Fuel 203 (2017) 23–31

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Fuel
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Full Length Article

Hydrogenation of biomass-derived ethyl levulinate into c-valerolactone

by activated carbon supported bimetallic Ni and Fe catalysts
Chuang Li, Guangyue Xu, Yongxiang Zhai, Xiaohao Liu, Yanfu Ma, Ying Zhang ⇑
iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory for Biomass Clean Energy and Department of Chemistry, University of Science
and Technology of China, Hefei 230026, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Bimetallic Ni-Fe/AC catalysts with

different Fe/Ni ratios are prepared.

Ni-Fe/AC catalysts are efficient for
catalyzing EL to GVL under mild
conditions.

The catalysts are characterized by
XRD, TEM, HRTEM, EDX, XPS, H2-TPR
and NH3-TPD.

Ni-Fe alloy and co-presented FeOx
contribute to the high catalytic
activity.

The Ni-Fe/AC catalysts can be easily
separated due to their strong magnet.

a r t i c l e i n f o a b s t r a c t

Article history: Gamma-valerolactone (GVL) has been identified as a sustainable high-value platform molecular for the
Received 7 February 2017 production of fuels and carbon-based chemicals. In this work, a series of activated carbon supported
Received in revised form 14 April 2017 low-cost bimetallic Ni-Fe catalysts (Ni-Fe/AC) with different molar content of Fe species were prepared
Accepted 19 April 2017
by using co-precipitation method for the liquid phase hydrogenation of ethyl levulinate (EL) to produce
Available online 27 April 2017
c-valerolactone. The Ni-Fe0.5/AC exhibited the highest activity among the bimetallic or monometallic cat-
alysts under mild reaction conditions (100 °C, 4 MPa H2, 6 h) and achieved 99.3% conversion of EL and
Keywords:
99.0% yield of GVL. Under more mild conditions (60 °C, 2 MPa H2) and prolonging the reaction time to
Ni-Fe catalysts
Hydrogenation
24 h, EL could be converted completely and the obtained GVL yield was more than 98%. The catalysts
Ethyl levulinate were characterized by various techniques including XRD, TEM, HRTEM, EDX, XPS, H2-TPR and NH3-
c-Valerolactone TPD. Based on the structure and activity relationship study, the formation of highly dispersed Ni-Fe alloy
Biomass conversion structure and the co-presented FeOx nanoparticles could be responsible for the high catalytic hydrogena-
Fuel tion activity.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Biomass is the most abundant, inexpensive and renewable
organic carbon resource, which is identified as an ideal promising
⇑ Corresponding author.
E-mail address: zhzhying@ustc.edu.cn (Y. Zhang).
green feedstock for the production of fuels and chemicals [1–4].
The related study is attracting more and more attention for the
environmental and sustainable concerns [5]. So far, biomass has
been converted into fuels and diverse value-added chemicals
including different alcohols [6,7], formic acid (FA) [8], gluconic acid
[9,10], etc. Various downstream products are obtained when glu-
cose monomers are further converted, such as levulinic acid (LA)

http://dx.doi.org/10.1016/j.fuel.2017.04.082
0016-2361/Ó 2017 Elsevier Ltd. All rights reserved.
24 C. Li et al. / Fuel 203 (2017) 23–31
[11,12] or levulinate esters [13,14], 2,5-furandicarboxylic acid
(FDCA) [15,16], furfural alcohol (FAL) [17], 2,5-dimethylfuran
(DMF) [18,19] and c-valerolactone (GVL) [20–22], etc. Among
these chemicals, levulinic acid or its esters is regarded as one of
the ten most important biomass platform molecule compounds
[23,24], as it can be obtained by the dehydration of carbohydrates
[25] or alcoholysis [26–28], meanwhile, it can be further converted
to fuels or various high-value products. Notably, the hydrogenation
of levulinic acid or its esters to GVL (as shown in Scheme 1) is one
of the key reactions in sustainable biomass conversion [29,30]. GVL
is highly stable, low toxic, safe to store and can be widely utilized
as liquid fuel, fuel additive, food additive, green solvent for biomass
processing and intermediate for the production of fine chemicals
[31–33]. Especially, GVL is ready used as the blending agent of
gasoline, diesel, or biodiesel fuel due to its heating value and
higher energy density. Horvath et al. [34] showed that a mixture
of 90% gasoline and 10% GVL has a similar octane value to a mix-
ture of 90% gasoline and 10% ethanol, while GVL improves the
burning characteristics of the fuel due to its low vapor pressure.
To date, a considerable amount of work has been done on the
hydrogenation of LA or its esters to GVL using homogeneous or
heterogeneous catalysts. According to the previous reports, homo-
geneous catalysts such as RuCl3, Ru(acac)3 ligated with P(Oct)3,
TPPTS or DPPDS have been successfully applied to hydrogenate
LA to GVL with excellent yields [35,36]. However, for practical
application, homogeneous catalysts suffer from noble metals and
complex ligands, and poor recyclability due to the difficulty in
the catalyst/product separation [37]. Heterogeneous catalysts
reported for the hydrogenation of LA primarily include various
metals (e.g. Pd, Pt, Au, Ru, Ir, Rh and Re) supported on activated
carbon (AC) or other carriers [38–42] converted LA to GVL with
over 95% yield, at 150 °C under 5.52 MPa H2 for 2 h. However,
the noble metal-based catalysts suffer from low abundance in
earth, which limited their large-scale industrial application to pro-
duce GVL [43].
It is highly desirable to develop economically feasible, abundant
and recyclable catalysts for GVL production [44]. Pravin et al. [45]
reported nanocomposite catalysts of Cu/SiO2 with tunable Cu load-
ings for almost full conversion of LA to GVL in vapor-phase condi-
tions (265 °C, 2.5 MPa H2). Mohan et al. [46] examined the Ni/
HZSM-5 catalyst at 250 °C and 1 bar H2 and achieved 100% LA con-
version and 92.2% selectivity to GVL. Velisoju et al. [47] screened Ni
(20 wt%) supported on SiO2, c-Al2O3 and ZrO2 catalysts for hydro-
genation of aqueous LA or esters to GVL at 270 °C and ambient
pressure. Up to now, most of the reported transition metal based
catalysts required relatively high reaction temperatures with H2
gas as H-donor, such as 265 °C for Cu/SiO2 catalysts and 250–
270 °C for Ni-based catalysts.
Currently, various multifunctional bimetallic catalysts including
Ru-Sn [48], Pd-Au [49], Ni-MoOx/C [37], Cu-Cr [50] and Cu-Fe [51]
Scheme 1. The transformation of cellulose to c-valerolactone.
were also employed in the hydrogenation of LA or its esters to GVL.
Thereinto, Li [50] synthesized stable and efficient CuCr catalyst and
it showed rather high catalytic capacity for the solvent-free hydro-
genation of ethyl levulinate (EL) to GVL in a yield up to 95%. Yan
[51] reported Cu-Fe catalyst, which exhibited highly efficient per-
formance in the hydrogenation of biomass-derived levulinic acid
with 90.1% GVL yield under mild vapor phase temperature
(200 °C). Recently, studies have shown that Fe species can act as
an electronic/chemical promoter to modify metal catalysts and
result in enhanced catalytic activity and selectivity because it
increases the surface area and dispersion of host metal elements
[52]. The multifunctional catalysts are becoming a hot research
topic owing to their tunable composition and size, excellent dis-
persion and electronic properties, which closely link to various
applications including magnetism, electronics and especially cat-
alytic activity [53–55]
Given the hydrogenation activity of Ni and the synergistic
effect of Fe as well as their low cost, herein, we developed an
activated carbon supported non-noble bimetallic Ni and Fe
heterogeneous catalyst (Ni-Fe/AC) for liquid phase hydrogenation
of EL to GVL. Using EL instead of LA as the feedstock is based on
the following consideration. LA is generally produced by the
dehydration of carbohydrates lignocellulose by hydrolysis in
strong acidic medium, wherein during this process, it is inevita-
bly generating polymeric humin due to the thermal decomposi-
tion of intermediates and leading to a low yield of LA [56,57].
However, the formation of humin can be significantly inhibited
(up to 70%) by alcoholysis in various alcoholic medium owing
to the formation of the corresponding levulinic esters in high
yield (95%) compared with LA (25%) from C6 sugars [58]. What’s
more, levulinate esters are more easily separated from the reac-
tion system and the efficient recycling advantage of alcohols dur-
ing the sustainable synthesis will greatly reduce the costs [59].
Furthermore, the catalytic hydrogenation of levulinic esters to
GVL route can effectively inhibit the active metal leaching from
the hydrogenation catalysts caused by the free carboxyl of LA
[28].
In this study, a series of activated carbon supported bimetallic
Ni-Fe catalyst were prepared by using co-precipitation method to
catalyze biomass-derived EL for the production of GVL. The various
effects including molar content of Fe species, reaction temperature,
H2 pressure and reaction time on the reaction were studied. Fur-
thermore, the relationship of the structure and activity was studied
systematically by various characterization techniques of X-ray
power diffraction (XRD), transmission electron microscopy (TEM),
high-resolution transmission electron microscopy (HRTEM),
energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron
spectroscopy (XPS), H2 temperature-programmed reduction (H2-
TPR) and the temperature-programmed desorption of ammonia
(NH3-TPD).
 C. Li et al. / Fuel 203 (2017) 23–31
2. Experimental section
2.1. Materials
All the reagents used in this study were analytical grade and
used without further purification. Ethyl levulinate (EL) was pur-
chased from Aladdin Chemistry Co; Ni(NO3)26H2O, Fe(NO3)39H2O
and N,N-dimethylformamide were supplied by Sinopharm
Chemical Reagent Co. Ltd; activated carbon (AC) was purchased
from TCI; deionized water was supplied by Hangzhou Wahaha
Group Co. Ltd.
2.2. Catalysts preparation
A series of Ni-Fe/AC catalysts with different Fe and Ni molar
ratios were prepared by co-precipitation method. All the bimetallic
Ni-Fe catalysts were prepared by keeping the Ni loading constant
at 7% but varying Fe/Ni molar ratios. The catalysts were labeled
as Ni-Fex/AC (x represent the molar ratio of Fe to Ni). A typical cat-
alyst preparing procedure was as follows: 1 g of AC was added into
100 g of deionized water in a 250 ml round-bottom flask and stir-
red at 45 °C. A certain amount of Ni(NO3)26H2O (346 mg) and a
pre-calculated amount of Fe(NO3)39H2O were dissolved in deion-
ized water (5 g) and then dropwise added into the above activated
carbon/deionized water under magnetic stirring. The mixture was
stirred vigorously for 4 h. After that, 0.1 molL1 aqueous ammonia
was slowly dripped into the mixture solution to get final pH value
of 10. The mixture was then stirred vigorously for another 3 h. Sub-
sequently, the suspension was filtered and washed with distilled
water for several times until the final pH value was 7. The solid
was transferred into an oven and dried at 105 °C for 12 h. After dry-
ing, the sample was calcined in a furnace with temperature raised
from 20 °C to 300 °C at a rate of 1 °Cmin1 and kept at 300 °C for
another 4 h to form the catalyst precursor. Before the experimental
reaction, the precursor was reduced in a tube furnace by 10%
H2/90% N2 mixed gas with the flow rate of 100 mlmin1. The tem-
perature reduction program of the tube furnace was raised from
20 °C to 120 °C by 3 °Cmin1, kept for 20 min at 120 °C and then
raised again from 120 °C to 400 °C with 1 °Cmin1 and kept for
another 4 h. All the as-reduced catalysts were stored by liquid seal
method.
2.3. Catalyst characterization
X-ray power diffraction (XRD) patterns of the catalysts were
measured by an X’pert (PANalytical) diffractometer, using CuKa
radiation at 40 kV and 40 mA, 2h ranges were 10°–70°. The crystal
sizes were calculated by Scherrer equation through the Ni (1 1 1)
and Fe (1 1 0) or their mixed crystal diffraction peak: < L >¼ bcosh
kk
,
where K is a constant and equal to 0.89, k is the X-ray wavelength
and equal to 0.154056 nm, b is the full width at half maximum
(rad) and h is the diffraction angle (rad).
The transmission electron microscopy (TEM) images were
taken with a JEOL JEM-2010 LaB6 transmission electron
microscope. Before the test, the samples were deposited on Cu
grids after ultrasonic dispersion of the milled catalyst samples in
ethanol.
The temperature-programmed reduction (TPR) was carried out
in a home-built reactor system coupled to a gas chromatograph.
Before TPR tests, the samples were pretreated in Ar flow at
200 °C for 1 h. The TPR was carried out in a 5% H2/Ar mixture gas
flow from 40 °C to 800 °C with a heating rate of 10 °C/min. The liq-
uid nitrogen/ethanol cooling bath was used to remove the mois-
ture from the effluent stream before the stream entered a
thermal conductivity detector (TCD).
25
The X-ray photoelectron spectroscopy (XPS) spectra were
obtained with a Thermo Scientific Escalab 250 X-ray photoelectron
spectrometer (ESCALAB250).
The temperature-programmed desorption of ammonia (NH3-
TPD) was carried out in a home-built reactor system coupled to a
gas chromatograph. The catalysts were treated at 500 °C under
Ar flow (ultrahigh purity, 20.5 mL/min) for 60 min, and the adsorp-
tion of ammonia (65.5 mL/min) was carried out at 40 °C for 60 min.
After that, the catalysts were flushed with Ar flow (ultrahigh pur-
ity, 20.5 mL/min) at 40 °C for 60 min, and the temperature-
programmed desorption of NH3 was run from 40 to 800 °C with
a heating rate of 10 °C/min. The desorbed ammonia was measured
by a gas chromatograph (GC-SP6890, Shandong Lunan Ruihong
Chemical Instrument Co. Ltd., Tengzhou China) with a thermal con-
ductivity detector (TCD).
2.4. Catalyst test
All catalytic reactions for hydrogenation of ethyl levulinate to c-
valerolactone were performed in a 25 ml Parr reactor. In a typical
experiment, 100 mg of ethyl levulinate, certain amount of catalyst
and solvent (10 ml of deionized water) were added into the reac-
tor. After purged for 6 times, H2 was filled to corresponding pres-
sure at ambient temperature. The reaction temperature and the
reaction time were kept at certain values with magnetic stirring.
After the reaction, when the reactor was cooled to room tempera-
ture, the products were separated from the catalyst by an external
magnet and then diluted with ethanol. Finally, the collected sam-
ple solution was identified by a gas chromatograph-mass spec-
trometer combination (GC–MS, Agilent 5975C) and quantified by
a gas chromatograph (Kexiao 1690) with HP-INNOWAX capillary
column (30 m * 0.250 mm * 0.25 lm). The GC detecting conditions
were as follows: nitrogen as carrier gas; injection port tempera-
ture: 280 °C; detector (FID) temperature: 280 °C; column tempera-
ture: 100 °C, heating up to 250 °C with a heating rate of 5 °C/min.
N,N-dimethylformamide was used as internal standard to quantify
the products. In this paper, the experiments were repeated for
three times and the data were the average value with experimental
error less than 2%.
The conversion and yield were calculated by mol%.
 
molar amount of EL after reaction
Conv:ð%Þ ¼ 1 
molar amount of EL in the starting material
 100%
molar amount of GVL product
Yieldð%Þ ¼  100%
molar amount of EL in the starting material
3. Results and discussion
3.1. Catalyst characterization
The XRD patterns of the as-reduced Ni-Fe/AC catalysts with dif-
ferent molar content of Fe species with constant Ni loading at
7.0 wt% are shown in Fig. 1. The broad diffraction peak at
2h = 25.0° was assigned to the activated carbon support. The XRD
patterns of the 7.0 wt% Fe/AC and Ni/AC catalysts are also given
for comparison. For the Fe/AC catalyst, only a weak diffraction peak
of Fe species was observed at 2h = 44.9°. The distinct diffraction
peaks of the Ni/AC at 2h = 44.7°, 51.9° were observed attributing
to Ni0 (1 1 1) and (2 0 0) (JCPDS Nos. 00-001-1258 and 00-001-
1262). For the Ni-Fe/AC catalysts, with Fe content increasing, the
position of the two diffraction peaks shifted to 44.3° and 51.5°,
respectively, which were ascribed to the diffractions of Ni3-Fe1
26 C. Li et al. / Fuel 203 (2017) 23–31
Fig. 1. XRD patterns of the as-reduced N-Fe/AC catalysts with different molar
content of Fe species: a) AC; b) Fe/AC; c) Ni/AC; d) Ni-Fe0.2/AC; e) Ni-Fe0.5/AC; f) Ni-
Fe1/AC; g) Ni-Fe2/AC.
alloy phase (PDF 00-038-0419), indicating the formation of Ni-Fe
alloy, which was consistent with the previous reports [60–62].
The XRD diffraction lines of the Ni-Fe alloy were similar to
monometallic Ni, which revealed their similar face-centered cubic
structures and lattice constants [60]. As the Fe amount further
increased, the diffraction peaks of Fe0 emerged at 2h = 44.9° in
samples of Ni-Fe1/AC and Ni-Fe2/AC comparing with the other cat-
alysts (Fig. 1c and d) because partial iron oxide was reduced at
400 °C, which was probably promoted by Ni. In the meantime,
the distinct diffraction peaks of Fe2O3 were observed at 30.2°,
35.6°, 57.3° and 62.9° of Ni-Fe2/AC, resulting from the excessive
Fe species in this sample.
The TEM images and particle size distributions of the as-
reduced samples are shown in Fig. 2. The mean size of the
monometallic Ni/AC was 8.0 nm. When adding a certain amount
of Fe into the monometallic Ni/AC, the mean nanoparticle sizes
of bimetallic Ni-Fe0.2/AC and Ni-Fe0.5/AC catalysts decreased to
7.6 nm and 7.1 nm, respectively. Especially, for the Ni-Fe0.5/AC cat-
alyst, the dispersion of metal nanoparticles was more uniform and
the particle size distribution was narrower than that of other sam-
ples. It could be attributed to the interactions between the two
metals, known as the geometric and stabilizing effect, and the
addition of moderate second metal promoter alters the geometry
of the particle size and improves the stability of the active metal
sites by inhibiting metal sintering during the preparation or reac-
tion [63]. However, the metal particle sizes of Ni-Fe1/AC catalyst
increased when further introducing a greater amount of Fe. Intro-
ducing excessive Fe species (Ni-Fe2/AC) led to particles aggregation
(Fig. 2e), which was similar to Fe/AC (Fig. 2f). The microstructure of
Ni-Fe0.5/AC was also characterized using high-resolution transmis-
sion electron microscopy (HRTEM) and energy dispersive X-ray
spectroscopy (EDX) (Fig. 2g and h). The clear crystalline fringe of
the selected domain was measured to be 0.205 nm, which corre-
sponds to the (1 1 1) interplanar spacing of the face-centered cubic
structure of the Ni-Fe alloy [64]. The EDX spectroscopy further pro-
vided the composition of Ni-Fe alloy particle in the Ni-Fe0.5/AC cat-
alyst. All these results further confirmed the formation of alloy
between Ni and Fe, which agreed well with the XRD results.
Fig. 3 shows the temperature-programmed reduction of hydro-
gen (H2-TPR) profiles of the as-calcined Ni-Fe/AC samples. For the
as-calcined 7.0 wt% Fe/AC catalyst, two distinct peaks appeared in
the TPR profile. The first peak at around 360 °C was assigned to the
reduction of Fe2O3 to Fe3O4, however, the less H2 consumption
than other catalysts indicating that only trace iron oxide was
reduced. In addition, the broad peak at approximately 600 °C was
assigned to the reduction of Fe3O4 to Fe0 and the results revealed
that Fe species could not be reduced to Fe0 at the reduction tem-
perature of 400 °C. The as-calcined sample for the monometallic
Ni/AC catalyst presented a broad peak ranging from 250 °C to
550 °C with the maximum at 350 °C, which is typically attributed
to the reduction of NiO to Ni0. The obtained TPR curves of the
bimetallic catalysts in the present work showed that when adding
Fe species into the Ni/AC system, the H2 consumption peak of the
as-calcined sample shifted to higher temperature and was stronger
than the NiO reduction peak, suggesting that some interactions
between Ni and Fe species possibly occurred and Fe species were
also reduced.
Characterization of the X-ray photoelectron spectroscopic (XPS)
were performed to identify the species of Ni and Fe after reduction.
Fig. 4 shows the Ni 2p and Fe 3p spectra of the Ni/AC, Fe/AC and Ni-
Fe0.5/AC samples. For the as-reduced monometallic Ni/AC and
bimetallic Ni-Fe0.5/AC samples showing in Fig. 4A, there are three
kinds of Ni could be identified, Ni0 (2p3/2: 852.4 eV and 2p1/2:
870.0 eV), NiO (2p3/2: 855.0 eV and 2p1/2: 873.3 eV) and Ni(OH)2
(2p3/2: 859.8 eV and 2p1/2: 879.5 eV). The peak at approximately
855.0 eV was attributed to NiO, probably because the as-reduced
Ni0 were partially oxidized by contacting with air. Table S1 showed
ratio analysis of the peaks in XPS spectra in Ni/AC and Ni-Fe0.5/AC
catalysts. The content of Ni0 on the surface of the bimetallic cata-
lyst increased obviously and its binding energy shifted 0.4 eV com-
paring to the monometallic Ni/AC, which indicated that the
electronic properties of Ni species changed with a second metal
introduction [65,63]. For the as-reduced Fe/AC sample (Fig. 4B),
the binding energy of Fe 2p3/2 at approximately 710.8 eV and
712.2 eV was typically attributed to Fe2O3, Fe3O4, respectively,
which demonstrated that the Fe species on AC were hardly reduced
to Fe0 under the present conditions (400 °C for 4 h). The diffraction
peaks of Fe3O4 could not be observed in the XRD patterns, probably
the structure of Fe3O4 was amorphous in the bimetallic samples.
However, a new peak appeared at 707.1 eV of the Ni-Fe0.5/AC cat-
alyst, which was assigned to Fe0 species. The Fe3O4 and Fe0
emerged in bimetallic catalysts indicating that the partial iron
oxide reduction was promoted by the exited Ni. These results also
could be confirmed by the H2-TPR and XRD analysis.
3.2. Catalytic hydrogenation of EL to GVL
Reaction conditions: 40 mg supported metal catalyst; 100 mg
EL; 10 mL water as solvent; 4 MPa H2; 100 °C; 6 h; 800 rpm; a.
Physical mixture of Ni/AC and Fe/AC.
The performance of the Ni-Fe/AC catalysts on the hydrogena-
tion of EL with different Fe/Ni molar ratios is listed in Table 1.
The monometallic Ni/AC catalyst prepared by precipitation method
was used to catalyze ethyl levulinate and the GVL yield was 51.7%.
The monometallic Fe/AC catalyst presented almost negligible effect
on the conversion of EL to GVL under identical conditions. How-
ever, when a small amount of Fe was added into Ni/AC (e.g. Ni-
Fe0.2/AC), EL conversion and GVL yield increased significantly. With
the increase of Fe amount in Ni-Fe/AC, the conversion and yield
further increased and reached a maximum (99.3% and 99.0%,
respectively) with Ni-Fe0.5/AC. According to the previous studies,
the synthesis process from EL to GVL involves two-step reaction:
hydrogenation and lactonization, thereinto, the first step of activa-
tion and hydrogenation of the carbonyl group is considered to be
the rate-determining step [66,67]. It has been reported that Lewis
acid sites are benefit to attract and activate carbanyl group (C@O)
through interactions with the electron pair of oxygen atom, which
should result in the enhancement of the reactivity of carbonyl
 C. Li et al. / Fuel 203 (2017) 23–31 27

Fig. 2. TEM images of (a) Ni/AC, (b) Ni-Fe0.2/AC, (c) Ni-Fe0.5/AC, (d) Ni-Fe1/AC, (e) Ni-Fe2/AC and (f) Fe/AC; (g) HRTEM image of the Ni-Fe0.5/AC catalyst; (h) EDX spectrum of a
single Ni-Fe alloy particle in the Ni-Fe0.5/AC catalyst.

compounds [48,68]. Herein, the acid sites of catalysts were mea-
sured by NH3-TPD (Fig. S1). It indicated that the Fe species in form
of FeOx increased the weak acid sites in Ni-Fe/AC samples. The acid
sites approached maximum as Fe/Ni molar ratio at 0.5, which
resulted in a remarked enhancement in the activation of the car-
bonyl group. Ni-Fe alloy, as hydrogenation active sites, can effi-
ciently hydrogenate the activated carbonyl groups of the
substrate [69]. Therefore, the bimetallic Ni-Fe/AC catalysts exhib-
ited higher catalytic activity for the hydrogenation of EL to GVL.
Notably, for the bimetallic Ni-Fe0.5/AC catalyst, both the activation
sites and the hydrogenation sites presented their optimal propor-
tion on the support. Furthermore, based on the TEM results, the
nanoparticles of the Ni-Fe alloy exhibited a better dispersion and
smaller particle size. All these contributed to the best catalytic
activity of the bimetallic Ni-Fe0.5/AC catalyst. A control experiment
was conducted with a physical mixture of Ni/AC and Fe/AC. The
28 C. Li et al. / Fuel 203 (2017) 23–31

Table 1
Catalytic performance of various Ni-Fe/AC catalysts for the hydrogenation of EL to
GVL by H2.

Entry Catalysts Conv. (%) Yield (%)

1 Ni/AC 53.5 51.7
2 Fe/AC 0 0
3 Ni-Fe0.2/AC 91.7 85.9
4 Ni-Fe0.5/AC 99.3 99.0
5 Ni-Fe1/AC 97.1 90.6
6 Ni-Fe2/AC 78.5 76.2
a
7 Ni/AC and Fe/AC 59.8 57.3

Fig. 3. H2-TPR profiles of Ni-Fe/AC catalysts with different molar content of Fe Table 2
species: a) Fe/AC b) Ni/AC; c) Ni-Fe0.2/AC; d) Ni-Fe0.5/AC; e) Ni-Fe1/AC; f) Ni-Fe2/AC. Catalytic performance of Ni-Fe0.5/AC catalyst for the hydrogenation of EL to GVL
under different reaction conditions.

Entry Temperature /°C Time / h P(H2) / MPa Conv. (%) Yield (%)
conversion and yield were similar to those of pure Ni/AC. There-
1 140 6 4 100 100
fore, the above experimental results indicated that the formation
2 120 6 4 100 >99.9
of FeOx and Ni-Fe alloy on the surface of Ni-Fe/AC catalyst, which 3 100 6 4 99.3 99.0
had been identified by XPS, XRD and TEM measurements, could 4 80 6 4 89.8 84.6
provide positive effects for the activation and hydrogenation of 5 60 6 4 75.4 66.3
substrate molecules, and thus showed excellent performance on 6 100 6 5 100 >99.9
conversion of EL to GVL. 7 100 6 4 99.3 99.0
Since the Ni-Fe0.5/AC catalyst showed the highest catalytic 8 100 6 3 92.9 92.1
9 100 6 2 90.4 89.7
activity, it was employed to explore the influence of various
10 100 6 1 81.5 80.9
parameters including reaction temperature, H2 pressure and reac-
11 60 24 2 100 >98
tion time on the conversion of EL to GVL.
Reaction conditions: 40 mg supported metal catalyst; 100 mg EL; 10 mL water as
solvent; 800 rpm.
3.3. Effect of reaction temperature

Temperature is one of the most important factors for the con-

version of EL to GVL, so the effect of temperature on the hydro-
genation of EL was investigated. It can be seen from Table 2 that
raising temperature from 60 to 140 °C improved the catalytic activ-
ity. EL was almost completely converted into GVL in 6 h when the
reaction was performed at higher temperature (above 100 °C). As
expected, the catalytic activity of Ni-Fe0.5/AC catalyst slightly
decreased with the experimental temperature decreasing. When
the reaction was conducted at 60 °C, the conversion of EL
decreased to 75.4% and the yield of GVL was only 66.3% in 6 h. In
the meantime, a new product was observed, which was identified
as an intermediate of ethyl 4-hydroxypentanoate (4-HPE) by H1
NMR in Fig. S2.

Fig. 4. XPS spectra (a) Ni 2p spectra of Ni/AC, (b) Ni 2p spectra of Ni-Fe0.5/AC, (c) Fe 2p spectra of Fe/AC, (d) Fe 2p spectra of Ni-Fe0.5/AC.
 C. Li et al. / Fuel 203 (2017) 23–31
3.4. Effect of hydrogen pressure
In addition to the reaction temperature, the effect of hydrogen
pressure in this process should be another important parameter
to establish suitable reaction conditions. The conversion of EL to
GVL was investigated under various pressures from 1.0 MPa to
5.0 MPa and the results are shown in Table 2. When the reaction
was carried out under 1 MPa, the conversion of EL and the yield
of GVL were 81.5% and 80.9%, respectively. With the increase of
hydrogen pressure, both the conversion and yield improved. At
4 MPa, the conversion and the yield were 99.3% and 99.0%, respec-
tively. Further increasing the H2 pressure to 5 MPa led to a com-
plete conversion of EL to GVL. From Table 2, it can be found that
the effect of hydrogen pressure on the catalytic activity is not sig-
nificant at selected temperature (100 °C), while it is more obvious
at lower reaction temperature of 80 °C (show in Table S2). Even
under pretty mild conditions, the bimetallic Ni-Fe/AC catalyst
exhibited excellent catalytic properties. Decreasing the reaction
conditions (60 °C, 2 MPa H2) and prolonging the reaction time to
24 h, EL can also be converted completely and the GVL yield was
more than 98%.
3.5. Effect of reaction time
The effect of the reaction time was investigated at 100 °C and
4 MPa H2 (Fig. 5). In order to obtain a preliminary insight into
the reaction pathway, the reaction was traced and analyzed at
the first 120 min. In the first 30 min, 21.3% of the reaction interme-
diate ethyl 4-hydroxypentanoate (4-HPE) was detected and the
GVL yield was only 30.1%. Then the 4-HPE decreased gradually
with the reaction proceeding. When the reaction was performed
for 60 min, the conversion of EL and the yield of GVL were
improved significantly to 80.9% and 73.6%, respectively. In the
meantime 4-HPE declined obviously, and was hardly detected after
240 min. It is shown in Fig. 5 that except for 4-HPE, no other inter-
Fig. 5. Influence of the reaction time. Reaction conditions: 100 mg EL;10 mL water
solvent; 40 mg Ni-Fe0.5/AC catalyst; reaction temperature 100 °C; 4 MPa H2.
Scheme 2. Conversion of ethyl levulinate to c-valerolactone.
29
mediate was detected. The conversion of EL and the yield of GVL
increased with increasing the reaction time from 1 to 6 h. When
the reaction was performed for 6 h, the conversion and the yield
reached 99.3% and 99.0%, respectively. Full conversion of EL and
more than 99.9% yield of GVL could be achieved by prolonging
reaction time to 8 h. Based on the above results, a possible reaction
pathway for the synergistic hydrogenation of EL on the composite
catalyst was proposed (as shown in Scheme 2). Firstly, there was a
strong interaction between the carbanyl group (C@O) of EL and the
surface Ni-Fe/AC. Namely, the C@O could be activated by the Lewis
acid sites of FeOx and then the carbonyl group was hydrogenated
on Ni-Fe alloy sites via activating hydrogen molecular to form 4-
HPE. Finally, the 4-HPE was converted into GVL with the removal
of ethanol through an intramolecular transesterification without
any other by-products.
3.6. Recyclability of the catalyst
The stability is of great importance for the commercial applica-
tion of heterogeneous catalysts. Finally, the recyclability of the
bimetallic Ni-Fe0.5/AC catalyst was investigated in the process of
the incomplete conversion of EL to GVL. Notably, the Ni-Fe0.5/AC
catalyst could be easily separated from the reaction system due
to its strong magnetism (Fig. S3). It can be seen from Fig. 6, at first
run, the conversion of EL and the yield of GVL were 90.4% and
89.7%, respectively, and the catalytic activity decreased with the
catalyst being recycled. When the catalyst was run for four times,
the conversion and the yield were 74.9% and 70.4%, respectively.
Probably the catalytic active sites were covered with organic sub-
strates resulting in the decrease of the GVL yield. To verify this pos-
sibility, the used Ni-Fe0.5/AC catalyst was re-calcined to remove the
organic matter on the surface of the catalyst and reduced again.
After regeneration treatment, the catalytic activity recovered to a
certain extent (EL conversion of 80.8% and GVL yield of 77.3%). Cat-
Fig. 6. Recycling results of Ni-Fe0.5/AC catalyst under the following reaction
conditions: 40 mg of the catalyst, 100 mg of ethyl levulinate (EL), 10 mL of water
solvent, P(H2) = 2.0 MPa, T = 100 °C, t = 6 h.
30 C. Li et al. / Fuel 203 (2017) 23–31
alytic metal leaching test found 3.46% of Ni and 6.78% of Fe were
lost which could lead to the decrease of catalytic activity. More
work needs to be done to improve the catalyst stability for the pos-
sible commercial application.
4. Conclusions
In conclusion, we prepared a series of activated carbon sup-
ported non-noble bimetallic Ni and Fe heterogeneous catalysts
(Ni-Fe/AC) for liquid phase hydrogenation of EL to GVL under mild
reaction conditions with hydrogen as hydrogen donor. The catalyst
(Ni-Fe0.5/AC) with an optimal Fe/Ni molar ratio of 0.5 exhibited the
highest catalytic activity comparing with the other bimetallic cat-
alysts or the monometallic catalysts. The EL conversion of 99.3%
and the GVL yield of 99.0% could be achieved under the mild reac-
tion conditions of 100 °C, 4 MPa H2, 6 h. Under more mild condi-
tions (60 °C, 2 MPa H2) and prolonging the reaction time to 24 h,
EL could be converted completely and the obtained GVL yield
was more than 98%. The high catalytic activity of Ni-Fe0.5/AC
catalyst can be attributed to the formation of highly dispersed
Ni-Fe alloy structure and the co-presented FeOx on the surface of
catalyst. The kinetic experiments revealed that the EL was
converted into GVL through the reaction intermediate ethyl
4-hydroxypentanoate (4-HPE). The catalyst can be easily separated
with a magnet and catalytic metal leaching (Ni 3.46% and Fe 6.78%)
was an important factor leading to a decrease in catalytic activity.
Therefore, more work needs to be done to improve the catalyst
stability for the possible commercial application.
Acknowledgements
We gratefully acknowledge the financial supports from the
NSFC (21572213), the National Basic Research Program of China
(2013CB228103), Program for Changjiang Scholars and Innovative
Research Team in University of the Ministry of Education of China
and the Fundamental Research Funds for the Central Universities
(wk 2060190040).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2017.04.082.
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