Fuel 293 (2021) 120457

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Full Length Article

Cooperation between hydrogenation and acidic sites in Cu-based catalyst

for selective conversion of furfural to γ-valerolactone
Yuewen Shao a, 1, Qingyin Li a, 1, Xinyi Dong a, Junzhe Wang a, Kai Sun a, Lijun Zhang a,
Shu Zhang b, Leilei Xu c, Xiangzhou Yuan d, Xun Hu a, *
a
School of Material Science and Engineering, University of Jinan, Jinan 250022, PR China
b
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, PR China
c
School of Environmental Science and Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, PR China
d
Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: The production of γ-valerolactone (GVL) receives increasing attention due to its extensive applications as a
Furfural promising fuel and fuel additive. In this study, the direct conversion of biomass-derived furfural to GVL with a
γ-Valerolactone unprecedent yield of 90.5% was achieved via consecutive hydrogenation and acid-catalyzed reactions over CuAl
Cu-based catalyst
for hydrogenation and a co-catalyst (i.e. H-ZSM-5) for acid-catalysis in ethanol. The relative abundance of the
H-ZSM-5
Hydrogenation
hydrogenation sites and acidic sites determines the reaction network and the transfer of the main products from
furfuryl alcohol (FA) to ethyl levulinate (EL) or GVL, as the acidic sites, especially the Brønsted acidic sites, not
only catalyze the formation of EL from FA, but also affect the hydrogenation activity of CuAl. However, the Lewis
acidic sites facilitate the opening ring of FA to 1,4-pentanediol, preventing the GVL formation. The acid catalyst
and hydrogenation catalyst deactivate via varied mechanisms in the conversion of furfural to GVL, which is
required to be considered in the further development of the robust catalysts.

1. Introduction the subsequent hydrolysis of HMF further produces levulinic acid or

With the depletion of fossil fuel resources, growing attention has
been focused on the exploitation of renewable and environmentally
friendly lignocellulosic biomass as the feedstock for the production of
biofuels and fine chemicals [1–3]. Among the biomass derived chemical
products, levulinic acid has been recognized as an important platform
chemical, which is produced from the hydrolysis of the cellulosic com­
ponents of biomass [4–6]. Levulinic acid can be further upgraded to
other value-added chemicals, such as γ-valerolactone (GVL) [8,9], lev­
ulinic esters [10,11] and 1,4-pentanediol (1,4-PDO) [12,13], etc. In
recent years, the production of GVL has been attracted much attention,
as GVL possesses important commercial significance for the application
as solvent, liquid fuel and the feedstock for manufacturing polymers
[14,15].
With regard to the production of GVL, it can be achieved by multistep
processes with biomass as the initial feedstock. On the one hand, the C6
sugars, such as glucose and fructose from the hydrolysis of cellulose, can
be firstly hydrolyzed to form 5-hydroxymethylfurfural (HMF), and then
levulinic ester in aqueous phase or alcohol medium, which can be
consequently converted to GVL via hydrogenation and lactonization
route [14,16]. On the other hand, the C5 sugars, including xylose and
arabinose originating from the hydrolysis of hemicellulose, can be
converted to furfural via dehydration [17]. Furfural is then further hy­
drogenated to furfuryl alcohol (FA), and the subsequent hydrolysis of FA
produces levulinic acid or esters in water or alcohol solvents, which can
also be further hydrogenated to GVL [18]. The conversion of sugars/
furans thus includes the multiple catalytic steps with the involvement of
both the hydrogenation and acid catalysis. Hence, the production of GVL
from the furans/sugars is rather challenging, and the delicate balance of
the dispersion of acidic sites and hydrogenation sites determines the
selectivity from the furans/sugars to GVL.
Taking furfural as one example, the industrial production of furfural
from corncob has been long established while the further selective
conversion of furfural to GVL is complicated and far from commercial­
ization [19]. From furfural to GVL, the reaction steps involve the hy­
drogenation of furfural to FA, the hydrolysis of FA to levulinic acid, the

* Corresponding author.
E-mail address: xun.hu@outlook.com (X. Hu).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.fuel.2021.120457
Received 1 December 2020; Received in revised form 23 January 2021; Accepted 5 February 2021
Available online 24 February 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
Y. Shao et al.
further hydrogenation of levulinic acid to 4-hydroxyvaleric acid, and the
lactonization of 4-hydroxyvaleric acid to GVL [7]. In addition to these
desirable routes, the side reactions such as the polymerization of
furfural/the reaction intermediates [11], the complete hydrogenation of
furfural to tetrahydrofurfuryl alcohol (THFA) [20], and the further
hydrogenolysis of GVL to 1,4-pentanediol (1,4-PDO) or the ether­
ification of 1,4-PDO to 2-methyltetrahydrofuran (2-MeTHF) would also
take place [7,21], as shown in Scheme 1. Both the conversion of furfural
to GVL and the side reactions are catalyzed by the acidic sites and/or
hydrogenation sites. Thus, the reaction network during the conversion
of furfural is dominated by the availability and relative abundance of
acidic sites and hydrogenation sites on the catalyst(s) employed.
To have the accessibility of both acidic sites/hydrogenation sites, the
development of bi-functional catalyst or the bi-functional catalytic sys­
tems via mixing the hydrogenation and acid catalysts together are two
parallel routes. The bi-functional catalysts, including Zr-beta zeolite
[17,18,22], ZrO2-SBA-15 [23], heteropolyacid supported on Zr-Beta
zeolite [24] and Hf-based metal organic frameworks [25], were suc­
cessfully synthesized to achieve the conversion of furfural or its de­
rivatives into GVL. Besides, Rode et al. investigated the conversion of FA
over sulfonic acid functionalized ILs and 5% Ru/C catalyst system for the
first time [26], indicating the importance of active metal sites. Other bi-
functional catalytic systems, such as Au-ZrO2 catalyst combined with
ZSM-5 [27] and highly cross-linked ionic liquid polymer and Co/TiO2
catalyst [28], were also developed for the hydrogenation of hemicellu­
lose or furan-derived compounds into GVL. In fact, the combination of
hydrogenation catalyst and acid catalyst is more flexible as the avail­
ability of acidic sites and hydrogenation sites could be simply adjusted
via adding more or less catalysts with the certain type. The hydroge­
nation or acid catalysis in the bi-functional catalytic systems could then
occur in two separated routes, which could also be advantageous as the
deactivation of the one type of the catalyst could be readily substituted
without replacing all the catalysts, reducing the usage cost of the
catalyst.
In this study, we demonstrated the sensitivity of the selectivity to the
main products via adjusting the availability of hydrogenation sites and
acidic sites in the one-pot conversion of furfural to GVL with both Cu-
based catalyst and acid catalyst in ethanol medium. With furfural as
the starting feedstock, via changing the total amount and the relative
amount of acidic sites/hydrogenation sites, the main product transferred
from FA, a product from sole hydrogenation of furfural, to ethyl levu­
linate (EL) with the aid of Brønsted acidic sites. The further increase of
Scheme 1. Proposed reaction pathways for the hydrogenation of furfural to GVL.
2
Fuel 293 (2021) 120457
the hydrogenation sites altered the main product from EL to GVL, as is
shown in Fig. 1. Under the optimized reaction conditions, the yield of
GVL produced from furfural was up to 90.5%, which was the highest
yield that has been reported using furfural as the reactant up to now.
With EL as the starting reactant, the yield of GVL further reached 97.7%.
2. Experimental
2.1. Materials
Furfural, lanthanum trifluoromethanesulfonate (LTMS) and FA were
purchased from Shanghai Aladdin Biochemical technology Co., Ltd.
Acetone and sulfuric acid were provided from Yantai Yuandong Fine
Chemical Co., Ltd. NaOH, Na2CO3, MgO, Cu(NO3)2⋅6H2O and Al
(NO3)3⋅9H2O were obtained from Sinopharm Chemical Reagent Co., Ltd.
EL was purchased from Shanghai Macklin Biochemical Co., Ltd. H-ZSM-
5 zeolite catalyst was purchased from Tianjin Nanhua Catalyst Co., Ltd.
D008, a commercial solid acid resin catalyst with polystyrene as the
building block and –SO3H as the functionality, was purchased from Cary
Environmental Technology, and the parameter of D008 can be referred
to previous reference [11]. All chemicals were used directly without any
pretreatment.
2.2. Synthesis of Cu-based catalyst
CuAl catalyst was prepared by using a co-precipitation method.
Typically, the mixed nitrate solutions (Cu2+: 0.25 mol/L and Al3+: 0.25
mol/L) and NaOH solution (4.0 mol⋅L− 1) were added dropwisely into a
Na2CO3 solution (0.125 mol⋅L− 1), and the pH value was maintained at
10 ± 0.5 at 40 ◦ C. After that, the mixture was heated to 65 ◦ C and stirred
for 30 min, and then the sample was aged at 65 ◦ C for 24 h. Finally, the
precipitate was filtered and washing until the filtrate was neutral, and
then the filter cake was dried at 80 ◦ C overnight, following by being
grinded to fine powder. Later, the sample was calcined at 400 ◦ C for 4 h
in a static air. Before the test, the calcined sample was also reduced at
300 ◦ C for 2 h.
2.3. Catalytic test
The hydrogenation experiments were carried out in an autoclave
reactor. Typically, the reactant was firstly mixed uniformly with the
solvent and the catalyst at room temperature, and then the mixture was
Y. Shao et al.
Fig. 1. Conversion of furfural to GVL over both hydrogenation and acidic sites. B acidic sites represent Brønsted acidic sites.
loaded into the reactor vessel with a volume of 10 mL. After that, high-
purity hydrogen was used to purge the reactor for three times, and then
the reactor was charged with hydrogen to the presetting pressure before
the heating. Subsequently, the reactor was heated to the required re­
action temperature within ca. 30 min and maintained for a specific re­
action time. Finally, the reactor was cooled down to room temperature
after completing the experiment. The liquid products were collected for
the quantitative analysis, and the catalyst was separated and collected
for the further characterization.
2.4. Characterization of the catalysts and the liquid products
A Rigaku Ultima Ⅳ X-ray diffraction spectrometer (XRD) was used to
characterize the crystallinity of the CuAl catalyst and spent catalysts
using a Cu target (K α-radiation source, λ = 1.5406 Å). The scanning
ranges from 5 to 80◦ and a scanning rate of 20◦ /min were used. To
measure the specific area, pore volume and size of the samples, N2
adsorption-desorption measurement was performed at 77 K with the
instrument of Biaode SSA-6000 using the Brunauer-Emmet-Teller (BET)
method. Before the analysis, the sample was treated at 120 ◦ C for 2 h to
remove the physically adsorbed moisture. The elemental component of
CuAl catalyst was recorded on a scanning electron microscope with
energy-dispersive X-ray (EDX) spectrometry (SEM; FEI QUANTA FEG
250).
Temperature programmed reduction in hydrogen (H2-TPR) was also
used to analyze the reduction behavior of the copper-based catalyst by
using a Vodo VDSorb 91x instrument. Typically, 20 mg of the sample
was used under a constant 5% H2/Ar atmosphere with a flow rate of 20
mL/min and the ramping rate was 20 ◦ C/min. The sample was heated
from room temperature to 600 ◦ C, and the signal was recorded with a
thermal conductivity detector (TCD). The reduction degree of Cu species
was also calculated by an external standard method.
The acidic sites of the sample were also determined by temperature
programmed desorption (Biaode PCA-1200 instrument) with NH3 as the
probing molecule (NH3-TPD). Generally, 100 mg of the sample was
used, and the pretreatment was performed at 150 ◦ C for 30 min under a
constant helium flow with a flow rate of 30 mL/min. After that, the
sample was cooled down to room temperature, and then NH3 was
introduced with a flow rate of 40 mL/min for 1 h for the adsorption.
Before the heating, the sample was firstly purged under a constant he­
lium flow (30 mL/min) for 30 min, and then the sample was heated from
room temperature to 700 ◦ C using a ramping rate of 20 ◦ C/min. Finally,
the signal was recorded by a TCD.
To investigate the distribution of Brønsted and Lewis acidic sites of
the catalysts, in-situ diffuse reflectance infrared Fourier transform
spectroscopy (DRIFTS) characterization of the catalysts was carried out
by using a modified Harrick Praying Mantis DRIFT cell. Typically, the
sample was pretreated at 150 ◦ C for 30 min in vacuum, and then the
sample was cooled to 35 ◦ C. Before introducing pyridine as the probing
molecule, the background spectrum was recorded. The adsorption of
3
Fuel 293 (2021) 120457
pyridine was performed at 35 ◦ C for 30 min, and then nitrogen with a
flow rate of 50 mL/min was used for the degassing to remove the
physically adsorbed pyridine. After that, the sample was heated from 35
to 400 ◦ C and the heating rate was 10 ◦ C/min. During the ramping
process, spectra were simultaneously recorded.
UV-fluorescence spectra of the soluble polymers in the liquid prod­
ucts were measured using a Shimadzu (RF-6000) fluorescence spec­
trometer. Before the analysis, the sample was diluted to 400 ppm with
ethanol as the solvent. The initial excitation wavelength was set at 230
nm with the scan rate of 600 nm/min, and the emission wavelength
constantly remained 20 nm gap from it. To investigate the functional
groups of the fresh and spent catalyst, the catalyst was also characterized
by Fourier Transform Infrared Spectroscopy (FT-IR) using Nicolet iS50
instrument.
To analyze the yield of the liquid products, a gas chromatography
coupling with a mass spectrometer (GC–MS, Shimadzu GC–MS–QP
2020) equipped with a Wax pillar column (30 m of length, 0.25 mm of
internal diameter, 0.25 μm of film thickness) was used. Typically, the
liquid products were firstly diluted to ca. 2 wt% using acetone as the
solvent. The external standard method was used to determine the con­
version and the yield of the liquid products, and the corresponding
factor of standard chemicals was obtained for the quantitative analysis
of the targeting products. To identify the chemical component of liquid
product, the standard spectra of the National Institute of Standards and
Technology library (NIST 2014) were used herein.
The conversion of the reactant was defined as follows:
Conversion (%) =
Mole of reactant converted
× 100% (1)
Mole of reactant loaded
The yield of the targeting products was defined as follows:
Mole of product produced
Yield (%) = × 100% (2)
Mole of reactant loaded
3. Results and discussion
3.1. Catalyst characterization
CuAl catalyst used in this study was systematically characterized,
and the results are shown in Supporting information. Fig. S1 shows the
XRD patterns of the dried, calcined and reduced Cu-based catalysts. The
Cu-based catalyst used copper aluminum hydrotalcite as the precursor,
and the subsequent calcination and reduction could form CuO phase and
metallic Cu phase, respectively. The CuAl sample showed the crystal
phases of the copper aluminum layer double hydroxides (LDH) and CuO
species [29]. The diffraction peaks of 32.5◦ , 35.5◦ , 38.7◦ , 48.7◦ and
61.5◦ were assigned to the (1 1 0), (1 1 − 1), (1 1 1), (2 0 − 2), and (1 1 − 3)
crystal faces of CuO (JCPDS 48-1548), and the calcined sample exhibited
the obvious diffraction peaks of CuO. The diffraction peaks at 2θ of
43.3◦ , 50.4◦ , and 74.1◦ were attributed to the (1 1 1), (2 0 0), and (2 2 0)
crystal planes of metallic Cu species (JCPDS 85-1326). As shown in
Y. Shao et al. Fuel 293 (2021) 120457

Table S1, the particles size of metallic Cu in the reduced Cu-based
catalyst was 9.7 nm. Nevertheless, the sintering of copper species was
observed after catalyzing the conversion of furfural in ethanol medium,
which will be discussed latter. The Cu content in CuAl catalyst was 44.0
wt% (Table S1).
The CuAl catalyst showed the mesoporous structure, which was
confirmed by the N2 adsorption-desorption isotherm and the corre­
sponding pore distribution shown in Fig. S2b and Table S1. The N2
adsorption-desorption isotherm of the catalyst belonged to type IⅤ and
the hysteresis loops was H3-type, which was attributed to the aggrega­
tion of the particles [30]. In addition, the reduction behavior of the CuAl
catalyst was also investigated and shown in Fig. S3. The peak at 294 ◦ C
was attributed to the reduction of the highly dispersed CuO particles,
while the peak at 314 ◦ C was ascribed to the reduction of crystalline CuO
with bigger size or strong interaction between CuO and the carrier
[31,32]. The copper oxide exhibited the weak interaction with alumina
support and could be reduced easily at the temperature around 300 ◦ C,
as confirmed by the XRD result (Fig. S1). Besides, the reduction degree
of Cu species in CuAl catalyst was 87.2%, as shown in Table S1.
The acidic properties of the CuAl catalyst are also shown in Table S1
and Fig. S4. A low abundance of acidic sites was observed in CuAl
catalyst with mainly weak and moderate strength [33]. In comparison,
more acidic sites were observed for the H-ZSM-5 zeolite, as shown in
Table S1. The acidic sites in H-ZSM-5 zeolite were mainly assigned to the
acidic sites with weak and moderate strength. It has been reported that
H-ZSM-5 zeolite with both Al2O3 and SiO2 components possessed
abundant Brønsted acidic sites and Lewis acidic sites, especially for
Brønsted acidic sites [34]. Fig. 2a to 2d shows the pyridine-FTIR of H-
ZSM-5, CuAl and D008 catalysts. The peak centered at 1540 cm− 1 was
related to Brønsted acidic sites, and the peak centered at 1490 cm− 1
belonged to Brønsted and Lewis acidic sites. Besides, the peaks centered
at 1450, 1570 and 1560 cm− 1 were attributed to Lewis acidic sites

Fig. 2. Pyridine FT-IR spectra of (a) and (b): H-ZSM-5, (c): CuAl and (d): D008 catalysts under different desorption temperatures. (e) FT-IR spectra and (f) XRD
patterns of fresh CuAl, fresh H-ZSM-5 and spent CuAl/H-ZSM-5 catalysts. Spent CuAl/H-ZSM-5-catalyst-1 represents: the catalyst loading was 3 wt% and the spent
catalyst was collected. Spent CuAl/H-ZSM-5-catalyst-2 represents: the catalyst loading was 2 wt% and the spent catalyst was collected.

4
Y. Shao et al. Fuel 293 (2021) 120457

[35,36]. Because D008 has a lower operating temperature (190 ◦ C), the
pyridine-FTIR characterization was thus performed below 150 ◦ C. D008,
as a commercial solid acid catalyst, contains solely Brønsted acidic sites
originating from the -SO3H group, as is shown in Fig. 2d. In a word, more
Brønsted acidic sites were present in H-ZSM-5 catalyst, and CuAl catalyst
mainly contained Lewis acidic sites and a lower amount of Brønsted
acidic sites. These varied types and abundance of acidic sites in the
catalysts may play important roles in affecting the conversion of furfural
to GVL, which was further investigated.
3.2. Catalytic evaluation
Table 1 shows the distribution of the products in hydrogenation of
furfural in the co-presence of CuAl and the acid catalysts at the varied
temperatures. At 60 ◦ C, when CuAl was used as the single catalyst,
furfural could be converted to furfuryl alcohol (FA) with little by-
products observed. The introduction of acid as the catalyst affected
the activity of CuAl for the hydrogenation, as the conversion of furfural
changed obviously. When acid catalysts, such as H2SO4, D008, H-ZSM-5
or LMTS, were used as the co-catalyst of CuAl, the conversion of furfural
decreased dramatically (Table 1, Entries 1 to 5). The acid catalyst sup­
pressed the activity of CuAl catalyst for the hydrogenation at 60 ◦ C. It
was probably due to that the acidic sites of the catalyst were coordinated
with furfural, deterring its conversion via hydrogenation. Increasing
reaction temperatures enhanced the conversion of furfural (Table 1,
Entries 6 to 10), except that with H2SO4 as the co-catalyst (Table 1, Entry
7). Further to this, the distribution of the products also changed versus
the varied catalysts. Ethyl levulinate (EL) was obtained in the co-
presence of Brønsted acidic sites originating from the D008 and the
hydrogenation sites (Table 1, Entry 8), as the Brønsted acidic sites could
catalyze the alcoholysis of FA to form EL [37]. It was noted that 2-ethox­
ymethyl-furan (2-EF) was formed as the reaction intermediates through
the etherification of FA and ethanol (Table 1, Entries 7, 9 and 10), which
was not further converted to EL possibly due to a lack of Brønsted acidic
sites. Additionally, a higher yield of 1,4-pentanediol (1,4-PDO) was
obtained when Lewis acidic sites from LTMS were introduced (Table 1,
Entry 10), indicating that Lewis acidic sites might facilitate the opening
ring of FA to form 1,4-PDO. The higher reaction temperatures resulted in
the further conversion of FA via the acid-catalyzed routes. Compared
with the hydrogenation sites in the CuAl catalyst, a relatively higher
reaction temperature was required for the acidic sites including both the
Brønsted acidic sites and Lewis acidic sites to work.
The further increasing reaction temperature to 140 ◦ C promoted the
further conversion of FA and EL, which were acted as the two main
reaction intermediates (Table 1, Entries 13 and 14). D008 contained
exclusively the Brønsted acidic sites, which was the most effective cat­
alysts for catalyzing the conversion of the EL intermediate to GVL.
However, H-ZSM-5 also contained abundant acidic sites including
Brønsted acidic sites and Lewis acidic sites, which mainly converted
furfural into 2-EF and EL. The generation of 2-EF further demonstrated
that more Brønsted acidic sites were essential as H-ZSM-5 contained a
lower amount acidic sites in comparison with the D008. From the con­
version of EL to GVL, the initial step was the hydrogenation of the
carbonyl functionality into hydroxyl group in EL [7], which was mainly
related to the activity of the CuAl catalyst, but not the acid catalyst.
Therefore, it was possible that the coordination between H-ZSM-5 and
EL existed that could inhibit its further conversion. As the reaction
temperature further rose to 180◦ , the similar results were observed.
However, more polymerization reactions might be enhanced with the
increasing temperature and in the presence of the individual Lewis
acidic sites, impairing the formation targeting products and lower the
product yields. As the co-catalysts of CuAl catalyst, the effects of basic
catalysts on the distribution of the products from hydrogenation of
furfural were investigated, and the results are shown in Table 2. MgO, a
basic oxide, could improve the conversion of furfural via the hydroge­
nation (Table 2, Entry 1), which was attributed to the synergistic effects
with the CuAl catalyst, as is confirmed by the previous work [30]. With
NaOH used as the strong base catalyst, the hydroxyl group might also
coordinate with furfural or interfere with the copper sites for the hy­
drogenation reaction, affecting the catalytic activity of Cu-based catalyst
and further impairing the furfural conversion (Table 2, Entry 1). With
the increasing of reaction temperatures, the introduced base as the co-
catalysts (MgO, NaOH) did not promote the further conversion of FA,
achieving the FA yields of 98.5% and 97.0% (Table 2, Entries 3 and 4),
respectively. FA could maintain stable in the alkaline environment,
which suppressed the formation of levulinic acid or other side-products
via the hydrolysis of FA, and the acidic sites were of great importance for
the alcoholysis of FA into levulinic esters. It should be noted that MgO
could facilitate the hydrogenolysis of FA to produce pentanediols
(Table 2, Entry 7), which was not merely due to the alkalinity of MgO
because such an effect was not observed from NaOH as the co-catalyst.
The above results showed that the presence or absence of the catalytic

Table 1
Distribution of the products in hydrogenation of furfural in ethanol over CuAl and acid catalysts.a
Entry Catalysts T (◦ C) Con. (%) Yield (%)

FA EL GVL 2-EF 1,4-PDO 1,2-PDO 1,5-PDO

1 CuAl 60 81.8 79.4 0.0 0.0 0.0 0.0 0.0 0.0

2 CuAl + H2SO4 60 16.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0
3 CuAl + D008 60 40.3 39.3 0.0 0.0 0.0 0.0 0.0 0.0
4 CuAl + H-ZSM-5 60 44.9 36.3 0.0 0.0 0.0 0.0 0.0 0.0
5 CuAl + LTMS 60 56.3 55.6 0.0 0.0 0.0 0.0 0.0 0.0
6 CuAl 100 100.0 97.9 0.0 0.0 0.0 0.0 0.0 0.0
7 CuAl + H2SO4 100 22.2 5.7 1.5 0.0 7.8 0.0 0.0 0.0
8 CuAl + D008 100 100.0 14.0 30.6 0.0 0.0 12.4 0.0 0.0
9 CuAl + H-ZSM-5 100 100.0 39.0 18.7 0.0 26.8 0.0 0.0 0.0
10 CuAl + LTMS 100 100.0 8.7 0.0 0.0 57.6 20.1 0.0 0.0
11 CuAl 140 100.0 94.3 0.0 0.0 0.0 0.6 2.5 0.5
12 CuAl + H2SO4 140 100.0 11.9 6.1 0.0 17.9 0.0 0.0 0.0
13 CuAl + D008 140 100.0 0.0 0.0 51.0 0.0 0.0 0.0 0.0
14 CuAl + H-ZSM-5 140 100.0 0.0 43.8 2.2. 35.6 0.0 0.0 0.0
15 CuAl + LTMS 140 100.0 0.0 0.0 0.0 0.0 21.6 0.0 0.0
16 CuAl 180 100.0 81.2 0.0 0.0 0.0 3.4 7.3 1.7
17 CuAl + H2SO4 180 100.0 0.0 10.7 0.0 4.4 6.7 0.0 0.0
18 CuAl + D008 180 100.0 0.0 0.0 53.6 0.0 0.0 0.0 0.0
19 CuAl + H-ZSM-5 180 100.0 0.0 40.5 7.5 33.1 0.0 0.0 0.0
20 CuAl + LTMS 180 100.0 0.0 0.0 4.4 0.0 3.5 0.0 0.0
a
Reaction conditions: t = 2 h; PH2 = 5.0 MPa (at room temperature); stirring speed = 600 rpm; catalyst loading: 1 wt%; furfural-ethanol solution (2 wt%): 4 g; H2SO4
or NaOH solution (1.0 mol/L): 100 μL. The amount of acidic sites of D008 catalyst was 1.55 mmol/g and that of H-ZSM-5 zeolite catalyst was 0.42 mmol/g.

5
Y. Shao et al. Fuel 293 (2021) 120457

Table 2
Distribution of the products in hydrogenation of furfural in ethanol over CuAl and base catalysts.a
Entry Catalysts T (◦ C) Con. (%) Yield (%)

FA EL GVL 2-EF 1,4-PDO 1,2-PDO 1,5-PDO

1 CuAl + MgO 60 91.4 88.3 0.0 0.0 0.0 0.0 0.0 0.0
2 CuAl + NaOH 60 45.4 29.7 0.0 0.0 0.0 0.0 0.0 0.0
3 CuAl + MgO 100 100.0 98.5 0.0 0.0 0.0 0.0 0.0 0.0
4 CuAl + NaOH 100 100.0 97.0 0.0 0.0 0.0 0.0 0.0 0.0
5 CuAl + MgO 140 100.0 87.5 0.0 0.0 0.0 0.0 4.4 1.4
6 CuAl + NaOH 140 100.0 89.4 0.0 0.0 0.0 0.0 0.0 0.0
7 CuAl + MgO 180 100.0 64.8 0.0 0.0 0.0 1.1 11.1 2.4
8 CuAl + NaOH 180 100.0 85.0 0.0 0.0 0.0 0.0 1.6 0.5
a
Reaction conditions: t = 2 h; PH2 = 5.0 MPa (at room temperature); stirring speed = 600 rpm; catalyst loading: 1 wt%; furfural-ethanol solution (2 wt%): 4 g; NaOH
solution (1.0 mol/L): 100 μL.

sites in the co-catalyst system affected significantly the conversion of
furfural. The impacts of the availabilities of both hydrogenation sites
and the acidic sites in the co-catalyst on the conversion of furfural to EL
or GVL were further investigated.
3.3. Availabilities of hydrogenation sites and the acidic sites on EL/GVL
formation
The availabilities of hydrogenation sites and the acidic sites in the
reaction medium were achieved by altering the loading of CuAl catalyst
and acid catalysts to optimize the distribution of hydrogenation sites and
acidic sites for achieving the high yields of EL or GVL, as shown in
Table 2. With the increasing loading of CuAl catalyst, more FA was
consumed via hydrogenolysis route, producing more pentanediols
(Table 3, Entries 1 and 2). Varied amount of D008 catalysts was added as
the co-catalyst to change the availability of the acidic sites. It was found
that a higher amount of acid catalyst made the acid-catalyzed reaction
dominant and thus the reactivity of hydrogenation catalyst decreased
(Table 3, Entries 3 to 7). At the same time, D008 with abundant Brønsted
acidic sites could directly catalyze the alcoholysis of FA to EL, and the
negligible 2-EF yield was observed (Table 3, Entries 3 to 13). EL was
produced as the final product when the loading of D008 catalyst was
higher than that of CuAl catalyst, and the further hydrogenation of EL
did not occur, possibly due to the deactivation of CuAl catalyst. On the
contrary, a higher loading of CuAl catalyst made the hydrogenation
reaction predominant, as evidenced by the formation of GVL via the
hydrogenation of EL. Further to this, a higher loading of CuAl catalyst
also promoted the hydrogenation of GVL to 1,4-PDO via the ring-
opening reaction of the GVL, resulting in the decreased yield of GVL.
It is worth noting that the presence of abundant Brønsted acidic sites also
resulted in the formation of soluble polymers, which could not be
detected by GC–MS.
To further investigate the competition of acidic sites and hydroge­
nation sites on the selectivity of the targeting products, the loading of
CuAl and H-ZSM-5 catalysts was also further adjusted. Under a relatively
higher loading of H-ZSM-5 catalyst, furfural was difficult to be converted
and the activity of CuAl catalyst was suppressed (Table 3, Entries 14 and
15), and thus EL could not be further hydrogenated to GVL. The

Table 3
Distribution of the products in hydrogenation of furfural in ethanol under different mass ratio of Cu-based catalyst and D008 catalyst.a
Entry Mass ratio (wt%/wt%) Con. (%) Yield (%)

FA EL GVL 2-EF 1,4-PDO 1,2-PDO 1,5-PDO 1-PO

1 1/0 100.0 78.4 0.0 0.0 0.0 0.0 3.0 0.0 0.4
2 2/0 100.0 64.7 0.0 0.0 0.0 0.5 10.2 2.3 2.8
3 0.25/1b 79.3 0.0 29.8 0.0 0.0 0.0 0.0 0.0 0.0
4 0.5/1b 100.0 0.0 69.4 0.0 0.0 0.0 0.0 0.0 0.0
5 0.75/1b 100.0 0.0 43.0 0.0 0.0 0.0 0.0 0.0 0.0
6 1/2b 85.3 17.3 36.6 0.0 0.0 0.0 0.0 0.0 0.0
7 1/3b 100.0 0.0 55.3 0.0 0.0 0.0 0.0 0.0 0.0
8 1/0.25b 100.0 0.0 0.0 38.4 0.0 2.7 0.0 0.0 0.0
9 1/0.5b 100.0 0.0 0.0 51.3 0.0 0.0 0.0 0.0 0.0
10 1/0.75b 100.0 0.0 0.0 57.0 0.0 0.0 0.0 0.0 0.0
11 1/1b 100.0 0.0 0.0 58.4 0.0 0.0 0.0 0.0 0.0
12 2/1b 100.0 0.0 0.0 61.0 5.6 5.9 0.0 0.0 0.0
13 3/1 b 100.0 0.0 0.0 47.5 0.0 13.3 0.0 0.0 0.0
14 0.25/1c 18.0 0.0 4.9 0.0 0.3 0.0 0.0 0.0 0.0
15 0.5/1c 28.1 0.0 6.6 0.0 5.9 0.0 0.0 0.0 0.0
16 0.75/1c 92.7 0.0 26.2 0.0 51.4 0.0 0.0 0.0 0.0
17 1/1c 100.0 0.0 60.9 0.0 33.3 0.0 0.0 0.0 0.0
18 1/2c 100.0 0.0 40.1 0.0 18.8 0.0 0.0 0.0 0.0
19 1/3c 100.0 0.0 18.1 0.0 0.6 0.0 0.0 0.0 0.0
20 2/1c 100.0 0.0 0.0 64.6 18.5 0.6 0.0 0.0 0.0
21 3/1c 100.0 0.0 0.0 65.7 16.0 1.5 0.0 0.0 0.0
22 2/2c 100.0 0.0 0.0 73.7 17.2 0.0 0.0 0.0 0.0
23 3/2c 100.0 0.0 0.0 69.0 19.5 1.5 0.0 0.0 0.0
24 4/2c 100.0 0.0 0.0 64.4 19.6 2.8 0.0 0.0 0.0
25 3/3c 100.0 0.0 0.0 79.0 12.6 0.9 0.0 0.0 0.0
26 2/3c 100.0 0.0 23.2 61.7 9.1 0.0 0.0 0.0 0.0
27 2/4c 100.0 0.0 56.7 0.0 1.4 0.0 0.0 0.0 0.0
a
Reaction conditions: T = 140 ◦ C; t = 2 h; PH2 = 5.0 MPa (at room temperature); stirring speed = 600 rpm; furfural-ethanol solution (2 wt%): 4 g.
b
Mass ratio represents the ratio of CuAl and D008 catalysts.
c
Mass ratio represents the ratio of CuAl and H-ZSM-5 catalysts.

6
Y. Shao et al. Fuel 293 (2021) 120457

targeting product was 2-EF, indicating that acidic sites and hydroge­
nation sites were not sufficient for the conversion of furfural and FA.
With the increment of loading of CuAl and H-ZSM-5 catalysts (Table 3,
Entries 17 and 18), the conversion of furfural reached 100%, but a low
yield of EL was obtained due to the polymerization reaction catalyzed by
an excessive amount of acidic sites (Table 3, Entries 18 and 19). The
further increase of the loading of CuAl catalyst shifted the main product
from EL to GVL, as the hydrogenation of EL was catalyzed by the hy­
drogenation sites (Table 3, Entries 20 and 21). In the subsequent trails,
when the loading of CuAl catalyst was dominant, GVL was produced as
the major product (Table 3, Entries 22 to 25). The reduction in the ratio
of CuAl catalyst conversely transferred the main product from GVL to EL
(Table 3, Entries 26 and 27). The further conversion of EL to GVL was
very sensitive towards the availability of the hydrogenation sites, while
the formation of EL from FA was sensitive to the acidic sites. In a word,
the relative loading of CuAl and H-ZSM-5 catalysts significantly affected
the yield of GVL and other products. On this basis, the other principal
parameters, such as reactant loading, reaction temperatures and reac­
tion time, were further optimized to enhance selectivity of the products.
The effects of reactant loading on the production of GVL were
investigated. In Table S3, the results indicated that an increasing reac­
tant loading was not beneficial to the production of GVL. For example,
when the higher furfural concentrations such as 10 and 5 wt% were
used, more FA was formed and retained, which was not further con­
verted to EL and GVL. This observation confirmed that the acidic sites
were crucial for the alcoholysis of FA. When FA was used as the reactant,
the higher concentration led to the incomplete conversion of FA and
most fractions might be polymerized in the reaction medium.
As is shown in Table 4, at 120 ◦ C, furfural as the reactant obtained a
higher GVL yield than that with FA as the reactant (Table 4, Entries 1 to
4). It has been known that FA is prone to be polymerized in the presence
of acid catalyst [38], which led to the lower yields of GVL. Although the
conversion of furfural to GVL would also produce FA as the reaction
intermediate, whereas the formed FA could be promptly converted to EL
and thus the concentration of FA in the system was low, resulting in a
higher yield of GVL. When the reaction temperature was further
increased to 160 ◦ C, the GVL yield was highly improved using furfural as
the reactant rather than with FA as the reactant. In addition, the
increasing reaction temperature also resulted in the opening ring of GVL
to form 2-MeTHF under the catalysis of both acidic sites and hydroge­
nation sites (Table 4, Entry 5). The lower loading of the hydrogenation
catalyst and acid catalyst impaired the production of 2-MeTHF while
correspondingly enhanced the formation of GVL (Table 4, Entry 7). With
FA as the starting reactant, the EL intermediate formed could not be
effectively hydrogenated to GVL, which was due to the decreased ac­
tivity for hydrogenation that probably resulted from the sintering of
metallic Cu species. The conversion of furfural, FA and EL to GVL were
also performed at 120 ◦ C via prolonging the reaction time. It was found
that the highest yield of GVL from furfural (90.5%, Table 4, Entry 12)
was achieved with the reaction conditions employed. When EL was used
as the reactant, the yield of GVL reached 97.7%. In addition, the bi-
functional catalytic system developed in this study, including CuAl
and H-ZSM-5 catalyst system, also exhibited the superior catalytic per­
formance with the catalysts or catalytic systems reported in the previous
literatures [7,17,22–28,39], as shown in Fig. S5.
The assembly of the above-mentioned reaction steps formed a pic­
ture of reaction network concerning the conversion of furfural over the
hydrogenation sites and acidic sites, which are summarized in Scheme
2b. When the single hydrogenation catalyst was used, FA derived from
the hydrogenation of furfural was prone to produce both 1,5-pentane­
diol (1,5-PDO) and 1,2-pentanediol (1,2-PDO) via the hydrogenolysis
[40], as is shown in Scheme 2a. When the co-catalyst such as H-ZSM-5
catalyst including Brønsted acidic sites was introduced, FA could be
further converted to EL via the alcoholysis route, and then EL was
readily hydrogenated to GVL over the hydrogenation sites. To achieve a
higher yield of GVL, the opening ring of GVL to produce 1,4-PDO or 2-
MeTHF should be suppressed, as shown in Scheme 2b.
3.4. Catalyst reusability
The reusability of the CuAl and H-ZSM-5 catalysts for the conversion
of furfural was investigated under the typical reaction conditions. As
shown in Fig. 3, the catalysts with the varied loadings were reused for
four times in the conversion of furfural to GVL. An obvious deactivation
of the co-catalyst system was observed. The catalytic system with a
higher catalyst loading (3/3 wt%) could maintain the catalytic activity
until the third reuse. When the respective loading of H-ZSM-5 and CuAl
was 2 wt%, FA was produced as the main products at the third cycle. The
retaining of FA and the little formation of EL in the reaction medium
suggested that the H-ZSM-5 catalyst might deactivate as FA was difficult
to be further hydrolysed over the acidic sites. To further confirm the
speculation, fresh H-ZSM-5 catalyst was added to the catalytic system in
the fifth cycle of the experiments. It can be observed that the yield of
GVL was recovered to some extent, indicating that the reduced pro­
duction of GVL was due to the deactivation of the H-ZSM-5 catalyst. The
liquid products collected from the reuse at the fourth and fifth time were
analyzed with the UV fluorescence measurement to probe the soluble
polymer formed during the reaction process (Fig. S6), and the results

Table 4
Distribution of the products in hydrogenation of different reactants in ethanol under different mass ratio of Cu-based catalyst and H-ZSM-5 catalyst.a
Entry Reactants Mass ratiob (wt%/wt%) T (◦ C) Yield (%)

EL GVL 2-EF 1,4-PDO 2-MeTHF

1 FUR 3/3 120 0.0 73.9 16.1 0.9 2.8

2 FA 3/3 120 1.6 63.7 24.6 1.1 5.3
3 FUR 2/2 120 1.0 70.3 21.9 0.7 2.4
4 FA 2/2 120 0.4 54.1 17.2 0.5 1.6
5 FUR 3/3 160 0.0 70.3 0.0 0.0 25.2
6 FA 3/3 160 45.4 25.6 0.0 0.0 4.9
7 FUR 2/2 160 0.0 85.4 0.0 0.0 12.7
8 FA 2/2 160 59.4 21.2 0.0 0.0 8.1
9 FUR 3/3 120c 0.0 85.0 0.0 1.8 5.5
10 FA 3/3 120c 0.0 69.5 13.3 1.3 8.0
11 EL 3/3 120c 0.0 96.9 0.0 1.1 0.6
12 FUR 2/2 120c 0.0 90.5 0.0 1.0 4.9
13 FA 2/2 120c 0.0 84.3 5.8 1.1 4.6
14 EL 2/2 120c 0.0 97.7 0.0 1.1 0.0
a
Reaction conditions: t = 2 h; PH2 = 5.0 MPa (at room temperature); stirring speed = 600 rpm; furfural-ethanol solution (2 wt%): 4 g. Conversion of the reactant was
100.0% in all runs.
b
Mass ratio represents the ratio of CuAl and H-ZSM-5 catalysts.
c
Reaction time = 4 h.

7
Y. Shao et al. Fuel 293 (2021) 120457

Scheme 2. The proposed reaction routes for the conversion of furfural over (a): copper-based catalyst (b): copper-based and H-ZSM-5 catalysts.

indicated that the crystallinity of H-ZSM-5 decreased after the reuse,

which might be due to the formation of coke. In addition, the spent CuAl
catalyst exhibited an obvious growth of Cu particle size (17/16.8 nm in
the used catalyst versus 9.7 nm in the fresh catalyst, Table S2), which
together with the formation of polymer accounted for the decreasing
GVL yields during the reusability test. How to tackle the polymerization
reactions and the sintering of metallic Cu species via the rational design
of the catalysts for achieving the high reusability of the catalytic system
are the remaining issues to be resolved.

4. Conclusions

In summary, one-pot conversion of biomass-derived furfural to GVL

was achieved via the hydrogenation of furfural to FA, the alcoholysis of
FA to EL and the further hydrogenation of EL to GVL with high selec­
tivity over dual catalyst system including CuAl and acid catalyst.
Copper-based catalyst can catalyze the hydrogenation of furfural to FA,
whereas the hydrogenation reactivity of EL was compromised with the
presence of acid catalyst, affecting the formation of the reaction in­
Fig. 3. Reusability tests of hydrogenation of furfural over CuAl and H-ZSM-5 termediates and final products. With relatively more acid catalyst like
catalysts. Reaction conditions: T = 120 ◦ C; t = 4 h; PH2 = 5.0 MPa (at room
D008 or H-ZSM-5, EL was formed as the main product as the further
temperature); stirring speed = 600 rpm; furfural-ethanol solution (2 wt%): 4 g.
hydrogenation of EL was suppressed. On the contrary, the higher
Run-5 represents fresh H-ZSM-5 was further used and the loading of H-ZSM-5
catalyst was 3 wt% or 2 wt%.
abundance of CuAl in the co-catalyst system make the hydrogenation of
EL as the governing reaction, producing GVL as the major product. In
addition, acid types in acid catalyst also impacted the reaction path­
indicated the formation of the soluble polymers with the π-conjugated
ways. The Brønsted acidic sites in D008 or H-ZSM-5 catalyze the alco­
structures [41]. The polymer formed on the surface of H-ZSM-5 could
holysis of FA to EL and the lactonization reactions to GVL, while
led to the deactivation of the catalyst. Although the introduction of
suppress the hydrogenolysis route of FA. The Lewis acidic sites in LTMS
additional H-ZSM-5 catalyst could recover the yield of GVL to some
facilitate the opening ring of FA to form 1,4-PDO. The abundance of the
extent, the yield of GVL was still lower than that in the first cycle. The
acidic sites, hydrogenation sites and the nature of acidic sites together
CuAl catalyst might also deactivate during the reaction process. The
governs the shift of the targeting products from FA to EL, GVL or 1,4-
spent H-ZSM-5 and CuAl catalysts were further characterized by FT-IR
PDO. The conversion of furfural to GVL involves the formation of the
and XRD analysis. As is shown in Fig. 2e, the FT-IR results indicated
by-products that tend to polymerize, which was the main reason for the
that C–
– O, C–– C of aromatic ring and –CH2– groups were present in the
deactivation of the H-ZSM-5 catalyst. CuAl as the hydrogenation catalyst
spent H-ZSM-5 and CuAl catalysts [11], further proving the occurrence
suffered not only from the deposition of polymers, but from the sintering
of the polymerization reaction. The XRD patterns shown in Fig. 2f
of metallic Cu particles in the ethanol medium. These are the remaining

8
Y. Shao et al.
issues to be further resolved via the rational design of catalysts.
CRediT authorship contribution statement
Yuewen Shao: Conceptualization, Methodology, Investigation,
Validation, Writing - original draft, Visualization. Qingyin Li: Data
curation, Validation, Investigation, Writing - review & editing. Xinyi
Dong: Software, Investigation, Visualization. Junzhe Wang: Software,
Validation, Investigation. Kai Sun: Methodology, Investigation. Lijun
Zhang: Supervision, Project administration. Shu Zhang: Supervision,
Project administration. Leilei Xu: Supervision, Writing - review &
editing. Xiangzhou Yuan: Supervision, Writing - review & editing. Xun
Hu: Conceptualization, Methodology, Resources, Writing - review &
editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (No. 51876080), the Program for Taishan Scholars of Shandong
Province Government, the Agricultural Innovation Program of Shan­
dong Province (SD2019NJ015), the R&D program of Shandong Basan
Graphite New Material Plant and Innovative Training Program for
College Students (S202010427072).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.120457.
References
[1] Kabir G, Hameed BH. Recent progress on catalytic pyrolysis of lignocellulosic
biomass to high-grade bio-oil and bio-chemicals. Renew Sustain Energy Rev 2017;
70:945–67. https://doi.org/10.1016/j.rser.2016.12.001.
[2] Tian S-Q, Zhao R-Y, Chen Z-C. Review of the pretreatment and bioconversion of
lignocellulosic biomass from wheat straw materials. Renew Sustain Energy Rev
2018;91:483–9. https://doi.org/10.1016/j.rser.2018.03.113.
[3] Baral NR, Sundstrom ER, Das L, Gladden J, Eudes A, Mortimer JC, et al.
Approaches for more efficient biological conversion of lignocellulosic feedstocks to
biofuels and bioproducts. ACS Sustain Chem Eng 2019;7(10):9062–79. https://doi.
org/10.1021/acssuschemeng.9b01229.
[4] Kang S, Fu J, Zhang G. From lignocellulosic biomass to levulinic acid: a review on
acid-catalyzed hydrolysis. Renew Sustain Energy Rev 2018;94:340–62. https://doi.
org/10.1016/j.rser.2018.06.016.
[5] Khan AS, Man Z, Bustam MA, Nasrullah A, Ullah Z, Sarwono A, et al. Efficient
conversion of lignocellulosic biomass to levulinic acid using acidic ionic liquids.
Carbohydr Polym 2018;181:208–14. https://doi.org/10.1016/j.
carbpol.2017.10.064.
[6] Xie C, Song J, Zhou B, Hu J, Zhang Z, Zhang P, et al. Porous Hafnium Phosphonate:
novel heterogeneous catalyst for conversion of levulinic acid and esters into
γ-valerolactone. ACS Sustainable Chem Eng 2016;4(11):6231–6. https://doi.org/
10.1021/acssuschemeng.6b02230.
[7] Shao Y, Sun K, Li Q, Liu Q, Zhang S, Liu Q, et al. Copper-based catalysts with
tunable acidic and basic sites for the selective conversion of levulinic acid/ester to
γ-valerolactone or 1,4-pentanediol. Green Chem 2019;21(16):4499–511. https://
doi.org/10.1039/C9GC01706B.
[8] Song J, Wu L, Zhou B, Zhou H, Fan H, Yang Y, et al. A new porous Zr-containing
catalyst with a phenate group: an efficient catalyst for the catalytic transfer
hydrogenation of ethyl levulinate to γ-valerolactone. Green Chem 2015;17(3):
1626–32. https://doi.org/10.1039/C4GC02104E.
[9] Tan J, Cui J, Deng T, Cui X, Ding G, Zhu Y, et al. Water-promoted hydrogenation of
levulinic acid to γ-valerolactone on supported ruthenium catalyst. ChemCatChem
2015;7(3):508–12. https://doi.org/10.1002/cctc.v7.310.1002/cctc.201402834.
[10] Zhou L, He Y, Ma Li, Jiang Y, Huang Z, Yin L, et al. Conversion of levulinic acid into
alkyl levulinates: using lipase immobilized on meso-molding three-dimensional
macroporous organosilica as catalyst. Bioresour Technol 2018;247:568–75.
https://doi.org/10.1016/j.biortech.2017.08.134.
[11] Shao Y, Hu X, Zhang Z, Sun K, Gao G, Wei T, et al. Direct conversion of furfural to
levulinic acid/ester in dimethoxymethane: understanding the mechanism for
9
Fuel 293 (2021) 120457
polymerization. Green Energy Environ 2019;4(4):400–13. https://doi.org/
10.1016/j.gee.2018.10.002.
[12] Mizugaki T, Nagatsu Y, Togo K, Maeno Z, Mitsudome T, Jitsukawa K, et al.
Selective hydrogenation of levulinic acid to 1,4-pentanediol in water using a
hydroxyapatite-supported Pt–Mo bimetallic catalyst. Green Chem 2015;17(12):
5136–9. https://doi.org/10.1039/C5GC01878A.
[13] Cui J, Tan J, Zhu Y, Cheng F. Aqueous hydrogenation of levulinic acid to 1,4-
pentanediol over Mo-modified Ru/activated carbon catalyst. ChemSusChem 2018;
11(8):1316–20. https://doi.org/10.1002/cssc.v11.810.1002/cssc.201800038.
[14] Zhang Z. Synthesis of γ-valerolactone from carbohydrates and its applications.
ChemSusChem 2016;9(2):156–71. https://doi.org/10.1002/cssc.v9.210.1002/
cssc.201501089.
[15] Dutta S, Yu IKM, Tsang DCW, Ng YH, Ok YS, Sherwood J, et al. Green synthesis of
gamma-valerolactone (GVL) through hydrogenation of biomass-derived levulinic
acid using non-noble metal catalysts: a critical review. Chem Eng J 2019;372:
992–1006. https://doi.org/10.1016/j.cej.2019.04.199.
[16] Hu X, Song Y, Wu L, Gholizadeh M, Li C-Z. One-pot synthesis of levulinic acid/ester
from C5 carbohydrates in a methanol medium. ACS Sustain Chem Eng 2013;1(12):
1593–9. https://doi.org/10.1021/sc400229w.
[17] Bui L, Luo H, Gunther WR, Román-Leshkov Y. Domino reaction catalyzed by
zeolites with Brønsted and Lewis acid sites for the production of γ-valerolactone
from furfural. Angew Chem Int Ed 2013;125(31):8180–3. https://doi.org/
10.1002/ange.v125.3110.1002/ange.201302575.
[18] Melero JA, Morales G, Iglesias J, Paniagua M, López-Aguado C, Wilson K, et al.
Efficient one-pot production of γ-valerolactone from xylose over Zr-Al-Beta zeolite:
rational optimization of catalyst synthesis and reaction conditions. Green Chem
2017;19(21):5114–21. https://doi.org/10.1039/C7GC01969F.
[19] Zhang L, Yu H, Wang P, Li Y. Production of furfural from xylose, xylan and corncob
in gamma-valerolactone using FeCl3⋅6H2O as catalyst. Bioresour Technol 2014;
151:355–60. https://doi.org/10.1016/j.biortech.2013.10.099.
[20] Yin D, Ren H, Li C, Liu J, Liang C. Highly selective hydrogenation of furfural to
tetrahydrofurfuryl alcohol over MIL-101(Cr)-NH2 supported Pd catalyst at low
temperature. Chin J Catal 2018;39(2):319–26. https://doi.org/10.1016/S1872-
2067(18)63009-8.
[21] Xie Z, Chen B, Wu H, Liu M, Liu H, Zhang J, et al. Highly efficient hydrogenation of
levulinic acid into 2-methyltetrahydrofuran over Ni-Cu/Al2O3-ZrO2 bifunctional
catalysts. Green Chem 2019;21(3):606–13. https://doi.org/10.1039/
C8GC02914H.
[22] Hernández B, Iglesias J, Morales G, Paniagua M, López-Aguado C, García Fierro JL,
et al. One-pot cascade transformation of xylose into γ-valerolactone (GVL) over
bifunctional Brønsted-Lewis Zr-Al-beta zeolite. Green Chem 2016;18(21):5777–81.
https://doi.org/10.1039/C6GC01888B.
[23] Iglesias J, Melero JA, Morales G, Paniagua M, Hernández B, Osatiashtiani A, et al.
ZrO2-SBA-15 catalysts for the one-pot cascade synthesis of GVL from furfural. Catal
Sci Technol 2018;8(17):4485–93. https://doi.org/10.1039/C8CY01121D.
[24] Winoto HP, Fikri ZA, Ha J-M, Park Y-K, Lee H, Suh DJ, et al. Heteropolyacid
supported on Zr-Beta zeolite as an active catalyst for one-pot transformation of
furfural to γ-valerolactone. Appl Catal B Environ 2019;241:588–97. https://doi.
org/10.1016/j.apcatb.2018.09.031.
[25] Li W, Cai Z, Li H, Shen Yu, Zhu Y, Li H, et al. Hf-based metal organic frameworks as
bifunctional catalysts for the one-pot conversion of furfural to γ-valerolactone. Mol
Catal 2019;472:17–26. https://doi.org/10.1016/j.mcat.2019.04.010.
[26] Hengne AM, Kamble SB, Rode CV. Single pot conversion of furfuryl alcohol to
levulinic esters and γ-valerolactone in the presence of sulfonic acid functionalized
ILs and metal catalysts. Green Chem 2013;15(9):2540. https://doi.org/10.1039/
c3gc41098f.
[27] Zhu S, Xue Y, Guo J, Cen Y, Wang J, Fan W. Integrated conversion of hemicellulose
and furfural into γ-valerolactone over Au/ZrO2 catalyst combined with ZSM-5. ACS
Catal 2016;6(3):2035–42. https://doi.org/10.1021/acscatal.5b02882.
[28] Zhou H, Song J, Kang X, Hu J, Yang Y, Fan H, et al. One-pot conversion of
carbohydrates into gamma-valerolactone catalyzed by highly cross-linked ionic
liquid polymer and Co/TiO2. RSC Adv 2015;5(20):15267–73. https://doi.org/
10.1039/C4RA14363A.
[29] Ahmed NS, Menzel R, Wang Y, Garcia-Gallastegui A, Bawaked SM, Obaid AY, et al.
Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced
catalysts for carbon-carbon coupling via Ullmann reaction. J Solid State Chem
2017;246:130–7. https://doi.org/10.1016/j.jssc.2016.11.024.
[30] Shao Y, Wang J, Du H, Sun K, Zhang Z, Zhang L, et al. Importance of magnesium in
Cu-based catalysts for selective conversion of biomass-derived furan compounds to
diols. ACS Sustain Chem Eng 2020;8(13):5217–28. https://doi.org/10.1021/
acssuschemeng.9b07841.
[31] Liu H, Huang Z, Kang H, Xia C, Chen J. Selective hydrogenolysis of biomass-
derived furfuryl alcohol into 1,2- and 1,5-pentanediol over highly dispersed Cu-
Al2O3 catalysts. Chin J Catal 2016;37:700–10. https://doi.org/10.1016/j.
catcom.2018.10.023.
[32] Meng H, Liu J, Du Y, Hou B, Wu X, Xie X. Novel Cu-based oxides catalyst from one-
step carbothermal reduction decomposition method for selective catalytic
reduction of NO with NH3. Catal Commun 2019;119:101–5. https://doi.org/
10.1016/S1872-2067(15)61080-4.
[33] Tiwari MS, Gawade AB, Yadav GD. Magnetically separable sulfated zirconia as
highly active acidic catalysts for selective synthesis of ethyl levulinate from
furfuryl alcohol. Green Chem 2017;19(4):963–76. https://doi.org/10.1039/
c6gc02466a.
[34] Iglesias J, Melero JA, Morales G, Paniagua M, Hernández B. Dehydration of xylose
to furfural in alcohol media in the presence of solid acid catalysts. ChemCatChem
2016;8(12):2089–99. https://doi.org/10.1002/cctc.v8.12.
Y. Shao et al.
[35] Liu C, Sun J, Brown HM, Marin-Flores OG, Bays JT, Karim AM, et al. Aqueous
phase hydrodeoxygenation of polyols over Pd/WO3-ZrO2: role of Pd-WO3
interaction and hydrodeoxygenation pathway. Catal Today 2016;269:103–9.
https://doi.org/10.1016/j.cattod.2015.10.034.
[36] Hong E, Sim H-I, Shin C-H. The effect of Brønsted acidity of WO3/ZrO2 catalysts in
dehydration reactions of C3 and C4 alcohols. Chem Eng J 2016;292:156–62.
https://doi.org/10.1016/j.cej.2016.01.042.
[37] Shao Y, Du W, Gao Z, Sun K, Zhang Z, Li Q, et al. Sulfated TiO2 nanosheets
catalyzing conversion of biomass derivatives: influences of the sulfation on
distribution of Brønsted and Lewis acidic sites. J Chem Technol Biotechnol 2020;95
(5):1337–47. https://doi.org/10.1002/jctb.v95.510.1002/jctb.6318.
[38] Hu X, Westerhof RJM, Wu L, Dong D, Li C-Z. Upgrading biomass-derived furans via
acid-catalysis/hydrogenation: the remarkable difference between water and
methanol as the solvent. Green Chem 2015;17(1):219–24.
10
Fuel 293 (2021) 120457
[39] Winoto HP, Ahn BS, Jae J. Production of γ-valerolactone from furfural by a single-
step process using Sn-Al-Beta zeolites: Optimizing the catalyst acid properties and
process conditions. J Ind Eng Chem 2016;40:62–71. https://doi.org/10.1016/j.
jiec.2016.06.007.
[40] Liu H, Huang Z, Zhao F, Cui F, Li X, Xia C, et al. Efficient hydrogenolysis of
biomass-derived furfuryl alcohol to 1,2- and 1,5-pentanediols over a non-precious
Cu-Mg3AlO4.5 bifunctional catalyst. Catal Sci Technol 2016;6(3):668–71. https://
doi.org/10.1039/C5CY01442E.
[41] Sun K, Zhang L, Shao Y, Li Q, Fan H, Gao G, et al. Conversion of monosaccharides
into levulinic acid/esters: impacts of metal sulfate addition and the reaction
medium. J Chem Technol Biotechnol 2019;94(11):3676–86. https://doi.org/
10.1002/jctb.v94.1110.1002/jctb.6172.