An efficient and reusable bimetallic Ni3Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to Γ-valerolactone

Article abstract of DOI:10.1016/S1872-2067(18)63105-5

Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity, selectivity and stability in catalytical conversion. Herein, we report a facile one-pot carbothermal route to in-situ controllable synthesize heterogeneous bimetallic Ni₃Fe NPs@C nanocatalyst. The X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-description results reveal that the Ni₃Fe alloy nanoparticles are evenly embedded in carbon matrix. The as-prepared Ni₃Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid (LA) to γ-valerolactone (GVL) via both direct hydrogenation (DH) and transfer hydrogenation (TH). In DH of LA, the bimetallic catalyst achieved a 93.8% LA conversion efficiency with a 95.5% GVL selectivity and 38.2 mmol g^?1 h^?1 GVL productivity (under 130 °C, 2MPa H₂ within 2 h), which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts, respectively. In addition, the identical catalyst displayed a full conversion of LA with almost 100% GVL selectivity and 167.1 mmol g^?1 h^?1 GVL productivity at 180 °C within 0.5 h in TH of LA. Under optimal reaction conditions, the DH and TH catalytic performance of 500-Ni₃Fe NPs@C(3:1) catalyst for converting LA to GVL is comparable to the state-of-the-art noble-based catalysts. The demonstrated capability of bimetallic catalyst design approach to introduce dual-catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.

Full text of DOI:10.1016/S1872-2067(18)63105-5

Chinese Journal of Catalysis 39 (2018) 1599–1607
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article
An efficient and reusable bimetallic Ni3Fe NPs@C catalyst for
selective hydrogenation of biomass‐derived levulinic acid to
γ‐valerolactone
Haojie Wang a,b, Chun Chen a,#, Haimin Zhang a, Guozhong Wanga, Huijun Zhao a,c,
*
a Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and
Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, Anhui, China
b University of Science and Technology of China, Hefei 230026, Anhui, China
c Centre for Clean Environment and Energy, Griffith University, Queensland 4222, Australia
A R T I C L E I N F O
A B S T R A C T
Article history:
Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity, se‐
lectivity and stability in catalytical conversion. Herein, we report a facile one‐pot carbothermal
route to in‐situ controllable synthesize heterogeneous bimetallic Ni3Fe NPs@C nanocatalyst. The
X‐ray diffraction, transmission electron microscopy, X‐ray photoelectron spectroscopy and N2 ad‐
sorption‐description results reveal that the Ni3Fe alloy nanoparticles are evenly embedded in car‐
bon matrix. The as‐prepared Ni3Fe NPs@C catalyst shows excellent selective hydrogenation cata‐
lytic performance toward the conversion of levulinic acid (LA) to γ‐valerolactone (GVL) via both
direct hydrogenation (DH) and transfer hydrogenation (TH). In DH of LA, the bimetallic catalyst
achieved a 93.8% LA conversion efficiency with a 95.5% GVL selectivity and 38.2 mmol g–1 h–1 GVL
productivity (under 130 °C, 2MPa H2 within 2 h), which are 6 and 40 times in comparison with
monometallic Ni NPs@C and Fe NPs@C catalysts, respectively. In addition, the identical catalyst
displayed a full conversion of LA with almost 100% GVL selectivity and 167.1 mmol g–1 h–1 GVL
productivity at 180 °C within 0.5 h in TH of LA. Under optimal reaction conditions, the DH and TH
catalytic performance of 500‐Ni3Fe NPs@C(3:1) catalyst for converting LA to GVL is comparable to
the state‐of‐the‐art noble‐based catalysts. The demonstrated capability of bimetallic catalyst design
approach to introduce dual‐catalytic functionality for DH and TH reactions could be adoptable for
other catalysis processes.
Received 29 March 2018
Accepted 25 May 2018
Published 5 October 2018
Keywords:
Levulinic acid
γ‐valerolactone
Bimetallic catalyst
Hydrogenation
Dual‐catalytic functionality
© 2018, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
and value‐added chemicals has proven to be a suitable solution
because biomass is the most abundant non‐fossil car‐
The ever increased demand for fuels and chemicals adding
to the rapidly diminished fossil resources call for renewable
resource to secure sustainable economic development [1]. In
this regard, the effectively utilizing biomass to produce fuels
bon‐neutral and renewable resource on earth [2]. To date, ex‐
tensive effort has been devoted to convert biomass and its de‐
rivatives into fuels, fine chemicals and commodity materials
[3].For example, the massively produced levulinic acid (LA) via
* Corresponding author. Tel: +86‐551‐65591263; Fax: +86‐551‐65591434; E‐mail: h.zhao@griffith.edu.au
# Corresponding author. Tel: +86‐551‐65591263; Fax: +86‐551‐65591434; E‐mail: chenchun2013@issp.ac.cn
This work was supported by the National Natural Science Foundation of China (51502297, 51372248, 51432009), and the Instrument Developing
Project of the Chinese Academy of Sciences (yz201421).
DOI: 10.1016/S1872‐2067(18)63105‐5 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 39, No. 10, October 2018

1600
Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
cellulose hydrolysis and dehydration biorefinery processes is
one of the Top 10 most promising biomass derived platform
molecules [4–6]. It can be converted, through selective hydro‐
approach to synthesize desirable nanostructured bimetallic
Ni3Fe catalyst on carbon support.
Herein, we report a facile one‐pot carbothermal approach to
in‐situ controllable synthesize highly stable bimetallic Ni3Fe
alloy NPs evenly embedded in active carbon support (denoted
as Ni3Fe NPs@C). Importantly, the resultant Ni3Fe NPs@C cat‐
alyst exhibit excellent selective hydrogenation catalytic activi‐
ties toward the conversion of LA to GVL via both direct hydro‐
genation (DH) and transfer hydrogenation (TH) under moder‐
ate reaction conditions. The best performed Ni3Fe NPs@C cat‐
alysts can achieve 6 and 40 times enhanced GVL productivity
when compared to its monometallic counterparts (e.g., Ni
NPs@C and Fe NPs@C). The finding of this work paves a way to
developing high performance and low‐cost nonprecious cata‐
lysts for effective biomass utilization.
genation,
into
valuable‐added
chemicals
such
as
γ‐valerolactone (GVL), which can be directly utilized as gaso‐
line blender, food additive or solvent, and used as precursors
for the production of plastics, polymers, hydrocarbons (aro‐
matics, alkenes and alkanes) and other valuable chemicals
[7–11].
LA can be converted into GVL by homogeneous and hetero‐
geneous catalysis. However, heterogeneous catalysis is pre‐
ferred because homogeneous catalysis suffers from shortcom‐
ings of requiring catalyst separation and recovery [12]. To date,
a variety of heterogeneous catalysts (e.g., PtO2, Raney‐Ni,
Ni/MoOx/C, Cu/ZrO2, CuB23/graphene, Au‐Pd/TiO2, Ru/C,
Ir/CNT, NiCu/Al2O3, RuSn/C and Mo2C) have been reported for
selective hydrogenation of LA to produce GVL [13–22]. Among
the reported heterogeneous catalysts, the activated carbon
supported ruthenium catalyst (Ru/C) has been deemed as one
of the best performed catalysts, capable of achieving a 97.5%
GVL yield at room temperature, but suffered critical drawbacks
of aggregation and metal leaching [18]. Although precious met‐
als‐based catalysts generally possess high LA conversion effi‐
ciency, their expensive and scarcity nature adding to poor sta‐
bility greatly limit the large‐scale applications of precious met‐
als‐based catalysts. Development of high performance nonpre‐
cious catalysts is therefore vitally important to achieve eco‐
nomically viable large‐scale conversion of LA, but highly chal‐
lenging [23].
2. Experimental
2.1. Chemicals
All reagents and starting materials are commercially sup‐
plied and used as received without further purification. The
commercial activated carbon and levulinic acid (chromatog‐
raphy purity) are purchased from Aladdin Industrial Corpora‐
tion. Ni(NO3)2·6H2O, Fe(NO3)3·9H2O, methanol, ethanol, iso‐
propanol, formic acid are of analytically purity and purchased
from Sinopharm Chemical Reagent Co. Ltd.
2.2. Catalyst synthesis
The activation and hydriding of carbonyl group in LA mole‐
cule is an important elemental step to selectively convert LA to
GVL. Gallezot et al. [24] demonstrated that incorporating a
secondary metal into Ni‐based catalysts could promote the
activation of C=O bonds and increase catalytic activity. Yang et
al. [25] confirmed the promotional effect of bimetal catalyst by
density function theory (DFT) calculations of Ni3Fe alloy. To
this end, various Ni‐Fe bimetallic heterogeneous catalysts, es‐
pecially those supported on carbon, have been reported for
hydrogen generation and biomass conversion [26–28]. Based
on these reported findings, the nanostructure bimetallic Ni3Fe
alloy could possess superior selective hydrogenation activity to
efficiently convert LA into GVL，which has not yet been fully
exploited.
Various methods have been used to synthesis Ni3Fe bime‐
tallic nanocrystals, including chemical reduction, co‐reduction,
hydrothermal, thermal decomposition, electrochemical reduc‐
tion, sol‐gel method, mechanical alloying, microwave plasma
methodand the nano‐templating approach [29–38]. Neverthe‐
less, these methods exhibit drawbacks of low yield of alloy na‐
noparticles (NPs), containing impurity phases and large grain
sizes, and involving complex procedures, unsuitable for con‐
trollable synthesis. As a solid‐state metathesis reaction, the
carbothermal reduction has been widely utilized to obtain car‐
bon supported metallic materials due to its simplicity, control‐
lability, low‐cost and environmentally friendly nature [39].
Inspired by this and based on our previous works [40,41], we
envisage that carbothermal reduction could be an effective
A typical Ni3Fe NPs@C catalyst contains 20 wt% of Ni3Fe
NPs. In a typical carbothermal synthesis procedure, 1.0 g of
activated carbon was immersed with 1.0 mL solution contain‐
ing 2.58 mmol Ni(NO3)2·6H2O and 0.86 mmol Fe(NO3)3·9H2O
(Ni:Fe = 3:1), respectively, and subjected to an incipi‐
ent‐wetness impregnation treatment for 0.5 h. The treated
material was dried at 60 °C overnight in a vacuum oven and
used as the precursor. The ready to used Ni3Fe NPs@C catalyst
with 20 wt% of Ni3Fe NPs was obtained by calcining the pre‐
cursor in a tubular furnace at 500°C (with a ramp rate of 5 °C
min−1) for 2 h under nitrogen atmosphere (150 mL min–1).
For comparison purposes, the monometallic Ni NPs@C, Fe
NPs@C and a series of bimetallic NiFe NPs@C catalysts were
synthesized using similar experimental procedures under dif‐
ferent carbothermal temperatures (400 to 700 °C) and with
different Ni:Fe molar ratios (denoted as T‐NiFe NPs@C(x:y)),
where T referred to the treatment temperature and x:y indicate
the precursor Ni:Fe molar ratios.
2.3. Catalyst characterization
Powder X‐ray diffraction (XRD) patterns were recorded
with Philips X‐Pert Pro X‐ray diffractometer using a Cu Kα radi‐
ation (λ =0.15406 nm) at 40 kV and 40 mA. Samples were
scanned from 5° to 85° with a scanning rate of 2.67° min–1 and
a step size of 0.033°. High resolution TEM (HRTEM) and trans‐
mission electron microscopy (TEM) images were obtained us‐

Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
1601
ing a Tecnai G2 F30 S‐TWIN instrument (FEI Co., USA) operated
at an accelerating voltage of 200 kV. BET specific surface area
and pore structures were measured by a pulsed N2 adsorp‐
tion–desorption method at –196 °C using a surface area and
porosity analyzer (Autosorb iQ Station 2). X‐ray photoelectron
spectroscopy (XPS) were obtained using an ESCALAB 250
X‐ray photoelectron spectrometer (Thermo, USA) with Al Kα1,2
monochromatized radiation at 1486.6 eV X‐ray source. The
measure XPS energies were corrected using the C 1s peak of the
pollutant carbon at 284.6 eV. The metal elements content were
determined by inductively coupled plasma atomic emission
spectroscopy (ICP‐AES, ICP‐6300, Thermo Fisher Scientific)
after microwave digestion of the samples.
vated carbon acts synchronously as the reducing agent, stabi‐
lizer and support matrix. As shown in Fig. 1(b), the XRD peaks
of the as‐synthesized 500‐Ni3Fe NPs@C(3:1) at 44.1°, 51.4° and
75.7° can be assigned to (111), (200) and (220) reflections of
Ni3Fe (JCPDS‐ICDD card No. 65‐3244) [42]. TEM images (Fig.
1(c) and (d)) confirm that the Ni3Fe NPs with uniform particle
sizes are homogenously embedded in the sheet‐like carbon
support. The HRTEM (Fig. 1(e)) shows lattice fringes with a
spacing of 2.05 Å corresponding to (111) planes of Ni3Fe [42].
The corresponding fast Fourier transform (FFT) pattern fur‐
ther confirm the existence of (111) facets (insert in Fig. 1(e)).
The selected area electron diffraction (SAED) image (Fig. 1(f))
reveals the presence of polycrystalline components, the ob‐
served rings correspond to (111), (220), (311), (331), and
(551) planes of Ni3Fe, respectively. The elemental mapping
images indicate that Ni and Fe are uniformly distributed over
the entire carbon support matrix (Fig. 1(g)). The Ni3Fe bimetal‐
lic structure was further confirmed by the compositional line
scanning profiles (Fig. S1). It reveals a uniform alloy composi‐
tion of Ni3Fe NPs without significant segregation of each com‐
ponent. A Ni:Fe molar ratio of 75.9:24.1 in the catalyst can be
obtained from the EDX spectrum (Fig. 1(h)), while an almost
precisely 3:1 Ni:Fe molar ratio was determined by ICP. The N2
adsorption‐desorption isotherms (Fig. 1(i)) display a typical
type‐I isotherms with a high BET surface area of 854.6 m2 g–1
and a pore size distribution centralized around 4 nm (insert in
Fig. 1(i)). The XPS spectra of Ni 2p3/2 and 2p1/2 features with
energy peaks at 853.1 and 870.5 eV, attributing to Ni0 species
(Fig. 1(j)), while the Fe 2p3/2 and 2p1/2 spectra reveal the char‐
acteristic energy peaks of Fe0 at 707.2 and 720.3 eV, respec‐
tively [26,43]. Based on the above characterization results, it
can be concluded that the synthesized 500‐Ni3Fe NPs@C(3:1)
catalyst is a Ni3Fe alloy form of NPs and homogeneously em‐
bedded in carbon supporting matrix.
2.4. Catalyst performance evaluation
DH of LA experiments were performed in a 25‐mL stainless
steel autoclave equipped with a mechanical stirrer, a pressure
gauge and an automatic temperature control apparatus. In a
typical catalyst evaluation procedure, 30 mg catalyst was dis‐
persed into a mixture solution of 0.5 mmol LA and 10 mL iso‐
propanol in the reactor. The reactor was sealed, purged three
times with N2, followed by pressurizing with 2 MPa H2 and
heating to a target temperature with mechanical stirred at 500
r/min–1. Likewise, the TH of LA experiments was conducted
under the same procedure, except for that N2 was used to re‐
place H2 as the pressurized gas. When the reaction was over,
the autoclave was rapidly cooled down to the room tempera‐
ture and the product was separated from the catalyst by a
magnet. Where needed, the recovered catalyst was reused after
washed with water, acetone, and ethanol in turns and dried
under flowing nitrogen at 60 °C. The resultant supernatant was
sampled and analyzed by GC‐FID (Shimadzu, GC‐2010 Plus)
equipped with a KB‐WAX capillary column (30 m × 0.25 mm ×
0.25 μm). GVL and LA were quantified using n‐octanol as an
internal standard. The product was also confirmed by a GC‐MS
system (Thermos Fisher Scientific‐TXQ Quntum XLS, col‐
umn‐TG‐WAXMS, 30 m × 0.25 mm × 0.25 μm).
3.2. Catalytic performance
The hydrogenation performances of 500‐Ni3Fe NPs@C(3:1)
catalyst were systematically evaluated for conversion of LA to
GVL via DH and TH reaction routes, respectively.
LA conversion, GVL selectivity and productivity were calcu‐
lated according to Eqs. (1) to (3):
Fig. 2 shows the DH performance of the 500‐Ni3Fe
NPs@C(3:1) catalyst in isopropanol. The effect of reaction time
was firstly investigated under 130 °C reaction temperature of
and 2 MPa H2 pressure (Fig. 2(a)). The results revealed that
both LA conversion efficiency and GVL selectivity increased as
the reaction proceeded. A 93.8% LA conversion efficiency with
a 95.5% GVL selectivity and 38.2 mmol g–1 h–1 GVL productivity
can be achieved within 2 h of reaction (Table S1, entry 9). The
effect of reaction time under 150 °C reaction temperature was
also investigated (Fig. S2). When reaction time is less than 2 h,
the obtained LA conversion efficiency and GVL selectivity un‐
der 150 °C are significantly higher than that obtained from the
corresponding reaction time under 130 °C. Almost 100% GVL
selectivity and full LA conversion can be readily attained within
2 h reaction. These key DH performance indicators surpass the
performance of most reported high‐performance DH catalysts,
including noble metal‐based catalysts such as Ru/C, Ir/C, Re/C,
Remaining amount of LA
(1)
LA conversion (%) = (1 
)  100%
Initial amount of LA
Amount of GVL
(2)
(3)
GVL selectivity (%) =
 100%
Sum amount of products
Amount of GVL
GVL productivity =
Metal weight in catalyst (g)  Reaction time (h)
3. Results and discussion
3.1. Material characteristics of bimetallic Ni3Fe NPs@C catalyst
Fig. 1 summarizes the synthesis procedure and the mor‐
phology, chemical composition, electronic structure properties
of 500‐Ni3Fe NPs@C(3:1) catalyst. Fig. 1(a) schematically illus‐
trates the carbothermal synthetic procedure, where the acti‐

1602
Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
Fig. 1. (a) The preparation scheme of bimetallic Ni3Fe NPs@C; XRD pattern (b), TEM (c, d) images (inset: particle size distribution diagram), HRTEM
(e) image (inset: corresponding FFT pattern), SAED (f) image, elemental mappings (g), EDS spectrum (h), nitrogen adsorption‐desorption isotherm
and Pore size distribution (i) (inset), Ni 2p and Fe 2p XPS spectra (j, k) of the as‐prepared 500‐Ni3Fe NPs@C(3:1).
Pt/C and Pd/C (Table S1, entries 1–6). The DH performance of
the monometallic catalysts of Ni NPs@C and Fe NPs@C synthe‐
sized with the same procedure as that of bimetallic counter‐
parts were also investigated. Under the same reaction condi‐
tions (2 MPa H2, 130 °C, 2 h), the achieved LA conversion effi‐
ciency, GVL selectivity and productivity by Ni NPs@C and Fe
NPs@C are 23.9%, 60.1%, 6.1 mmol g–1 h–1, and 10.9%, 19.7%,
0.9 mmol g–1 h–1, respectively (Table S1, entries 7 and 8). These
monometallic catalysts performance results confirm the effec‐
tiveness of enhancing DH performance via bimetallic catalyst
design.
effect of reaction temperature on LA conversion efficiency and
GVL selectivity under 2 MPa H2 with 2 h reaction time. An in‐
crease in temperature from 90 to 130 °C leads to rapid in‐
creases in both conversion efficiency and selectivity. A full
conversion of LA with almost 100% GVL selectivity can be
achieved when the reaction temperatures ≥150 °C. It should be
noted that beside the targeted GVL, a portion of LA was con‐
verted to 4‐hydroxypentanoic acid (denoted as H1) via the
reduction of C=O bonds at lower reaction temperature (e.g.,
<150 °C) (Fig. S3(a)). However, no observable side reactions
occurred at high reaction temperatures (e.g., >150 °C) (Fig.
S3(a)), suggesting the synthesized bimetallic catalyst only pos‐
sesses catalytic activity toward DH of LA to GVL at high tem‐
perature. This is because the produced 4‐hydroxypentanoic
The reaction temperature and H2 pressure are important
reaction parameters and their effect on DH performance of
500‐Ni3Fe NPs@C(3:1) were investigated. Fig. 2(b) shows the

Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
1603
Fig. 2. DH performance of 500‐Ni3Fe NPs@C(3:1) catalyst. (a) Effect of reaction time under 130 °C and 2 MPa H2; (b) Effect of reaction temperature
under 2 MPa H2 with 2 h reaction time; (c) Effect of H2 pressure under 130 °C with 2 h reaction time; (d) Recyclability test under 130 °C, 2 MPa H2 and
1 h reaction time.
acid can be further transformed into GVL at high temperature
via intramolecular lactonization [8]. Fig. 2(c) shows the effect of
H2 pressure on LA conversion efficiency and GVL selectivity
under 130 °C reaction temperature and 2 h reaction time. As
expected, the LA conversion efficiency increased with the H2
pressure. Interestingly, the GVL selectivity is almost independ‐
ent of the H2 pressure when varied from 0.5 to 2 MPa. As shown
in Figs. 2 and S3(a), the DH of LA to produce GVL will undergo
two steps: LA transformation to form 4‐hydroxypentanoic acid
(H1) through hydrogenation and the conversion of intermedi‐
ate H1 to form GVL via intramolecular lactonization. The first
step involves active H* release and adsorption on the catalyti‐
cally active site, which is highly correlated to the reaction tem‐
perature, time and H2 pressure. As such, the LA conversion can
be greatly enhanced by these parameters. However, the intra‐
molecular lactonization in the second step is independent of
the active H* but associated with reaction temperature and
time. In addition, the generated intermediate H1 is unstable.
Therefore, the GVL selectivity depends obviously on the reac‐
tion time and temperature rather than hydrogen pressure.
For practical applications, the catalyst reuse is highly desir‐
able. Fig. 2(d) shows the recyclability test result. It was found
that no noticeable decay in both LA conversion efficiency and
GVL selectivity can be observed after four reuse cycles, signify‐
ing an excellent stability and reusability of the bimetallic cata‐
lyst. To further confirm this, the catalyst after four cycles of
reuse was characterized by XRD, TEM, EDS, XPS (Fig. S4).
Comparing to the as‐synthesized 500‐Ni3Fe NPs@C(3:1) (Fig.
1(b)–(k)), the reused catalyst showed insignificant changes in
particle size, morphology, crystal structure and composition.
Only worth mentioning changes resulting from the reuse are
the slightly deceased Fe3+ and increased Fe2+ and Fe0 contents
due to the reductive reaction environment. The leaching cata‐
lyst materials were also examined by ICP analysis. Less than
1% metal contents loss was determined from the catalyst after
four reuse cycles (Table S2, entry 6).
Comparing to DH, TH possesses a distinctive advantage of
not requiring the use of high pressure H2. In this work, the ap‐
plication of 500‐Ni3Fe NPs@C(3:1) catalyst was also extended
to convert LA to GVL via TH reaction route using isopropanol as
the H‐donor. The effect of the reaction time on LA conversion
efficiency and GVL selectivity was firstly investigated under
180 °C reaction temperature (Fig. 3(a)). A full conversion of LA
with almost 100% GVL selectivity can be attained within 0.5 h.
Under the reaction conditions, a GVL productivity of 167.1
mmol g–1 h–1 can also be obtained (Table S1, entry 15). The

1604
Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
LA(0.5mmol), isopropanol(10ml)
TH of LA:
Cat(30mg), N2
LA
GVL
100
80
60
40
20
0
100
80
60
40
20
0
LA Conversion
GVL Selectivity
100
80
100
80
LA Conversion
GVL Selectivity
100
100
80
60
40
20
0
(b)
(c)
(a)
80
60
40
20
0
60
60
40
40
20
20
LA Conversion
GVL Selectivity
Ethanol
Methanol
Isopropanol Formic acid
130
150
Reaction temperature (oC)
180
170
0
30
60
90
120 150 180
Reaction time (min)
Different solvent
Fig. 3. Catalytic performance of 500‐Ni3Fe NPs@C(3:1) catalyst in TH of LA. (a) Effect of reaction time, at 180 °C, and 2 MPa N2; (b) Effect of reaction
temperature, at 2 MPa N2, 2 h; (c) Effect of solvent, at 180 °C, 2 MPa N2, within 2 h.
effect of the reaction temperature on LA conversion efficiency
and GVL selectivity was then investigated (Fig. 3(b)). When the
reaction time was fixed at 2 h, both LA conversion efficiency
and GVL selectivity are increased almost linearly with reaction
temperature. A full conversion of LA with almost 100% GVL
selectivity can be obtained when 180 °C reaction temperatures
was employed. The GVL selectivity increase with reaction tem‐
perature implies that the esterification of LA and isopropanol
are dominant reactions at lower reaction temperatures, which
can be evidenced by the detected esterification products (T1
and T2, which are isopropyl levulinate and isopropyl
4‐hydroxypentate) under lower reaction temperature (Fig.
S3(b)). When the reaction temperature reaches 180 °C, the
dehydrogenation activity is greatly enhanced as evidenced by
the formation of large amount of acetone (Fig. S3(b)). Under
the circumstance, a sufficient amount of active H can be real‐
ized to facilitate the formation of GVL, leading to a high GVL
selectivity. The above results also suggest that the release of
active H from isopropanol is a control step of GVL formation
reaction. In this regard, the chemical nature of H‐donor could
strongly affect the rate of active H release. The effect of
H‐donors on LA conversion efficiency and GVL selectivity was
subsequently investigated using different H‐donors including
isopropanol, methanol, ethanol and formic acid (Fig. 3(c)). The
results reveal a conversion efficiency performance trend of
isopropanol > primary alcohols > formic acid. However, the
primary alcohols such as methanol and ethanol could not lead
to the production of GVL due to the formation of stable T1 (e.g.,
methyl‐levulinate or ethyl‐levulinate), a type of esterification
products that are difficult to be further converted to GVL.
Comparing to alcohols, formic acid possesses low LA conver‐
sion efficiency but exhibits ~23% GVL selectivity, indicating it
can be used as H‐donor for converting LA to GVL. However,
formic acid exhibits stronger corrosion effect of on Ni3Fe
NPs@C catalyst, leading to a poor catalyst stability (Table S2,
entry 4). The above results suggest that under the optimal re‐
action conditions, the TH performance of 500‐Ni3Fe
NPs@C(3:1) catalyst for converting LA to GVL is comparable to
the state‐of‐the‐art Ru‐based catalysts (Table S1, entries
10–12). The TH performance of the monometallic catalysts of
Ni NPs@C and Fe NPs@C were also investigated. Under the
reaction temperature of 180 °C and within 2 h, the achieved LA
conversion efficient, GVL selectivity and productivity by Ni
NPs@C and Fe NPs@C are 82.3%, 98.9%, 34.3 mmol g–1 h–1,
and 77.1%, 15.6%, 5.1 mmol g–1 h–1, respectively (Table S1,
entries 13 and 14). These monometallic catalysts performance
results confirm the effectiveness of enhancing TH performance
via bimetallic catalyst design.
The above results demonstrate superior DH and TH catalyt‐
ic performances of 500‐Ni3Fe NPs@C(3:1) catalyst. To acquire
an in‐depth understanding on the catalyst structure and cata‐
lytic activity relationship, different Ni‐Fe based catalysts were
synthesized and evaluated for their DH and TH performance for
converting LA to GVL (Table 1, Figs. 4, and S5). For a given car‐
bothermal temperature of 500 °C, a change in Ni:Fe ratio used
during synthesis leads to compositional and structural changes
of the resultant materials. When a Ni:Fe ratio of 1:1 was used,
the resultant material (500‐NiFe NPs@C(1:1)) was found to be
composed by Fe3O4 and metallic NiFe alloy (Figs. 4(a) and
S5(a)). While a Ni:Fe ratio of 1:3 used during synthesis
(500‐NiFe NPs@C(1:3)) leads to the formation of Fe3O4, metal‐
lic NiFe alloy and Ni (Figs. 4(a) and S5(b)). With increased ratio
of Ni:Fe, the chemical states of the resultant catalysts changed
from the Ni/Fe3O4 hybrid to the bimetallic Ni3Fe alloy, leading
to the catalytic performance improvement for both DH and TH
reactions (Table 1). When the Ni:Fe ratio used during the syn‐
thesis was fixed at 3:1, changes in carbothermal temperatures
can also lead to compositional, structural and particle size
changes of the resultant materials. A low carbothermal tem‐
perature of 400 °C results in the formation of NiO and Fe2O3
(400‐NiFe NPs@C(3:1)) (Figs. 4(b) and S5(c)), while higher
carbothermal temperatures of 600 and 700 °C (600‐NiFe
NPs@C(3:1) and (700‐NiFe NPs@C(3:1)) lead to the formation
of NiFe alloy (Figs. 4(b), S5(d), and S5(e)), which coincides with
the phase diagram of Ni‐Fe shown in Fig. S6. Also, the size of
NPs increased obviously with increased carbothermal temper‐
atures. The formation of NiFe alloy and increased NPs size un‐
der high carbothermal temperatures result in a decrease in the
catalytic activity for both DH and TH reactions.
The effects of these structural and compositional changes
are directly reflected in their catalytic performances (Table 1).
The 500‐Ni3Fe NPs@C(3:1) possesses the best performance

Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
1605
Table 1
Catalytic performance and structural information of 500‐Ni3Fe NPs@C and other related catalysts in DH and TH of LA.
DH of LA b
TH of LAc
Average NPs size a
(nm)
LA
GVL
LA
GVL
Entry
Catalyst
Phase
Conversion
efficiency (%)
Selectivity
(%)
Conversion
efficiency (%)
Selectivity
(%)
1
2
3
4
5
6
500‐NiFe NPs@C(1:3) Fe3O4/NiFe/Ni
500‐NiFe NPs@C(1:1) Fe3O4/NiFe
6.7
8.7
9.8
49.4
60.6
93.8
13.9
62.5
23.9
80.2
95.1
95.5
29.9
84.2
69.1
68.0
81.4
99.7
79.7
99.1
58.3
15.3
57.2
99.5
25.8
86.5
71.8
500‐Ni3Fe NPs@C(3:1)
400‐NiFe NPs@C(3:1)
600‐NiFe NPs@C(3:1)
700‐NiFe NPs@C(3:1)
Ni3Fe
NiO/Fe2O3
NiFe
6.6
24.1
33.5
NiFe
a The average NPs size derived from the particle size distribution diagram in Fig. 1(d) and Fig. S5;
b DH reaction condition: 0.5 mmol LA, 30 mg catalyst, 10 mL isopropanol, 130 °C, 2 MPa H2, 2 h;
c TH reaction condition: 0.5 mmol LA, 30 mg catalyst, 10 mL isopropanol, 180 °C, 2 MPa N2, 2 h.
Fig. 4. XRD patterns of the catalyst samples with variation of Ni:Fe molar ratio (a) and variation of carbothermal temperature (b).
among all catalysts investigated. These results suggest that all
bimetallic Ni‐Fe containing catalysts possess a certain degree of
catalytic activity towards DH and TH transformation of LA to
GVL. Their catalytic activities depend on the Ni:Fe ratio and
particle size.
can readily occur to form an intermediate of isopropyl levuli‐
nate (T1) [10]. When the reaction temperature reaches a key
point (ca. 180 °C), the catalyst promotes the 2‐propanol disso‐
ciation to release active H*. The carbonyl group of T1 and H* are
TH
DH
3.3. Possible mechanistic pathways of DH and TH reaction
routes
③
GVL
Possible mechanistic pathways for DH and TH reaction
routes to convert LA to GVL with bimetallic Ni‐Fe catalyst is
proposed based on the determined intermediates (Fig. 5).
With DH reaction route, the active H* is provided by the
dissociation of molecule hydrogen (H2). The carbonyl group in
LA and H* are specifically absorbed onto and activated by the
catalyst to form 4‐hydroxypentanoic acid (H1) as an interme‐
diate product. This can be evidenced by the fact that H1 was the
only detectable intermediate during DH process (Fig. S3(a)).
The produced 4‐hydroxypentanoic acid intermediate is unsta‐
ble and can be easily converted to GVL via intramolecular lac‐
tonization [8,44], especially under a relative high temperature.
With TH reaction route, the esterificationreaction between
the hydroxyl group of isopropanol and carboxyl group of LA
T2
R‐O‐H
②
*
H
H1
②
H*
①
T1
H2
R‐O‐H
①
Levulinic acid (LA)
Fe
Ni
γ‐valerolactone (GVL)
Isopropanol (R‐O‐H)
LA
4‐hydroxypentanoic acid (H1)
Isopropyl levulinate (T1)
Activated carbon
Isopropyl 4‐hydroxypentate (T2)
Fig. 5. Proposed mechanistic pathway for DH and TH of LA to GVL over
Ni3Fe NPs@C catalyst.

1606
Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
2014, 35, 929–936.
catalyzed by the catalyst to convert T1 into T2 (isopropyl
4‐hydroxypentate), which is unstable and inclined to take the
intramolecular lactonization reaction to generate target prod‐
uct of GVL.
[9] I. T. Horvath, Green Chem., 2008, 10, 1024–1028.
[10] D. Li, W. Ni, Z. Hou, Chin. J. Catal., 2017, 38, 1784–1793.
[11] V. Fábos, M. Y. Lui, Y. F. Mui, Y. Y. Wong, L. T. Mika, L. Qi, E. Cséfal‐
vay, V. Kovács, T. Szűcs, I. T. Horváth, ACS Sustainable Chem. Eng.,
2015, 3, 1899–1904.
4. Conclusions
[12] M. Chalid, A. A. Broekhuis, H. J. Heeres, J. Mol. Catal. A, 2011, 341,
14–21.
We have demonstrated superior catalytic performance of
bimetallic Ni‐Fe NPs supported on activated carbon catalysts to
convert LA to GVL via both DH and TH reaction routes. The
bimetallic Ni‐Fe catalysts in a form of Ni3Fe NPs@C possesses
the best catalytic performance that can be synthesized under a
500 °C carbothermal temperature using a Ni:Fe molar ratio of
3:1. Under the optimal reaction conditions, Ni3Fe NPs@C cata‐
lyst can respectively achieve LA conversion and GVL selectivity
of 93.8% and 95.5% via DH reaction route and 99.7% and
99.5% via TH reaction route. Such superior DH and TH catalytic
performances surpass the performance of most reported cata‐
lysts including precious metal based catalysts. The demon‐
strated capability of bimetallic catalyst design approach to in‐
troduce dual‐catalytic functionality for DH and TH reactions
could be adoptable for other catalysis processes.
[13] H. A. Schuette, R. W. Thomas, J. Am. Chem. Soc., 1930, 52,
3010−3012.
[14] K. Shimizu, S. Kanno, K. Kon, Green Chem., 2014, 16, 3899–3903.
[15] A. M. Hengne, C. V. Rode, Green Chem., 2012, 14, 1064–1072.
[16] S. Y. Fu, Y. Z. Li, W. Chu, C. Lia, D. G. Tong, Catal. Sci. Technol., 2015,
5, 1638–1649.
[17] W. Luo, M. Sankar, A. M. Beale, Q. He, C. J. Kiely, P. C. Bruijnincx, B.
M. Weckhuysen, Nat. Commun., 2015, 6, 6540.
[18] Z. P. Yan, L. Lin, S. J. Liu, Energy Fuels, 2009, 23, 3853–3858.
[19] X. Du, Y. Liu, J. Wang, Y. Cao, K. Fan, Chin. J. Catal., 2013, 34,
993–1001.
[20] I. Obregon, E. Corro, U. Izquierdo, J. Requies, P. L. Arias, Chin. J.
Catal., 2014, 35, 656–662.
[21] S. G. Wettstein, J. Q. Bond, D. M. Alonso, H. N. Pham, A. K. Datye, J. A.
Dumesic, Appl. Catal. B, 2012, 117, 321–329.
[22] E. F. Mai, M. A. Machado, T. E. Davies, J. A. Lopez‐Sanchez, V.
Teixeira da Silva, Green Chem., 2014, 16, 4092–4097.
[23] M. A. A. Aziz, A. A. Jalil, S. Triwahyono, A. Ahmad, Green Chem.,
2015, 17, 2647–2663.
References
[24] P. Gallezot, P. J. Cerino, B. Blanc, G. Flèche, P. Fuertes, J. Catal.,
1994, 146, 93–102.
[25] K. Yang, M. Zhang, Y. Yu, Phys. Chem. Chem. Phys., 2015, 17,
29616–29627.
[26] S. K. Singh, A. K. Singh, K. Aranishi, Q. Xu, J. Am. Chem. Soc., 2011,
133, 19638–19641.
[27] G. Chieffi, M. Braun, D. Esposito, ChemSusChem, 2015, 8,
3590–3594.
[28] G. Chieffi, C. Giordano, M. Antonietti, D. Esposito, J. Mater. Chem. A,
2014, 2, 11591–11596.
[29] X. G. Lu, G. Y. Liang, Y. M. Zhang, Mater. Sci. Eng. B, 2007, 139,
124–127.
[1] X. Li, P. Jia, T. Wang, ACS Catal., 2016, 6, 7621–7640.
[2] G. W. Huber, S. Iborra, A. Corma, Chem Rev., 2006, 106,
4044–4098.
[3] B. Liu, Z. Zhang, ACS Catal., 2016, 6, 326–338.
[4] M. Besson, P. Gallezot, C. Pinel, Chem. Rev., 2014, 114, 1827–1870.
[5] J. Q. Bond, D. M. Alonso, D. Wang, R. M. West, J. A. Dumesic, Science,
2010, 327, 1110–1114.
[6] C. X. Xiao, T. W. Goh, Z. Y. Qi, S. Goes, K. Brashler, C. Perez, W. Y.
Huang, ACS Catal., 2016, 6, 593–599.
[7] C. Michel, J. Zaffran, A. M. Ruppert, J. Matras‐Michalska, M.
Jedrzejczyk, J. Grams, P. Sautet, Chem. Commun., 2014, 50,
12450–12453.
[30] D. G. Tong, D. M. Tang, W. Chu, G. F. Gu, P. Wu, J. Mater. Chem. A,
[8] F. Pileidis, M. Tabassum, S. Coutts, M. M. Ttitirici, Chin. J. Catal.,
Graphical Abstract
Chin. J. Catal., 2018, 39: 1599–1607 doi: 10.1016/S1872‐2067(18)63105‐5
An efficient and reusable bimetallic Ni3Fe NPs@C catalyst for selective
hydrogenation of biomass‐derived levulinic acid to γ‐valerolactone
Haojie Wang, Chun Chen *, Haimin Zhang, Guozhong Wang, Huijun Zhao *
Institute of Solid State Physics, Chinese Academy of Sciences, China;
University of Science and Technology of China, China;
Griffith University, Australia
Isopropanol, H2
Catalyst
Levulinic acid
γ‐valerolactone
Ni3Fe NPs@C
Isopropanol, N2
A controllable carbothermal synthesized bimetallic Ni‐Fe NPs supported on
activated carbon catalyst (Ni3Fe NPs@C) possesses superior dual catalytic
functionality towards both direct hydrogenation (DH) and transfer hydro‐
genation (TH) of Levulinic Acid (LA) into value‐added γ‐Valerolactone
(GVL).

Haojie Wang et al. / Chinese Journal of Catalysis 39 (2018) 1599–1607
1607
2013, 1, 6425–6532.
[31] Q. Liao, R. Tannenbaum, Z. L. Wang, J. Phys. Chem. B, 2006, 110,
14262–14265.
[39] L. B. Hoch, E. J. Mack, B. W. Hydutsky, J. M. Hershman, J. M.
Skluzacek, T. E. Mallouk, Environ. Sci. Technol., 2008, 42,
2600–2605.
[32] D. K. Liu, A. L. Lai, R. J. Chin, Mater. Lett., 1991, 10, 318–322.
[33] S. Xue, M. Li, Y. Wang, X. Xu, Thin Solid Films, 2009, 517,
5922–5926.
[34] L. Q. Xu, L. Y. Chen, H. F. Huang, R. Xie, W. B. Xia, J. Wei, W. Zhong, S.
L. Tang, Y. W. Du, J. Alloys Compd., 2014, 593, 93–96.
[35] P. Y. Li, J. A. Syed, X. K. Meng, J. Alloys Compd., 2012, 512, 47–51.
[36] X. M. Zhou, X. W. Wei, Cryst. Growth Des., 2009, 9, 7–12.
[37] J. L. H. Chau, Mater. Lett., 2007, 61, 2753–2756.
[38] J. H. Kim, J. Kim, S. K. Lim, C. K. Kim, C. S. Yoon, J. Magn. Magn. Ma‐
ter., 2007, 310, 2402–2404.
[40] W. B. Gong, C. Chen, H. M. Zhang, Y. Zhang, Y. X. Zhang, G. Z. Wang,
H. J. Zhao, Mol. Catal., 2017, 429, 51–59.
[41] W. Gong, C. Chen, Y. Zhang, H. Zhou, H. Wang, H. Zhang, Y. Zhang, G.
Wang, H. Zhao, ACS Sustainable Chem. Eng., 2017, 5, 2172–2180.
[42] G. T. Fu, Z. M. Cui, Y. F. Chen, Y. T. Li, Y. W. Tang, J. B. Goodenough,
Adv. Energy Mater., 2017, 7, 1601172.
[43] G. H. Yu, C. L. Chai, F. W. Zhu, J. M. Xiao, W. Y. Lai, Appl. Phys. Lett.,
2001, 78, 1706–1708.
[44] O. A. Abdelrahman, A. Heyden, J. Q. Bond, ACS Catal., 2014, 4,
1171–1181.
乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni3Fe NPs@C
双金属催化剂
王豪杰a,b, 陈 春a,#, 张海民a, 汪国忠a, 赵惠军a,c,*
a中国科学院固体物理研究所, 环境与能源纳米材料中心, 安徽合肥230031, 中国
b中国科学技术大学, 安徽合肥230026, 中国
c格里菲斯大学, 清洁环境与能源中心, 昆士兰4222, 澳大利亚
摘要: 生物质经催化转化合成燃料及化学品是当前研究的热点. 目前, 生物质的催化转化主要聚焦于纤维素、半纤维素和
木质素的解聚及其下游产物合成. 其中, 乙酰丙酸(LA)作为纤维素解聚的主要产物之一, 是一种极具竞争力的平台化合物
和重要的生物质转化中间体. LA通过催化转化可以合成各类高附加值的化学品, 例如, 通过催化加氢LA可选择性合成γ-戊
内酯(GVL). 所合成的GVL用途广泛, 可作为绿色溶剂、食品、燃料添加剂、(塑料、高分子、烃类或者其它高附加值化学
品)前驱体等. 目前, LA-to-GVL的研究主要着眼于非均相催化体系, 包括负载型贵金属和非贵金属催化剂体. 其中, 贵金属
催化剂主要有Ru, Au, Pd, Rh, Ir和Pt, 虽然催化效率高, 条件温和, 但是成本高, 难以实现工业化. 此外对于广泛使用的Ru/C
催化剂, 存在金属-载体间相互作用不强. 活性组分易流失、导致催化剂稳定性差等问题；而非贵金属则普遍存在催化活性
不佳及反应条件苛刻等缺点. 因此, 开发高效、稳定、反应条件温和且具有工业化应用前景的非贵金属催化剂具有显著的
研究意义, 这也是当前的研究趋势.
在特定温度下, 金属离子与碳基底存在较强的相互作用. 鉴于此, 本文通过一步碳热还原法合成了活性炭负载的Ni3Fe
双金属催化剂(Ni3Fe NPs@C). 该催化剂在LA-to-GVL转化体系中展现了直接加氢(DH)和转移加氢(TH)双功能催化特性.
首先, 考察了其在DH体系中的反应特性: 在130 ºC和2 MPa氢压反应条件下经2 h反应, LA转化率达到93.8%, GVL选择性
为95.5 %, GVL产率是相应的单金属Ni/C和Fe/C催化剂的6倍和40倍. 此外, 在TH催化反应体系中, 在180 ºC, 0.5 h和无外加
氢源的反应条件下, 以异丙醇为反应溶剂和供氢体, LA几乎完全转化为GVL, 其反应效率同样相较于单金属Ni/C和Fe/C催
化剂大幅度提高. 所合成的Ni3Fe NPs@C双金属催化剂DH和TH催化性能优于绝大多数报道的LA加氢贵金属和非贵金属
催化剂. 而且, 该催化剂具有良好的循环利用性能, 经过四次循环, 其结构和化学状态没有发生明显的改变, 稳定性明显优
于商业化的Ru/C催化剂. 此外, 通过系统分析其催化性能以及材料结构, 明确了该催化剂在LA的DH和TH反应体系中的活
性位点, 并提出了可能的反应路径. 该研究为其它类型的DH和TH反应体系以及生物质高效转化过程提供了新的催化剂设
计思路. 并且这种催化剂及其制备方法简单、绿色, 易于工业化推广和应用.
关键词: 乙酰丙酸; γ-戊内酯; 双金属催化剂; 氢化; 双催化功能
收稿日期: 2018-03-29. 接受日期: 2018-05-25. 出版日期: 2018-10-05.
*通讯联系人. 电话: (0551)65591263; 传真: (0551) 65591434; 电子信箱: h.zhao@griffith.edu.au
#通讯联系人. 电话: (0551)65591263; 传真: (0551) 65591434; 电子信箱: chenchun2013@issp.ac.cn
基金来源: 国家自然科学基金(51502297, 51372248, 51432009); 中国科学院科研装备研制项目(yz201421).
本文的电子版全文由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).