Efcient hydrogenation of biomass-derived furfural and levulinic acid

on the facilely synthesized noble-metal-free CueCr catalyst

Kai Yan
*
, Aicheng Chen
Department of Chemistry, Lakehead University, 955 Oliver Road, Thunder Bay, ON P7B 5E1, Canada
a r t i c l e i n f o
Article history:
Received 17 January 2013
Received in revised form
5 May 2013
Accepted 11 May 2013
Available online 29 June 2013
Keywords:
CueCr Catalyst
Hydrogenation
Furfural
Levulinic acid
Biofuel
a b s t r a c t
Biomass-derived platform intermediate furfural and levulinic acid were efciently hydrogenated to the
value-added furfuryl alcohol and promising biofuel g-valerolactone, respectively, using a noble-metal-
free CueCr catalyst, which was facilely and successfully synthesized by a modied co-precipitation
method using the cheap metal nitrates. In the rst hydrogenation of furfural, 95% yield of furfuryl
alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the
hydrogenation of levulinic acid, 90% yield of g-valerolactone was highly selectively produced at 97.8%
conversion. Besides, the physical properties of the resulting CueCr catalysts were studied by XRD (X-ray
diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray
photoelectron spectroscopy) to reveal their inuence on the catalytic performance. Subsequently,
different reaction parameters were studied and it was found that Cu
2
/Cr
3
ratios (0.5, 1 and 2), reaction
temperature (120e220

C) and hydrogen pressure (35e70 bar) presented important inuence on the
catalytic activities. In the end, the stability of the CueCr catalysts was also studied.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Biomass is one of the most plentiful resources of renewable
energy existed in the world [1e3]. An imperative current challenge
for researchers, industry, engineering and government is the
development of efcient technologies that utilize biomass or
biomass-derivedchemicals tothelargest extent [3e5]. Inmost of the
approaches being investigated, the platform intermediate furfural
and levulinic acid (LA) were often hydrogenated to the value-added
chemicals (e.g. FA (furfuryl alcohol), GVL (g-valerolactone)) and
attractive biofuels (e.g. MF (2-methylfuran), GVL) [6e9].
Arising from the reduction of the carbonyl group (C]O), FA
could be produced as shown in Scheme 1a, it is a commercial
product as green solvent and has been widely employed in the
biorenery and pharmaceutical industry [10,11]. It is soluble in
common organic solvents and miscible with water [12], thus it is
often used as a chemical building block for pharmaceutical drug
synthesis [12]. In principle, FA can be selectively produced through
the cleavage of C]O bond. However, many side compounds are
often simultaneously produced from the secondary or side re-
actions (e.g. hydrogenation to tetrahydrofurfuryl alcohol (THFA),
hydrogenolysis of FA to MF, decarbonylation of furfural to furan)
[6,10,11]. Developing an efcient catalytic system for the highly
selective production of FA is becoming vital.
In the last decades, different types of catalysts have been
developed for the production of FA. Homogeneous catalysts based
on Ru- or Rh-complex often appeared very attractive, high con-
version (over 90%) as well as good selectivity of FA (over 95%) were
obtained [13e15]. Due to its environmental benignity, easier
recycle and reuse, heterogeneous catalyst display more attractive.
The hydrogenation of furfural has been studied using the noble-
metal catalysts (e.g. Ru, Pd and Pt). Sometimes another metal (e.g.
Sn) or promoter (e.g. heteropoly acids, CO
2
) is added to improve the
catalytic performance [16e19]. Among the various heterogeneous
catalysts, copper catalysts (Cu-nanoparticles and copper chromite)
have been shown to preferentially cleave CeO bond for the pro-
duction of FA with minor CeC cleavage or hydrogenation of the
furan ring [17,19,20]. It was found that the molecularly adsorbed
furfural interacted with the Cu surface via the lone pair of oxygen
[20], which played a crucial role in the selective hydrogenation. For
the typical copper chromite (Cu
2
Cr
2
O
5
) catalyst, Cu
0
and/or Cu

species were often claimed as primary active species in the catalytic

cycle [21,22]. Recently, Cu
0
was also reported to be the active specie
and primarily responsible for the activity in the CeO hydro-
genolysis of 5-methylfurfuryl alcohol [23]. These above-mentioned
catalytic systems using noble-metal and copper chromite were
advanced, however, the catalytic performance was still relatively
low, the high cost of noble-metal, the easy deactivation and limited
* Corresponding author. Tel.: 1 807 627 3059.
E-mail address: kyan@lakeheadu.ca (K. Yan).
Contents lists available at SciVerse ScienceDirect
Energy
j ournal homepage: www. el sevi er. com/ l ocat e/ energy
0360-5442/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2013.05.035
Energy 58 (2013) 357e363
stability of the Cu-catalysts were a problem, which would inuence
the application [24,25]. An efcient, cheap and stable catalyst for
the selective hydrogenation of furfural is still largely needed.
Through the hydrogenation of LA, GVL can be produced. It was
recently proposed that GVL, a frequently used food additive, ex-
hibits the most important characteristics of an ideal green solvent
possibly for the production of either energy or carbon-based con-
sumer products [7,26,27]. In addition, GVL does not form peroxides
in a glass ask under air inweeks, making it a safe material for large
scale use. Comparative evaluation of GVL and ethanol as fuel ad-
ditives shows very similar properties [28].
The hydrogenation of LA to GVL using the homogeneous Ru-
complex catalysts often appeared very attractive [29e31]. Howev-
er, the recovering of the expensive metal catalysts fromthe reaction
residue is still a challenge. Subsequently, the supported metal
catalysts were often employed, the typical hydrogenation of LA to
GVL have been performed in solvent free or in organic solvents like
dioxane, ethylether [32e34]. Chang et al. [35] reported that carbon
supported Ru, Pt and Pd noble metal for the selective hydrogena-
tion of LA under vapour phase in a continuous down owxed-bed
reactor system, where 5% Ru/C catalyst gave GVL with perfect
selectivity. Although the employed Ru catalysts display good per-
formance, the expensive cost and easy deactivation of Ru catalysts
would greatly limit their utilizations [33].
In this work, a stable and noble-metal-free CueCr catalyst was
facilely and successfully synthesized by a modied co-precipitation
method using the cheap metal nitrates. The CueCr catalysts were
systematically studied for the hydrogenation of biomass-derived
furfural and LA. In the hydrogenation of furfural, 95% yield of FA
was highly selectively achieved at 99% conversion of furfural. For
the hydrogenation of LA, 90% yield of GVL was highly selectively
produced at 97.8% conversion. Subsequently, the reaction parame-
ters (e.g. Cu
2
/Cr
3
ratios, reaction temperature with time, and
hydrogen pressure) and catalyst stability were systematically
studied.
2. Material and methods
2.1. Catalyst preparation
All the chemicals were directly used after purchase. The meth-
odology for the synthesis of CueCr catalysts is shown in Fig. S1 (in
the Supplementary Information). The CueCr hydrotalcite precursor
was transferred to the metal oxides by heating to a certain tem-
perature, which involved dehydration, dehydroxylation, decom-
position of anions, formation of oxide and spinel in series or in
overlapping manner (more details are described in the
Supplementary Information) [36e39].
In the rst step, the CueCr hydrotalcite precursor was synthe-
sized using a modied co-precipitation method [35,37]. The typical
procedure was as following: one solution (A) containing the pre-
calculated amount of metal nitrates of 1 mol/L Cr(NO
3
)
3
$9H
2
O and
1 mol/L Cu(NO
3
)
2
$3H
2
O with different Cu
2
/Cr
3
ratios (0.5, 1, 2)
and the other (B) with precipitating agent solution (1 mol/L NaOH),
a
b
Scheme 1. Hydrogenation of furfural (a) and hydrogenation of LA (b).
K. Yan, A. Chen / Energy 58 (2013) 357e363 358
were added simultaneously into a 250 mL beaker, and the pH value
was kept in the range of 5.5e6.0 under the vigorous stirring at room
temperature. The obtained slurry was further aged for 0.5 h under
vigorous stirring and then transferred into Teon-lined autoclave
for hydrothermal treatment. The autoclave was maintained at
120

C for 6 h in the oven. Thereafter the precipitate was collected
by centrifugation and rinsed three times using the distilled water.
Finally, the obtained powder was dried at 80

C for 12 h and the
CueCr hydrotalcite precursor was achieved. In the second step, the
CueCr catalyst was obtained through the calcination of CueCr
hydrotalcite precursor at 950

C for 10 h with a heating rate of 2

C/
min in the air oven. The resultant CueCr catalyst with the Cu
2
/
Cr
3
ratio of 0.5, 1 and 2, hereafter dened as CueCr0.5, CueCr1
and CueCr2.
2.2. Catalyst characterizations
The powder X-ray diffraction (XRD) patterns for qualitative
phase analysis were collected on a Phillips PW 1050e3710 trans-
mission diffract meter with Cu Ka radiation (l 1.5406

A) with
intervals of 0.05

. For the hydrotalcite precursors, the data were

collected in the range of 5e85

with a step width of 0.05

/2q. For
the calcinated CueCr catalysts, the data were collected in the range
of 15e85

with a step width of 0.05

/2q.
Thermogravimetric analysis (TG) and differential thermal anal-
ysis (DTA) were performed on WCT-2 differential thermal balance
using owing N
2
. Samples were dried at 100

C for 24 h prior to
analysis and w10 mg samples were heated at a heating rate of
10

C/min up to 1000

C.
Transmission electron microscopy (TEM) was used to investi-
gate structural features of the catalysts with a JEOL 2010 instru-
ment. Energy-dispersive X-ray analysis (EDX) was obtained with
Hitachi SU-70 operating at an acceleration voltage of 10 kV.
X-ray photoelectron spectroscopy (XPS) measurements were
performed with an ESCALAB 250 spectrometer with hemispherical
analyzer and monochromatized AlKa X-ray source (E 1486.6 eV),
operated at 15 kV and 15 mA. For the narrow scans, analyzer pass
energy of 40 eV was applied.
2.3. Selective hydrogenation of furfural
The hydrogenation of furfural was performed in a 25 mL micro-
autoclave (Parr Company) with an internal glass reactor. 2.0 mL
furfural was added into 5 mL octane solvent followed by the
addition of 0.1 g catalyst. In order to remove the air, the autoclave
was slowly ushed with argon three times before it was charged
with hydrogen. A stirring speed of 1000 rpm was employed
through the whole reaction procedure. Reaction time zero (t
0
) was
dened when the inner temperature of the autoclave reached the
desired temperature. After reaction, the autoclave was cooled down
to room temperature using a water bath. The product mixture was
rstly centrifuged at the speed of 3000 rpmfor 30 min, and then by
a ltration and followed by the dilution using dichloromethane.
The subsequent samples were analyzed by GC (Shimadzu 2014,
column: 30 m SE-54, FID) using external method. The column
temperature was raised from 40

C to 250

C with a heating rate of
5

C/min. The injector temperature was 350

C, which was loaded
with a sample volume of 2 mL.
2.4. Hydrogenation of LA
The hydrogenation of LA into GVL was performed in a 25 mL
micro-autoclave. The typical procedure was as following: 1.02 g LA
was dissolved in 5 mL deionized water followed by the addition of
w100 mg catalyst. To remove the internal air, the autoclave was
slowly ushed with argon three times before hydrogenwas input. A
stirring speed of 1000 rpm was employed through the whole re-
action procedure. After reaction, the autoclave was cooled down to
room temperature using a water bath. The product mixture was
rstly centrifuged at the speed of 3000 rpm for 30 min, and then
ltrated to obtain the clear solution. In the end, 1-hexanol was
added as internal standard and then dilution using acetone. The
subsequent samples were analyzed by GC (Shimadzu 2014, and
column: 30 m DBWaxetr, FID). The column temperature was raised
from 40 to 250

C with a heating rate of 3

C/min. The injector
temperature was 350

C, which was loaded with a sampling vol-
ume of 0.2 mL.
3. Results and discussion
3.1. Characterization of catalysts
The X-ray diffraction (XRD) patterns (Fig. S2) of CueCr hydro-
talcite precursor indicated that CueCr hydrotalcite precursors were
single phase and well crystallized with the hydrotalcite-type
structure, where the characteristic peaks of hydrotalcite indexed
as (003) at 10.2

, (006) at 20.1

, (009) at 34.5

, (110) at 60.5

[38,40,41]. Fig. S3 shows the representative TG-DTA analysis of Cue

Cr hydrotalcite with the Cu
2
/Cr
3
ratio of 2. DTA curve of CueCr
hydrotalcite showed a weak peak at w105

C, which was associated

with the loss of the physisorbed water. The second sharp appeared
peak at w280

C, corresponding to the loss of coordination water
between the hydrotalcite layers. The peaks appeared between 500
and 660

C, which were due to the elimination of the hydroxyl
groups and the removal of nitrate groups in the form of H
2
O and
NO
x
, thus transforming the hydrotalcite into the mixture of metal
oxide (CuO) and spinel phase (CuCr
2
O
4
) with the layered structures
collapsing. After heating to above 850

C, there was no weight loss
observed due to the transformation into the stable metal oxide of
CuO and spinel CuCr
2
O
4
.
The XRD patterns of the resulting CueCr catalysts are shown in
Fig. 1. The typical peaks of 2q indexed with (101) approximately at
19.8

, (200) at 29.6

, (112) at 31.5

, (211) at 35.2

, (202) at 37.8

,
(220) at 41.0

, (321) at 56.4

, (400) at 61.5

, (411) at 64.9

and (422)
at 74.9

, can be attributed to the spinel CuCr

2
O
4
phase (PDF No. 34-
0424). The typical diffraction peaks with 2q indexed approximately
20 30 40 50 60 70 80
(
4
2
2
)
(
4
0
0
)
(
4
1
1
)
(
3
1
1
)
(
2
2
0
)
(
2
0
2
)
(
2
1
1
)
(
1
1
2
)
(
2
0
0
)
: CuO
2 (degree)
(a)
(b)
(c)
(
1
0
1
)

Fig. 1. XRD patterns of the resultant CueCr catalysts with different Cu

2
/Cr
3
ratios:
(a) 0.5; (b) 1; (c) 2.
K. Yan, A. Chen / Energy 58 (2013) 357e363 359
at 32.3

, 36.2

, 42.2

, 53.6

, 58.1

and 71.6

, which can be assigned

to the crystalline phase of CuO (PDF No. 45-0937). Additionally,
with the Cu
2
/Cr
3
ratio increasing, the intensity of CuO peak
appeared stronger, which was likely due to the vigorous Jahne
Teller effect of Cu
2
. With the amount of Cu
2
increasing, it would
enhance the difculty for Cu
2
to coordinate with Cr
3
in the layer
of CueCr hydrotalcite [42,43], the redundant Cu
2
was transformed
into CuO in the calcination procedure.
The compositions of the resultant CueCr catalysts have direct
inuence on their catalytic performances, thus EDX (Fig. S4) are
employed to verify the successful incorporation of Cu
2
and Cr
3
in
the catalysts. As shown in Fig. S4, the present position of two
prominent Cu and Cr peaks where they are expected to be. Table S1
depicts the EDX results of numeric analysis. At low Cu
2
/Cr
3
ratio
of 0.5 (No. 1), the detected value was 0.45, which was very close to
the initial ratio. With the Cu
2
/Cr
3
ratio increasing to 1 and 2, the
values of 0.71 (No. 2) and 1.63 (No. 3) were obtained, respectively,
which were a little lower than the initial ratios. As above-
mentioned, this was possible due to the rigid JahneTeller effect
[42,43], resulting in the slight leach of Cu
2
. In general, the EDX
analysis conrmed the successful incorporation of Cu
2
and Cr
3
in
the CueCr catalysts.
The chemical state of the metal in the catalyst often presents
crucial inuence on its redox properties, which are vital for the
understanding of the catalytic activity. Fig. S5 depicts the XPS
prole of the chemical state analysis of each element in the CueCr
catalyst with Cu
2
/Cr
3
ratio of 2. It can be noticed that the fresh
catalyst exhibited the Cu 2p
3/2
main peak (Fig. S5a) at 933.5 0.2 eV
with an FWHMof 3.11 eV. Good satellite intensity (Is) was observed
at 942 eV, indicating the existence of Cu
2
species [44]. The use of
the Auger parameter (2p
3/2
, L
3
M
45
M
45
) as well as an inspection of
the Auger peak-shape will allowfor a more accurate assignment for
these species. The peak appeared at 935.2 eV clearly indicated that
only the Cu
2
species existed (Fig. S5b). The XPS scans of the Cr 2p
region (Fig. S5c) with Cr 2p1/2 and Cr 2p3/2 lines at 587.2 eV and
577.7 eV, respectively, which indicated that Cr
3
species existed in
the sample. The O 1s spectrum (Fig. S5d) revealed a well-dened
peak at 530.01 eV with a shoulder cantered at 531.52 eV. The
peak at 530 eV was characteristic of CuO. The small shoulder peak
cantered at 531.52 eV could be attributed to the presence of
CuCr
2
O
4
spinel [45,46].
Representative TEM analysis (Fig. 2) is further performed.
Relatively uniform surface was observed in the case of CueCr
catalyst with the Cu
2
/Cr
3
ratio of 1 (Fig. 2a). With the Cu
2
/Cr
3
ratio increasing to 2 (Fig. 2b), larger particle with better crystallinity
was observed, which further indicated that the metal oxide CuO
was highly dispersed inside the fabricated CueCr catalyst.
3.2. Catalytic hydrogenation of furfural
3.2.1. Cu
2
/Cr
3
ratios inuence
Fig. 3 depicts the catalytic performance of the resultant CueCr
catalysts. In general, the resultant CueCr catalysts display good
performance in the hydrogenation of furfural, where FAwas mainly
produced with a few amounts of THFA and MF obtained simulta-
neously. For the rst CueCr catalyst with the Cu
2
/Cr
3
ratio of 0.5,
12% yield of FA was observed at 20.9% conversion of furfural. With
the Cu
2
/Cr
3
ratio increasing to 1, 32.5% yield of FAwas obtained at
46.3% conversion. The best performance with 83% yield of FA was
achieved at 94% conversion using the CueCr catalyst with the Cu
2
/
Cr
3
ratio of 2. These data conrmed that the Cu
2
/Cr
3
ratios could
alter the extent of hydrogenation, where the enhancement of the
yield of FAwas possible due to the presence of Cu
0
eM
2
eM
3
sites.
During the hydrogenation, the electron-decient Cu
2
and Cr
3
could attract the oxygen in the carbonyl group (C]O) through h
1
on-top adsorption and a close contact, which would activate the
C]O bond p-complexed to the surface of CueCr catalyst, where
copper was able to dissociate hydrogen, resulting in the preferred
hydrogenation of the C]O bond [47]. Meanwhile, the spinel
Fig. 2. TEM analysis of the resultant CueCr catalysts with different Cu
2
/Cr
3
ratios: (a) 1; (b) 2.
Cu-Cr0.5 Cu-Cr1 Cu-Cr2
0
10
20
30
40
50
60
70
80
90
100
C
o
n
v
.
&
Y
i
e
l
d
/
%
Conv./%
Y(FA)/%
Y(THFA)/%
Y(MF)/%
Fig. 3. Hydrogenation of furfural using the CueCr catalysts.
a
Reaction conditions:
V(furfural) 2.1 mL, V(octane) 5 mL, T 200

C, t 4 h, m(catalyst) 0.2 g,
p(H
2
) 60 bar, stirring speed 1000 rpm. CueCr0.5 catalyst: the Cu
2
/Cr
3
ratio of
0.5, CueCr1 catalyst: the Cu
2
/Cr
3
ratio of 1, CueCr2 catalyst: the Cu
2
/Cr
3
ratio of 2.
Conv., the conversion of furfural; Y(FA), the yield of FA; Y(THFA), the yield of THFA;
Y(MF): the yield of MF.
K. Yan, A. Chen / Energy 58 (2013) 357e363 360
CuCr
2
O
4
could not only serve as a support, but also could create the
highly unsaturated active sites and promote more homogeneous
distribution of these active sites [21e23]. As well conrmed by the
XRD analysis (Fig. 4a) in the subsection of recyclability tests, the
surface Cu
2
was reduced into Cu
0
, which was responsible for the
hydrogenation of furfural.
3.2.2. Optimization of the hydrogenation of furfural
Initial explore show that the resulting CueCr catalyst with the
Cu
2
/Cr
3
ratio of 2 presented the best activity, we envisaged that
the yield of FA could be further enhanced through the optimization
of reaction parameters. A new set of experimental design was
shown in Table 1 and endeavoured to nd the important factors
that inuenced the catalytic activities. Reaction temperature and
input hydrogen pressure turned out to be the most important
factors that inuenced the catalytic activities. The best activity was
achieved with 94.9% yield of FA at 99.2% conversion of furfural
under the condition of 200

C, 3 h and 70 bar H
2
(Entry 6). Rela-
tively poor performance was often observed at low temperature
(e.g. 120

C), the conversion was w8% in the rst set of four runs
(Entry 1e4). Better activities were achieved in the four runs (Entry
5e8) at the higher temperature of 200

C, conrming that the
hydrogenation rate was increased at the higher temperature. To
further clear about the inuence of reaction temperature, a range of
reaction temperature (Entry 9e11) was designed. It was interesting
to nd that the conversion of furfural increased stably with the
reaction temperature rising, which was because the high temper-
ature would enhance the hydrogenation rate and promoted faster
mass transportation. However, too high temperature (e.g. 220

C)
was found to be bad for the formation of FA (e.g. only 74.6% yield in
Entry 11), the side reactions such as further hydrogenolysis of FA to
MF were promoted clearly in parallel (Entry 11). Besides, at the
reaction temperature of 200

C, higher hydrogen pressure (e.g.
70 bar) was found to be benecial for achieving higher yield of FA at
a better conversion (e.g. Entry 5 vs. 6).
To benchmark the resulting CueCr catalysts, the catalytic per-
formances in the hydrogenation of furfural have been compared
with the representative results of the previously reported materials
as shown in Table S2. In comparison, to the best of our knowledge,
our results are among the top-list, which are even superior to the
performances of the noble metal-based catalysts.
3.2.3. Catalyst stability in the hydrogenation of furfural
The CueCr catalyst with Cu
2
/Cr
3
ratio of 2 exhibiting the best
catalytic efciency was recycled for several times to evaluate the
stability. Due to the possible carbon deposits from the organic re-
actants or products occurred on the surface of catalyst during the
catalytic reactions, 550

C was used for the calcination to rule out
the possibly adsorbed or deposited carbon species. XRDwas further
employed to monitor the structural evolvement between the spent
and the calcined catalyst. The XRD patterns are shown in Fig. 4. As
expected, Cu
0
was found in the spent CueCr catalyst, which
indexed as (111) at 43.6

, (200) at 50.8

, (220) at 74.4

. It further
conrmed that the Cu
2
on the surface was reduced into Cu
0
, which
was responsible for the catalytic activity, where the Cu
0
was
possibly produced from the reduction of CuO and/or CuCr
2
O
4
. The
appearance of CuCrO
2
(JCPDS 74-0983) in the spent catalyst further
conrmed that the partial reduction of CuCr
2
O
4
spinel occurred,
which has been conrmed by the previous studies [21,23]. On the
other hand, it indicated that the hydrogenation was initially
occurred on the site of CuO, where the CuCr
2
O
4
spinel might serve
as the support to create the highly unsaturated active sites and
Fig. 4. XRD analysis of the spent and calcinated CueCr catalyst with the Cu
2
/Cr
3
ratio of 2. (a) Spent; (b) Calcinated.
Table 1
Optimization of the hydrogenation of furfural on CueCr catalyst with Cu
2
/Cr
3
ratio of 2.
Entry T/

C Time/h H
2
/bar Conv./% Y(FA)/% Y(THFA)/% Y(MF)/%
1
a
120 6 35 <1 <1 0 0
2
a
120 6 70 1.5 <1 0 0
3
a
120 6 35 3.6 3.0 0 0
4
a
120 6 70 8.3 7.9 0 0
5
a
200 3 35 76 73.4 0.1 1.3
6
a
200 3 70 99.2 94.9 0.5 3.5
7
a
200 6 35 81.5 78.0 0.1 3.0
8
a
200 6 70 99.7 85.0 2.0 6.9
9
b
140 3 70 5.9 5.4 0.1 0
10
b
180 3 70 79.7 78.1 0.5 0.7
11
b
220 3 70 99.7 74.6 4.9 10.8
a
Reaction note: other reaction conditions were the same as Fig. 3.
b
Further reaction temperature inuence was investigated from Entry 9 to 11.
Cu-Cr0.5 Cu-Cr1 Cu-Cr2
0
10
20
30
40
50
60
70
80
90
100
C
o
n
v
.
&
Y
i
e
l
d
/
%
Conv./%
Y(GVL)/%
Y(PA)/%
Fig. 5. Hydrogenation of LA using the resulting CueCr catalysts.
a
Reaction conditions:
m(LA) 1.02 g, V(H
2
O) 5 mL, T 200

C, t 10 h, m(catalyst) 0.1 g, p(H
2
) 70 bar,
stirring speed 1000 rpm. CueCr0.5 catalyst: the Cu
2
/Cr
3
ratio of 0.5, CueCr1
catalyst: the Cu
2
/Cr
3
ratio of 1, CueCr2 catalyst: the Cu
2
/Cr
3
ratio of 2. Conv., the
conversion of LA; Y(GVL), the yield of GVL; Y(PA), the yield of PA.
K. Yan, A. Chen / Energy 58 (2013) 357e363 361
promote the more homogeneous distribution of these active sites.
With the reaction proceeding, the support CuCr
2
O
4
will be more
uncovered and partially reduced into CuCrO
2
(Fig. 4a). The calci-
nation will result in the recovery of the structure and potential
redispersion of the active sites on the surface (Fig. 4b), which de-
serves future attention to understand the structural evolvement
during the calcination.
In order to explore the recyclability of the CueCr catalyst, the
spent catalyst was separated through centrifugation at the speed of
3000 rpm for 30 min and then dried at 80

C in the oven with air
environment for 12 h. The spent catalyst was used for the hydro-
genation, and catalytic results were shown in Table 2. For the rst
run, 90% yield of FA was achieved at 95% conversion, which was a
little lower than the values of the fresh catalysts performance. In
the second run, much lower values were obtained, where 75.3%
yield was achieved at the conversion of 83.3%. This was more likely
due to more carbon deposit covered on the catalyst surface after the
consecutive runs [48,49]. To remove the potential carbon deposit,
the spent catalyst was calcinated under 550

C for 3 h and then
used for the next run. It was interesting to nd that very good
performance was achieved. On the other hand, the potential
redispersion of active sites occurred during the calcination, which
deserves for future attention. Besides, stable conversion and yield
of furfuryl alcohol was obtained in the next three runs (Run 3e5).
3.3. Hydrogenation of LA
The resultant CueCr catalysts are further evaluated in the hy-
drogenation of LA and the catalytic results are depicted in Fig. 5. In
general, the resultant CueCr catalysts continue to display very good
performances in the hydrogenation of LA. For the rst CueCr
catalyst with the Cu
2
/Cr
3
ratio of 0.5, 56.7% yield of GVL was
obtained at 70% conversion of LA. In the case of the second CueCr
catalyst with the Cu
2
/Cr
3
ratio of 1, 73.9% yield of GVL was ob-
tained at 83.6% conversion. The best performance was achieved
with 90.7% yield of GVL at close to perfect conversion using the Cue
Cr catalyst with the Cu
2
/Cr
3
ratio of 2. Besides, it was interesting
to nd that the Cu
2
/Cr
3
ratio can alter the extent of hydrogena-
tion, which again indicated that the copper sites were responsible
for the dissociative activation of H
2
and governed the catalytic
performance.
To better compare with previous works from literature, the
catalytic performance in the hydrogenation of LA in this work has
been compared with the representative results of the previously
reported materials as shown in Table S3. In comparison, to our
limited knowledge, our results are very good, which are even better
than the noble metal catalysts.
4. Conclusions
In conclusion, we have successfully fabricated a noble-metal-
free CueCr catalyst derived from its hydrotalcite precursor and
demonstrated that biomass-derived platformchemical furfural and
LA could be efciently hydrogenated to FA and GVL under mild
conditions, respectively. In the rst hydrogenation of furfural, 95%
yield of FA was highly selectively produced at 99% conversion of
furfural under mild conditions. For the hydrogenation of LA, 90%
yield of GVL was highly selectively produced at 97.8% conversion.
Besides, Cu
2
/Cr
3
ratios, hydrogen pressure and reaction tem-
perature presented important inuence on the catalytic activities.
The promising catalyst developed in this work may be a good
candidate for the mild hydrogenation of biomass-derived
monomers.
Acknowledgments
This work was supported by a Discovery Grant from the Natural
Sciences and Engineering Research Council of Canada (NSERC),
Ontario Postdoctoral Fellowship and the Centre for Research and
Innovation in the Bio-Economy (CRIBE).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.energy.2013.05.035.
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Glossary
LA: levulinic acid
GVL: g-valerolactone
FA: furfuryl alcohol
THFA: tetrahydrofurfuryl alcohol
MF: 2-methylfuran
XRD: powder X-ray diffraction
TG: thermo gravimetric analysis
DTA: differential thermal analysis
TEM: transmission electron microscopy
EDX: energy-dispersive X-ray
XPS: X-ray photoelectron spectroscopy
GC: gas chromatography
FID: ame ionization detector
K. Yan, A. Chen / Energy 58 (2013) 357e363 363