 95% without additional hydrogen
optimal reaction condition (Table 4, entry 1). Methylphenol derivatives gave methylcyclohexanols
under the optimal reaction condition (Table 4, entry 1). Methylphenol derivatives gave
with a poor conversion and yield under 220 ◦ C at a reaction time of 60 min. Therefore, we increased the
methylcyclohexanols with a poor conversion and yield under 220 °C at a reaction time of 60 min.
temperature from 220 ◦ C to 240 ◦ C. As excepted, methylphenol derivatives gave methylcyclohexanols
Therefore, we increased the temperature from 220 °C to 240 °C. As excepted, methylphenol
with both perfect conversion and yield (Table 4, entries 2–4). Hydroxy substituted phenol could not
derivatives gave methylcyclohexanols with both perfect conversion and yield (Table 4, entries 2–4).
achieve the CTH process under optimal conditions as well. Hence, 240 ◦ C was employed in our
Hydroxy substituted phenol could not achieve the CTH process under optimal conditions as well.
reaction system and a 79% yield of cyclohexane-1,2-diol was obtained in the reaction time of 60 min
Hence, 240 °C was employed in our reaction system and a 79% yield of cyclohexane-1,2-diol was
(Table 4, entries 5). Based on the relevant literature [34], the reason for the small decrease in the yields of
obtained in the reaction time of 60 min (Table 4, entries 5). Based on the relevant literature [34], the
corresponding cyclohexanol derivatives probably is the steric effect. Hence, the presence of substituent
reason for the small decrease in the yields of corresponding cyclohexanol derivatives probably is the
imposes a steric repulsion, which might lower the degree of adsorption and thus hydrogenation rate.
steric effect. Hence, the presence of substituent imposes a steric repulsion, which might lower the
Taken together, the transfer hydrogenation system was confirmed suitable for the hydrogenation of
degree of adsorption and thus hydrogenation rate. Taken together, the transfer hydrogenation system
diverse phenol derivatives with good to excellent results.
was confirmed suitable for the hydrogenation of diverse phenol derivatives with good to excellent
results.
 Energies
Energies
Energies
Energies 2020,
2020, 2020,
2020,
13,
2020, 13,
Energies
Energies 846
846
2020,
13, 13,
84613, 846
13,846
846 888 of
of 888 of
13
of 13
13 of 13
of 13
13

Table
Table Table
Table
4. 4.
4. Hydrogenation
Hydrogenation
Hydrogenation
4. 2020,
Hydrogenation of of
of phenol
phenol
of phenol
phenol with with
with substituted
substituted
with substituted
substituted functional
functional
functional
functional groups
groups
groups with with
groups
with with
20% 20%
20% Ni/CNT
20% Ni/CNTNi/CNT
Ni/CNT in
in in
in
Energies 13, 846 8 of 12
isopropanol.
isopropanol.
isopropanol. aa
isopropanol.
isopropanol. aa aa
a

Table 4. Hydrogenation of phenol with substituted functional groups with 20% Ni/CNT inYield
isopropanol a.
Yield
Yield Yield
of
of of
Yield of
of
Entry Entry
Entry
Entry Entry Substrate
Substrate
Substrate
Substrate
Substrate T( o T(
T(
T(oC)/t(min)
o
o C)/t(min)
oooC)/t(min) Conversion(%)
Conversion(%)
T( C)/t(min) Conversion(%)
C)/t(min) Conversion(%)
Conversion(%)
Entry Substrate T (◦ C)/t (min) Conversion (%) product(%)
product(%)
Yieldproduct(%)
product(%)
product(%)
of Product (%)

111 1 220/60 220/60 100100 100

11 220/60220/60
220/60 220/60 100 100
100 95
95
95 95
95

222 2 240/60 240/60 89 89 89

22 240/60240/60
240/60 240/60 89 89
89 80
80 80
80
80

333 3 240/60 240/60 90 90 90

33 240/60240/60
240/60 240/60 90 90
90
82
82
82
82
82 82
Energies Energies
2020,
Energies 2020,
13, 846
2020,
Energies 13,
13, 846
13, 846
2020, 846 9 of9913
9 of 13 of
of 13
13

444 4 240/60 240/60 85 85 85

44 240/60240/60
240/60 240/60 85 85
85 78
78 78
78
78
78

555 5 240/60 240/60 88 88 88

55 240/60240/60
240/60 240/60 88 88
88
79 79
79
79
79
aaaa Reaction
ReactionReaction
aaa Reaction
Reaction
a condition:
condition:
condition: 20%
condition:
Reaction
condition: 20%
20%
Ni/CNT Ni/CNT
Ni/CNT
20%20%
condition:
20% Ni/CNT (50
Ni/CNT (50
(50
mg),
Ni/CNT
(50 mg), mg),
mg),
mg),
(50 substrate
substrate
(50substrate
substrate (500 (500
(500
(500 mg),
mg),substrate
substrate mg),
mg), solvent
solvent
(500solvent
(500
mg), mg),
solvent (10 (10
(10
(10 mL).
mg),solvent
solvent(10(10
mL). mL).
mL).
mL).
mL).

2.6. 2.6. Mechanism

2.6. Mechanism
2.6. Mechanism
Mechanism Studies
Studies Studies
Studies
and
and the and
and
the the Recyclability
the Recyclability
Recyclability
Recyclability of
of Ni/CNT of Ni/CNT
of
Ni/CNT Ni/CNT
2.6.The
Mechanism Studies and the Recyclability of of Ni/CNT over 20% Ni/CNT was proposed in Figure 6.
The The mechanism
The mechanism mechanism
mechanism of
of thetheof the
the hydrogenation
ofhydrogenation
hydrogenation
hydrogenation of
of phenol of phenol
phenol phenol
over
over 20% overNi/CNT
20% 20% Ni/CNT
Ni/CNT was was proposed
was proposed
proposed in
in Figurein Figure
Figure 6.
6. 6.
According
According
According The
to the to
to the
the
mechanism
time time
time
courses courses
courses
of the
of of
of phenol
phenol
hydrogenation
phenol and and
and of
products
According to the time courses of phenol and products (Figure 4), the hydrogenation of phenol products
products
phenol (Figure over(Figure
(Figure 20%
4), the4),
4),
Ni/CNT the
the hydrogenation
hydrogenation
hydrogenation was proposed of of
of
in
phenol phenol
phenol
Figure 6.
proceeded
proceeded
proceededAccording
proceeded via via
via
to the
via cyclohexanone.cyclohexanone.
cyclohexanone.
time
cyclohexanone. In courses of
In order In
In
phenol
order to order
order and to
to corroborate
corroborate
products
to corroborate
corroborate this, (Figure
this, we this,
this,
4), the we
we investigated
investigated
hydrogenation
we investigated
investigated the of the
the
phenol
the activity activity
activity
activity of proceeded
of of
of
cyclohexanol
cyclohexanol
via cyclohexanone.
cyclohexanol
cyclohexanol and and
and cyclohexanone
and cyclohexanone cyclohexanone
cyclohexanone In order in
in thetoin
the in the
the process
corroborate
process
process process
of of
of transfer
this,
of transfer
transfer transfer
wehydrogenation.hydrogenation.
hydrogenation.
investigated
hydrogenation. the
When
When When
When
activitysolo of
solo solo
solo cyclohexanol
cyclohexanol
cyclohexanol
cyclohexanol
cyclohexanol and
was was
was
carried carried
carried
cyclohexanone
out in out
out
our in
in in our
our
the
catalytic catalytic
catalytic
process
system, system,
system,
of transfer
no no
no cyclohexanol
cyclohexanol
hydrogenation.
cyclohexanol
was carried out in our catalytic system, no cyclohexanol was transformed into cyclohexanone (Figurewas was
wasWhen
transformedtransformed
transformed
solo into
into
cyclohexanol
into cyclohexanone
cyclohexanone
cyclohexanone was carried
(Figure (Figure
(Figure
out in our
5a). 5a).
5a). The
The
Thecatalytic
5a). The results results
results
system,
results above
above above
above
show
show show
show
no cyclohexanol
the the
the hydrogenation
hydrogenation
the hydrogenation
hydrogenation was transformed
of
of phenol of
of
phenol tophenol
phenol
tointo to
to cyclohexanol
cyclohexanol
cyclohexanone
cyclohexanol
cyclohexanol via via
via cyclohexanone
cyclohexanone
(Figure 5a). The
via cyclohexanone
cyclohexanone under
under
results
under
under aa aboveaa
transfer
transfer
transfer
transfer show hydrogenation
hydrogenation
the
hydrogenation
hydrogenationhydrogenation process.
process. process.
process.
of
It phenol
It can
can Itbe
It be can
can tobe
seen
seen be seen from
seen
cyclohexanol
from
from from
Figure
Figure Figure
Figure
via
5b 5bfrom
5b that, from
that,
cyclohexanone
5b that,
that, from from
the the beginning
the
under
the beginning
beginning beginning
a transfer
of theof
of the of the process,
the process,
hydrogenation
process,
process,
the the
the
amount amount
amount
process. of It of
of
can cyclohexanone
cyclohexanone
cyclohexanone be seen from
decreased decreased
decreased
Figure and5b and
the amount of cyclohexanone decreased and cyclohexanol was observed. Cyclohexanone was was
and
that, cyclohexanol
cyclohexanol
from
cyclohexanol the was was
was
beginning
observed. observed.
observed.
of the Cyclohexanone
Cyclohexanone
process,
Cyclohexanone the amount
was wasof
completely
completely
cyclohexanone
completely
completely consumed
consumed consumed
consumed decreased
after
after 30 after
after
30 min
min 30
and min
30andmin and
cyclohexanol
and cyclohexanol
and cyclohexanol
cyclohexanol
cyclohexanol waswas was
observed.
was achieved
achieved achieved
was achievedCyclohexanone
in
in high
highin high
in yield
highwas
yield yield
yield
(over
(over (over
(over
completely
90%). 90%).
90%).90%). Apart Apart
Apart
consumed
Apart
from from
this,
after this,
acetone
30 acetone
min was
and was
also also
detected
cyclohexanol detected
in was the in the
catalytic
achieved catalytic
from this, acetone was also detected in the catalytic process. In Table 5, we could find that 95% of of
from this, acetone was also detected in the catalytic
process.
in high process.
process.
In
yield Table In
In
(over Table
Table
5, we
90%). 5,
5, we
we
could
Apart could
could
find
from find
find
thatthis, that
that
95% 95%
95%
of
acetone of
was
cyclohexanol,
cyclohexanol,
cyclohexanol,
cyclohexanol, 2%
also 2% of
detected 2%
2% of
of cyclohexanone,
cyclohexanone,
of cyclohexanone,
cyclohexanone, 5.8
in the catalytic 5.8
5.8
5.8 equivalents equivalents
equivalents
equivalents of
process. In Table of
of
of acetone acetone
acetone
acetone and
5, we and 33.6
could and
and 33.6
33.6
33.6 equivalents
find equivalents
equivalents
equivalents of
that 95% of of
of
of isopropanolisopropanol
isopropanol
cyclohexanol,
isopropanol 2% of
were were
were
were observed observed
observedobserved
for
for each
cyclohexanone, for
eachfor5.8 each
each equivalent
equivalentequivalent
equivalents
equivalent of
of phenol
phenolof
of of phenol
phenol
acetone consumed,
and
consumed, consumed,
consumed,
33.6which
equivalents
which which
which
suggested
suggested suggested
suggestedthat
that the
of isopropanol that
that
the the
the hydrogenation
hydrogenation
hydrogenation
were
hydrogenationobservedof of
of
offor each
phenol phenol
phenol
was a was
was a
a stoichiometric
stoichiometric
stoichiometric
equivalent of phenol reaction
consumed, reaction
reaction
and and
and
each
which each
each
phenol
suggested phenol
phenol
molecule
phenol was a stoichiometric reaction and each phenol molecule needed six isopropanol molecules forthat molecule
molecule
the needed needed
needed
hydrogenation six six
six
isopropanol
of isopropanol
isopropanol
phenol molecules
was molecules
molecules
a for
stoichiometric for
for
the the
the generation
generation
the generation
reaction
generation of
and
of of cyclohexanol.
of cyclohexanol.
cyclohexanol.
each
cyclohexanol. phenolTherefore,
molecule
Therefore,Therefore,
Therefore, the the
the
the detailed
needed detailed detailed
sixdetailed
mechanism
isopropanol
mechanism mechanism
mechanism couldcould
could
molecules could
be
befor be summarized
be
summarized
the
summarized summarized
generation in ofin
in Figurein
Figure Figure
Figure
6. 6.
6.
cyclohexanol. 6.
The The
The
The molecule molecule
molecule
Therefore,
molecule adsorptionadsorption
adsorption
the
adsorption of of
of
of isopropanol
detailed isopropanol
isopropanol
mechanism
isopropanol occurred occurred
occurred
could
occurred on
be the
on on
on the catalyst
the
catalyst
summarized
the catalyst catalyst
surface surface
surface
in Figure
surface to
to produce toThe
6.to
produce produce
produceH*
H* and
molecule
and H*followed
H* and
and followedof
followed
adsorption
followed
by by
by phenol
phenol adsorption
adsorption (i).
(i). Then,
Then, irreversible
irreversible phenol
phenol
by phenol adsorption (i). Then, irreversible phenol hydrogenation took place for the generation of
phenol adsorption
isopropanol (i).
occurred Then, on irreversible
the catalyst phenol
surface hydrogenation
hydrogenation
hydrogenation
to produce H* took
and took
took
place
followed place
place
for the
by for
for the
the
generation
phenol generation
generation of of
adsorption of(i).
cyclohexanone,
cyclohexanone,
cyclohexanone,
cyclohexanone, in
in which
Then, irreversible whichin which
in phenol
which
four four
four
four equivalents equivalents
equivalents
hydrogenation
equivalents of H*
of took of
H*ofwere H*
place
were were
H* wereconsumed
for
consumed consumed
theconsumed (ii–iv).
generation (ii–iv).
(ii–iv).(ii–iv).
ofIn the In the
theInfinal
Incyclohexanone,
final final
the step,
final step,
step,instep,
whichtwo
two
two twofour
equivalents
equivalents
equivalents of
equivalents H* of
ofwas
ofH*
H* H* was
was
employed
were employed
employed in
consumed the in
in the
the
catalytic
(ii–iv). catalytic
catalytic
Inprocess
the
equivalents of H* was employed in the catalytic process to transfer cyclohexanone to cyclohexanolprocess
process
to
final to
to
transfer
step, transfer
transfer
two cyclohexanone
cyclohexanone
cyclohexanone
equivalents of to
H* to
to cyclohexanol
cyclohexanol
cyclohexanol
was employed in the
(v).
(v).
(v). Based Based
Based
on the on
on the
the
study study
study
above, above,
above,
we we
we
propose propose
proposethe the
the
mechanism mechanism
mechanism in
catalytic process to transfer cyclohexanone to cyclohexanol (v). Based on the study above, we propose two in
in two
two
steps: steps:
steps:
(1) (1)
(1)
Conversion Conversion
Conversion of of
of
phenol phenol
phenol
to to
to
cyclohexanone
cyclohexanone
cyclohexanone
theFigure
cyclohexanone over
mechanism
5.Figure
over
Figure Time
Figureover
over
the
the
5. in
5. the
the
Ni/CNT
two
Time
Ni/CNT
course
Time
5. Time Ni/CNT
Ni/CNT
course catalyst.
ofsteps:
course
catalyst.
the
course catalyst.
catalyst.
(1)
of
ofyield
the
of the(2)
of(2)
yield
the of(2)
yield ofTransformation
(2) Transformation
Transformation
Conversion
yield of ofcarried
phenol
cyclohexanol
Transformation
cyclohexanol
cyclohexanol
cyclohexanol of
carried of
carried
ofout of
cyclohexanol
toin cyclohexanol
cyclohexanol
cyclohexanone
cyclohexanol
carried the
out out
out in
in the
intransfer
the from
from from
from
transfer
transfer
the transfer cyclohexanone
cyclohexanone
cyclohexanone
over the Ni/CNT
hydrogenation
cyclohexanone
hydrogenation
hydrogenation (a). Time
hydrogenation via
(a). (a).via
Time
(a).via
viacatalyst.
Time
Time
keto-enol
keto-enol
keto-enol(2) course tautomerism.
tautomerism.
tautomerism.
Transformation
of
course
keto-enol tautomerism. course
the
course yield
of the of of
the
of
yield
of the cyclohexanol
yield of
cyclohexanonecyclohexanone
of cyclohexanone
yield of cyclohexanonefrom
carried cyclohexanone
carried
out
carried in theout
out out
carried in
transfer
in the via
the keto-enol
transfer
hydrogenation
transfer
in the transfer tautomerism.
hydrogenation
hydrogenation
hydrogenation(b). (b).
(b). (b).

Table
Table
Table Distribution
5. 5.
5. Table 5.
Distribution
Table of of
products
5. Distribution of
of products
Distribution
Distribution with
of products
with
products 20%20%
with
with
products Ni/CNT
20%
Ni/CNT
20%
with in in
Ni/CNTisopropanol.
in
in isopropanol.
in isopropanol.
Ni/CNT
20% Ni/CNT isopropanol.
isopropanol.

Catalyst
Catalyst Catalyst Temperature/Time
Temperature/Time
Catalyst Temperature/Time
Catalyst Temperature/Time
Temperature/Time Conversion
Conversion
Conversion
Conversion
Conversion

Ni/CNT
Ni/CNT Ni/CNT
Ni/CNT
Ni/CNT 220
220 ◦ C/60 220
C/60min
220min
220 C/60min
C/60min
C/60min100%
o o 100%100%
oo 100%
100%95%
95% 95% 95%
2%
95%2%2% 2%
5.8
2% 5.8 5.8
equiv equiv
equiv
5.8
5.8 33.6 33.6
equiv
equiv 33.6
equiv equiv
equiv
33.6
33.6 equiv
equiv
Reaction Reaction condition:500
condition:500 mg mg
phenol phenol
(1.0 (1.0
equiv), equiv),
50 mg 50
20% mg 20%
Ni/CNT, Ni/CNT,
10mL 10mL isopropanol
isopropanol (40.0
Reaction condition:500 mg phenol (1.0 equiv), 50 mg 20% Ni/CNT, 10mL isopropanol (40.0 equiv). Yieldequiv).
Reaction condition:500
Reaction mg
condition:500 phenol
mg (1.0
phenol equiv),
(1.0 50
equiv), mg
50 20%
mg Ni/CNT,
20% Ni/CNT,10mL isopropanol
10mL (40.0
equiv).
(40.0
isopropanol (40.0 equiv).
equiv).
was
Yield wasYield
Yield
determined
Yield was
by determined
determined
was GC/MS
was by
determined GC/MS
with
determinedby by GC/MS
bywith
GC/MS
n-dodecane
GC/MS with
as with
n-dodecane
the n-dodecane
as
n-dodecane
internal
with standard.
n-dodecane as
as the
theasinternal
the internal
standard.
internal
the standard.
standard.
internal standard.
Energies 2020, 13, 846 9 of 12
Energies 2020, 13, 846 9 of 13

Figure 5. Time course of the yield of cyclohexanol carried out in the transfer hydrogenation (a).
Figure 5. Time course of the yield of cyclohexanol carried out in the transfer hydrogenation (a). Time
Energies
Time2020, 13, 846of the yield of cyclohexanone carried out in the transfer hydrogenation (b).
course 10 of 13
course of the yield of cyclohexanone carried out in the transfer hydrogenation (b).

Table 5. Distribution of products with 20% Ni/CNT in isopropanol.

Catalyst Temperature/Time Conversion

Ni/CNT 220oC/60min 100% 95% 2% 5.8 equiv 33.6 equiv

Reaction condition:500 mg phenol (1.0 equiv), 50 mg 20% Ni/CNT, 10mL isopropanol (40.0 equiv).
Yield was determined by GC/MS with n-dodecane as the internal standard.

Figure
Figure 6. Catalytic pathway
6. Catalytic pathway in
in the
the transfer
transfer hydrogenation
hydrogenation of
of phenol.
phenol.

In
In addition,
addition, the
the Ni/CNT
Ni/CNT catalyst
catalyst could
could bebe magnetically
magnetically recovered
recovered after
after aa simple
simple process
process
(washing ◦
(washingwith
withisopropanol
isopropanoland anddried over
dried 105105C)°C)
over for for
the the
subsequent recycling
subsequent tests.tests.
recycling The recycling tests
The recycling
for the Ni/CNT catalyst in the transfer hydrogenation of phenol under the optimal reaction
tests for the Ni/CNT catalyst in the transfer hydrogenation of phenol under the optimal reaction condition
condition was subsequently evaluated. Ni/CNT maintained its activity for four succeeding runs, and
no obvious decrease in cyclohexanol yield was observed, suggesting the good ability of the catalyst
(Figure 7b).
 Figure 6. Catalytic pathway in the transfer hydrogenation of phenol.

In addition, the Ni/CNT catalyst could be magnetically recovered after a simple process
(washing with
Energies 2020, isopropanol and dried over 105 °C) for the subsequent recycling tests. The recycling
13, 846 10 of 12
tests for the Ni/CNT catalyst in the transfer hydrogenation of phenol under the optimal reaction
condition was subsequently evaluated. Ni/CNT maintained its activity for four succeeding runs, and
was subsequently evaluated. Ni/CNT maintained its activity for four succeeding runs, and no obvious
no obvious decrease in cyclohexanol yield was observed, suggesting the good ability of the catalyst
decrease in cyclohexanol yield was observed, suggesting the good ability of the catalyst (Figure 7b).
(Figure 7b).

Figure
Figure7.7.(a)
(a)Possible
Possiblecatalytic
catalyticpathway
pathwayin inthe
thetransfer
transferhydrogenation
hydrogenationof
ofphenol.
phenol.(b)
(b)Result
Resultof
ofrecycling
recycling
tests
testsfor
forNi/CNT
Ni/CNT catalyst
catalyst in
in the
the transfer
transfer hydrogenation
hydrogenation ofof phenol.
phenol.

3.Conclusions
3. Conclusions
In this paper,
In paper,phenol
phenolwas waseffectively hydrogenated
effectively hydrogenated to cyclohexanol by 20%
to cyclohexanol by Ni/CNT
20% Ni/CNTcatalyst under
catalyst
a mild condition
under (220 ◦ C, 60
a mild condition min)
(220 using
°C, isopropanol
60 min) as the hydrogen-donor
using isopropanol solvent. The Ni/CNT
as the hydrogen-donor catalyst
solvent. The
not only had an excellent ability to catalyze the transfer hydrogenolytic cleavage of phenol
Ni/CNT catalyst not only had an excellent ability to catalyze the transfer hydrogenolytic cleavage of and diverse
phenol derivatives
phenol and diversebut also could
phenol be easilybut
derivatives recovered magnetically
also could be easilyfrom the reaction
recovered process for
magnetically the next
from the
four recycling
reaction processtests.
for Four succeeding
the next recycling
four recycling testsFour
tests. in thesucceeding
transfer hydrogenation
recycling testsof in
phenol proved
the transfer
the good stability
hydrogenation of the Ni/CNT
of phenol proved thecatalyst.
good The possible
stability of themechanism for the The
Ni/CNT catalyst. hydrogenation of phenol
possible mechanism
suggested
for that the possible
the hydrogenation pathway
of phenol might proceed
suggested via possible
that the the formation of cyclohexanone.
pathway might proceedThis viawork
the
will inspire
formation ofvarious studies on
cyclohexanone. thework
This hydrogenation
will inspireprocess
variousinstudies
the absence
on the ofhydrogenation
additional hydrogen.
process in
the absence of additional hydrogen.
Author Contributions: Conceptualization, M.Z. and J.J.; methodology, M.Z.; software, J.J.; validation, M.Z., B.K.S.
and J.J.; formal analysis, C.C.; investigation, C.C.; resources, P.L.; data curation, P.L.; writing—original draft
preparation, C.C.; writing—review and editing, M.Z.; visualization, M.Z.; supervision, J.J.; project administration,
M.Z.; funding acquisition, M.Z. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Fundamental Research Funds of CAF, grant number CAFYBB2018QB007
and the National Natural Science Foundation of China, grant number 31700645.
Acknowledgments: Authors are grateful for the financial support from the Fundamental Research Funds of CAF
(No. CAFYBB2018QB007) and the National Natural Science Foundation of China (31700645).
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
CNT Carbon nanotube
ICP Inductive Coupled Plasma Emission Spectrometer
XRD Powder X-ray diffraction
XPS X-Ray photoelectron spectroscopy
TEM Transmission electron microscopy
BET Brunauer- Emmett- Teller
GC/MS Gas Chromatograph/Mass Spectrometer
Energies 2020, 13, 846 11 of 12

References
1. Xiang, Y.; Ma, L.; Lu, C.; Zhang, Q.; Li, X. Aqueous system for the improved hydrogenation of phenol and its
derivatives. Green Chem. 2008, 10, 939–943. [CrossRef]
2. Xiang, Y.; Kong, L.; Xie, P.; Xu, T.; Wang, J.; Li, X. Carbon nanotubes and activated carbons supported
catalysts for phenol in situ hydrogenation: Hydrophobic/hydrophilic effect. Ind. Eng. Chem. Res. 2014, 53,
2197–2203. [CrossRef]
3. Porwal, G.; Gupta, S.; Sreedhala, S.; Elizabeth, J.; Khan, T.S.; Haider, M.A.; Vinod, C.P. Mechanistic insights into
the pathways of phenol hydrogenation on Pd nanostructures. ACS Sustain. Chem. Eng. 2019, 7, 17126–17136.
[CrossRef]
4. Song, Z.; Ren, D.; Wang, T.; Jin, F.; Jiang, Q.; Huo, Z. Highly selective hydrothermal production of cyclohexanol
from biomass-derived cyclohexanone over Cu powder. Catal. Today 2016, 274, 94–98. [CrossRef]
5. Sikhwivhilu, L.M.; Coville, N.J.; Naresh, D.; Chary, K.V.; Vishwanathan, V. Nanotubular titanate supported
palladium catalysts: The influence of structure and morphology on phenol hydrogenation activity. Appl. Catal.
A Gen. 2007, 324, 52–61. [CrossRef]
6. Wang, L.; Zhang, Y.; Du, R.; Yuan, H.; Wang, Y.; Yao, J.; Li, H. Selective one-step aerobic oxidation
of cyclohexane to -caprolactone mediated by N-hydroxyphthalimide (NHPI). ChemCatChem 2019, 11,
2260–2264. [CrossRef]
7. Alazman, A.; Belic, D.; Alotaibi, A.; Kozhevnikova, E.F.; Kozhevnikov, I.V. Isomerization of cyclohexane over
bifunctional Pt-, Au-, and PtAu-heteropoly acid Catalysts. ACS Catal. 2019, 9, 5063–5073. [CrossRef]
8. Kim, A.R.; Ahn, S.; Yoon, T.U.; Notestein, J.M.; Farha, O.K.; Bae, Y.S. Fast cyclohexane oxidation under
mild reaction conditions through a controlled creation of Redox-active Fe (II/III) Sites in a Metal-organic
Framework. ChemCatChem 2019, 11, 5650–5656. [CrossRef]
9. Chary, K.V.; Naresh, D.; Vishwanathan, V.; Sadakane, M.; Ueda, W. Vapour phase hydrogenation of phenol
over Pd/C catalysts: A relationship between dispersion, metal area and hydrogenation activity. Catal. Commun.
2007, 8, 471–477. [CrossRef]
10. Nelson, N.C.; Manzano, J.S.; Sadow, A.D.; Overbury, S.H.; Slowing, I.I. Selective hydrogenation of phenol
catalyzed by palladium on high-surface-area ceria at room temperature and ambient pressure. ACS Catal.
2015, 5, 2051–2061. [CrossRef]
11. Zhang, X.; Du, Y.; Jiang, H.; Liu, Y.; Chen, R. Insights into the stability of Pd/CN catalyst in liquid phase
hydrogenation of phenol to cyclohexanone: Role of solvent. Catal. Lett. 2019, 149, 1–10. [CrossRef]
12. Liu, T.; Zhou, H.; Han, B.; Gu, Y.; Li, S.; Zheng, J.; Zhong, X.; Zhuang, G.L.; Wang, J.G. Enhanced selectivity
of phenol hydrogenation in low-pressure CO2 over supported Pd catalysts. ACS Sustain. Chem. Eng. 2017, 5,
11628–11636. [CrossRef]
13. Sanyal, U.; Song, Y.; Singh, N.; Fulton, J.L.; Herranz, J.; Jentys, A.; Gutiérrez, O.Y.; Lercher, J.A. Structure
sensitivity in hydrogenation reactions on Pt/C in aqueous-phase. ChemCatChem 2019, 11, 575–582. [CrossRef]
14. Singh, N.; Lee, M.S.; Akhade, S.A.; Cheng, G.; Camaioni, D.M.; Gutiérrez, O.Y.; Glezakou, V.A.; Rousseau, R.;
Lercher, J.A.; Campbell, C.T. Impact of pH on aqueous-phase phenol hydrogenation catalyzed by
carbon-supported Pt and Rh. ACS Catal. 2018, 9, 1120–1128. [CrossRef]
15. Wang, L.; Zhang, J.; Yi, X.; Zheng, A.; Deng, F.; Chen, C.; Ji, Y.; Liu, F.; Meng, X.; Xiao, F.S. Mesoporous
ZSM-5 zeolite-supported Ru nanoparticles as highly efficient catalysts for upgrading phenolic biomolecules.
ACS Catal. 2015, 5, 2727–2734. [CrossRef]
16. Nakagawa, Y.; Ishikawa, M.; Tamura, M.; Tomishige, K. Selective production of cyclohexanol and methanol
from guaiacol over Ru catalyst combined with MgO. Green Chem. 2014, 16, 2197–2203. [CrossRef]
17. Martinez-Espinar, F.; Blondeau, P.; Nolis, P.; Chaudret, B.; Claver, C.; Castillón, S.; Godard, C. NHC-stabilised
Rh nanoparticles: Surface study and application in the catalytic hydrogenation of aromatic substrates. J. Catal.
2017, 354, 113–127. [CrossRef]
18. Kinoshita, A.; Nakanishi, K.; Yagi, R.; Tanaka, A.; Hashimoto, K.; Kominami, H. Hydrogen-free ring
hydrogenation of phenol to cyclohexanol over a rhodium-loaded titanium (IV) oxide photocatalyst. Appl. Catal.
A Gen. 2019, 578, 83–88. [CrossRef]
19. Wang, Y.; Yao, J.; Li, H.; Su, D.; Antonietti, M. Highly selective hydrogenation of phenol and derivatives over
a Pd@carbon nitride catalyst in aqueous media. J. Am. Chem. Soc. 2011, 133, 2362–2365. [CrossRef]
Energies 2020, 13, 846 12 of 12

20. Zhao, C.; Song, W.; Lercher, J.A. Aqueous phase hydroalkylation and hydrodeoxygenation of phenol by dual
functional catalysts comprised of Pd/C and H/La-BEA. ACS Catal. 2012, 2, 2714–2723. [CrossRef]
21. Li, Z.; Liu, J.; Xia, C.; Li, F. Nitrogen-functionalized ordered mesoporous carbons as multifunctional supports
of ultrasmall Pd nanoparticles for hydrogenation of phenol. ACS Catal. 2013, 3, 2440–2448. [CrossRef]
22. Galkin, M.V.; Sawadjoon, S.; Rohde, V.; Dawange, M.; Samec, J.S. Mild Heterogeneous Palladium-Catalyzed
Cleavage of β-O-40 -Ether Linkages of Lignin Model Compounds and Native Lignin in Air. ChemCatChem
2014, 6, 179–184. [CrossRef]
23. Paone, E.; Espro, C.; Pietropaolo, R.; Mauriello, F. Selective arene production from transfer hydrogenolysis of
benzyl phenyl ether promoted by a co-precipitated Pd/Fe3 O4 catalyst. Catal. Sci. Technol. 2016, 6, 7937–7941.
[CrossRef]
24. Wu, H.; Song, J.; Xie, C.; Wu, C.; Chen, C.; Han, B. Efficient and mild transfer hydrogenolytic cleavage of
aromatic ether bonds in lignin-derived compounds over Ru/C. ACS Sustain. Chem. Eng. 2018, 6, 2872–2877.
[CrossRef]
25. Zhang, Q.; Li, H.; Gao, P.; Wang, L. PVP-NiB amorphous catalyst for selective hydrogenation of phenol and
its derivatives. Chin. J. Catal. 2014, 35, 1793–1799. [CrossRef]
26. Gilkey, M.J.; Xu, B. Heterogeneous transfer hydrogenation as an effective pathway in biomass upgrading.
ACS Catal. 2016, 6, 1420–1436. [CrossRef]
27. Croston, M.; Langston, J.; Sangoi, R.; Santhanam, K.S.V. Catalytic oxidation of p-toluidine at multiwalled
functionalized carbon nanotubes. Int. J. Nanosci. 2002, 1, 277–283. [CrossRef]
28. Croston, M.; Langston, J.; Takacs, G.; Morrill, T.C.; Miri, M.; Santhanam, K.S.V.; Ajayan, P. Conversion of
aniline to azobenzene at functionalized carbon nanotubes: A possible case of a nanodimensional reaction.
Int. J. Nanosci. 2002, 1, 285–293. [CrossRef]
29. Gordon, M.; Santhanam, K.S.V. High product yield in a narrow column configuration of carbon nanotubes:
A Pathway for nanosynthetic machine. Proc. Electrochem. Soc. 2003, 13, 285–288.
30. Zhou, M.; Tian, L.; Niu, L.; Li, C.; Xiao, G.; Xiao, R. Upgrading of liquid fuel from fast pyrolysis of biomass
over modified Ni/CNT catalysts. Fuel Process. Technol. 2014, 126, 12–18. [CrossRef]
31. Zhou, M.; Zhu, H.; Niu, L.; Xiao, G.; Xiao, R. Catalytic hydroprocessing of furfural to cyclopentanol over
Ni/CNTs catalysts: Model reaction for upgrading of bio-oil. Catal. Lett. 2014, 144, 235–241. [CrossRef]
32. Zhang, J.; Chen, C.; Yan, W.; Duan, F.; Zhang, B.; Gao, Z.; Qin, Y. Ni nanoparticles supported on CNTs
with excellent activity produced by atomic layer deposition for hydrogen generation from the hydrolysis of
ammonia borane. Catal. Sci. Technol. 2016, 6, 2112–2119. [CrossRef]
33. Li, G.; Han, J.; Wang, H.; Zhu, X.; Ge, Q. Role of dissociation of phenol in its selective hydrogenation on Pt
(111) and Pd (111). ACS Catal. 2015, 5, 2009–2016. [CrossRef]
34. Song, Y.; Chia, S.H.; Sanyal, U.; Gutiérrez, O.Y.; Lercher, J.A. Integrated catalytic and electrocatalytic
conversion of substituted phenols and diaryl ethers. J. Catal. 2016, 344, 263–272. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).