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Highly efficient alloyed NiCu/Nb2O5 catalyst for

Cite this: Catal. Sci. Technol., 2020,
the hydrodeoxygenation of biofuel precursors into
10, 4256 liquid alkanes†
Peiying Wang,‡a Yaxuan Jing, ‡a Yong Guo, a
Yan Cui,b Sheng Dai, b

Xiaohui Liu a and Yanqin Wang *a

Received 5th April 2020,
Accepted 3rd June 2020
DOI: 10.1039/d0cy00684j
rsc.li/catalysis
Hydrodeoxygenation (HDO) is a crucial process for the synthesis of biofuels from renewable biomass. Here,
several bimetallic Ni–M/Nb2O5 catalysts (M = Fe, Co, Cu) were synthesized and evaluated in the HDO of
biofuel precursors (aldol adduct of furfural with acetone) to liquid alkane and it was found that Ni–Cu/
Nb2O5 has the best performance (86.5% yield of octane and 5.1% yield of heptane). Various
characterization techniques show that Ni–Cu alloy is formed over the Ni–Cu/Nb2O5 catalyst, which may
have the main active metal sites. Moreover, the Ni–Cu alloy has more sites for the adsorption–activation of
H2, leading to the high activity. During the HDO process, the ring-opening of the intermediate butyl-
tetrahydrofuran (BTHF) and the conversion of octanol are two rate-determining steps. The kinetic study
confirms that the ring-opening of BTHF over Ni–Cu/Nb2O5 is more favorable than that over Ni/Nb2O5.
More importantly, the Ni–Cu alloy significantly restrained the undesirable decarbonylation due to the weak
adsorption of carbonyl, which was key for the efficient production of Cn alkanes. This work provides an in-
depth understanding of the role of Ni–Cu alloys and new insights into the design of non-noble metal
catalysts for the HDO of biofuel precursors.

1. Introduction precursors with different structures. Compared with the C–C

Biomass, as the only sustainable source of organic carbon,
shows great potential to reduce the excessive dependence on
diminishing fossil fuel resources.1–4 With the increasing
demand for transportation fuels, developing carbon neutral
biofuels from renewable biomass has drawn particular
attention.5,6 The production of biofuels from biomass-derived
compounds goes through C–C coupling reactions following
hydrodeoxygenation (HDO) of the obtained fuel precursors.7–9
The past decade has seen a rapid development of research on
the C–C coupling reactions and various C–C coupling
reactions (e.g. aldol condensation,10–12 hydroxyalkylation/
alkylation,13–15 benzoic condensation,16 Michael addition,17
and Robinson annulation18) were developed to synthesize fuel
a
Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of
Industrial Catalysis, School of Chemistry and Molecular Engineering, East China
University of Science and Technology, 130 Meilong Road, Shanghai, 200237, P. R.
China. E-mail: wangyanqin@ecust.edu.cn
b
Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint
Research Center, Institute of Fine Chemicals, School of Chemistry & Molecular
Engineering, East China University of Science and Technology, Shanghai 200237,
P.R. China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d0cy00684j
‡ These authors contributed equally to this work.
coupling step, the HDO reaction is more challenging because
of the need for harsh reaction conditions (high temperature
and H2 pressure).18–21
HDO reactions are usually catalyzed by metal sulfides/
carbides/nitrides/phosphides and bifunctional catalysts
containing metals and acidic sites.22–27 Metal sulfides,
carbides, nitrides and phosphides are unstable, especially in
the hydrothermal environment, and their regeneration
causes environmental pollution,23,26,27 and noble metals are
finite and expensive.28 The exploitation of 3d-transition
non-noble-metal catalysts has therefore attracted more
attention.22,29–31 In addition, in the HDO process, the
undesirable cleavage of C–C bonds is inevitable through
decarbonylation, decarboxylation or hydrocracking,32–36
causing the carbon loss of target alkanes and even
poisoning of hydrogenation metals by carbon
monoxide.37–39 Therefore, designing state-of-the-art non-
noble-metal catalysts to restrain the C–C cracking while
exhibiting excellent activity is highly desirable.
Supported nickel-based catalysts have been commonly
employed in many catalytic processes owing to their
prominent hydrogenation activity and low costs. However,
monometallic Ni catalysts cannot avoid C–C bond
cracking.39,40,56 Bimetallic catalysts often exhibit unique
properties, since alloy or core–shell structures within

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bimetallic catalysts have different electronic or geometric
structures from their constituent metals.41–45,57–60 For
example, Li et al.21 elucidated that Pd/SiO2 catalysts modified
with iron species suppressed the decarbonylation reaction
during HDO. Inspired by the above understanding, we believe
that employing Ni as a base metal to construct bimetals is a
promising strategy to restrain C–C cracking. Our previous
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studies fully proved that Nb-based catalysts are highly
effective in the HDO of biomass-derived oxygenates owing to
the unique ability of NbOx to activate C–O bonds.20,25,46–48
Consequently, we intend to employ Nb2O5 as an acidic
support to prepare nickel-based catalysts.
Herein, we constructed several non-noble-metal-
fabricated Ni catalysts (denoted as Ni–M/Nb2O5, M = Fe, Co,
Cu) for the HDO of the aldol adduct of furfural with
acetone [4-(2-furanyl)-3-butene-2-one, FA]. It is found that Ni–
Cu/Nb2O5 had high HDO activity and superior ability to
suppress decarbonylation. The origin of the unique
properties was expounded by detailed characterization and
kinetic experiments. The formation of Ni–Cu alloys afforded
more H2 chemisorption which was favorable for the
hydrogenation and weak carbonyl chemisorption which
restrained the decarbonylation. The lower apparent
activation energy (Ea) of Ni–Cu/Nb2O5 for the ring-opening
of butyl-tetrahydrofuran (BTHF), compared with that of Ni/
Nb2O5, further illustrated the its higher activity. The
measured Ea for the dehydrogenative decarbonylation of
octanol to heptane provided a rational explanation for the
suppression of the C–C cleavage.
2. Experimental section
2.1 Catalyst preparation
Nb2O5 was synthesized by a hydrothermal method according
to our previous work.46 In a typical process, 19.2 g liquid
solution of self-made niobium oxalate (0.4 mol L−1 Nb) and
0.71 g ammonium oxalate monohydrate were dissolved in 50
mL deionized water. Then the aqueous solution was sealed in
a 100 mL Teflon-lined autoclave and heated at 180 °C for 24
h. The obtained white precipitates were filtered, washed with
deionized water and alcohol several times and dried at 80 °C
overnight. Finally, the obtained white powders were calcined
at 400 °C for 4 h in air with a linear heating rate of 10 °C
min−1. Ni/Nb2O5 and Cu/Nb2O5 were prepared by a wet-
impregnation (WI) method with a loading amount of 20 wt%,
and NiM/Nb2O5 catalysts (M = Fe, Co, and Cu) were prepared
by a WI method with a loading amount of 10 wt% for each
metal precursor. The metal precursors include NiIJNO3)2
·6H2O, CoIJNO3)2·6H2O, FeIJNO3)3·9H2O, and CuIJNO3)2·3H2O.
Nb2O5 was added into an aqueous solution of metal
precursors, and the molar ratio of Ni to M (Ni–M/Nb2O5) was
set to 1. After fully mixing at room temperature, the catalysts
were dried at 60 °C overnight. The resulting powder was
calcined at 400 °C for 3 h and then reduced at 500 °C under
a 30 mL min−1 10% H2/90% Ar flow for 4 h.
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2.2 Catalyst characterization
X-ray powder diffraction (XRD) patterns were recorded in the
θ–2θ mode on a D8 Focus diffractometer (CuKα1 radiation, k
= 1.5406 Å), operated at 40 kV and 40 mA, respectively,
within scattering angles of 10–80°; the scanning speed was
selected as 6° min−1; all the catalysts were pretreated in a
10% H2/90% Ar flow at 500 °C for 4 h. Scanning
transmission electron microscopy (STEM) characterization
was performed using a Thermo Fisher Talos F200X. High
angle annular dark field (HAADF)-STEM images were
recorded using a convergence semi angle of 11 mrad and
inner and outer collection angles of 59 and 200 mrad,
respectively. Energy dispersive X-ray spectroscopy (EDS) was
carried out using 4 in-column Super-X detectors. The Ni
metal dispersions over 20% Ni/Nb2O5 and 10% Ni 10% Cu/
Nb2O5 catalysts were recorded by using H2 pulse
chemisorption (Huasi DAS-7200 automatic chemisorption
instrument). The Ni dispersions were calculated based on
the chemically adsorbed H2 on the catalysts and the practical
amount of Ni determined by ICP-OES in the catalysts (H2 : Ni
= 1 : 1). All H2 pulse titration tests were carried out at
ambient temperature.
H2-temperature-programmed reduction (H2-TPR) profiles
were obtained using a Huasi DAS-7200 automatic chemisorption
instrument. 50 mg sample was pretreated in Ar (30 mL min−1)
at 300 °C for 30 min and then cooled to room temperature. A
reducing gas containing 5% H2/95% Ar was applied at a flow
rate of 30 mL min−1 and the samples were heated to 700 °C with
a heating rate of 10 °C min−1 from ambient temperature, using
a TCD to monitor the H2 consumption.
In situ Fourier transform infrared (FTIR) measurements of
the adsorption of octanal were recorded on a Nicolet Model
iS-50 FT-IR spectrometer equipped with an MCT/A detector.
The FT-IR spectra of the adsorption and desorption of
octanal were obtained with a resolution of 4 cm−1 and 32
scans. Before each experiment, the samples were in situ
reduced with 5% H2/Ar for 1 h at 500 °C and purged with an
Ar flow for another hour to remove the adsorbed H2 on the
catalyst surface and cooled down to room temperature.
Thermal gravimetric (TG) analysis was performed under
an air flow with a heating rate of 10 °C min−1 from R.T. to
800 °C using a WCT-2 thermal analyzer (PerkinElmer
Diamond TG-DTA).
2.3 Activity tests
The HDO of FA was evaluated in a high-pressure stainless-
steel autoclave (50 mL). Prior to the activity test, pure H2 was
purged into the sealed autoclave with a substrate, a catalyst,
and cyclohexane three times to expel the residual air. Then,
the reaction was conducted at the desired temperature and
hydrogen pressure stabilized for a selected reaction duration
with vigorous stirring. After the reaction, the autoclave was
immediately quenched in an ice-water bath. The qualitative
analysis of reaction products was carried out on a GC-MS
system (Agilent 7890A-5975C), and the quantitative analysis
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was performed on a GC system (Agilent 7890B) equipped with
an HP-5 column and an FID. The yields of liquid alkanes
were determined using an internal standard method by
adding pentadecane as an internal standard after the
experiment. The product yield for each product was
calculated as follows:
mol of the product produced
Yieldð%Þ ¼ × 100
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mol of the substrate fed
Intrinsic activities of the 20% Ni/Nb2O5 and 10% Ni 10%
Cu/Nb2O5 catalysts for the BTHF ring-opening and
hydrogenation of octanol reactions were measured at low
conversions (<30%), and preliminary experiments were
performed using varying stirring speeds (in the range of 600–
1200 rpm) to verify the selected stirring speed enabling the
reaction to proceed in the absence of diffusion limitation
under the present reaction conditions. The absence of mass
transfer effect in the kinetic reactions was also checked by
changing the catalyst mass (10–100 mg).
3. Results and discussion
3.1 Identification of NiCu/Nb2O5 as an enhanced catalyst
A series of Ni–M/Nb2O5 (M = Fe, Co, Cu) bimetallic catalysts
and monometallic Ni/Nb2O5 catalysts were prepared by using
a wet-impregnation method, the HDO of FA to octane was
selected as a model reaction to investigate the catalytic
performance of non-noble metal based catalysts, and the
reaction pathway is proposed according to our previous work
(Scheme 1).20 FA is first hydrogenated into THFA, which then
undergoes dehydration/hydrogenation to form BTHF by the
acidity of the Nb2O5 and the effect of metal sites. Next BTHF
goes through ring-opening to obtain 1-octanol, an
intermediate for dehydration and hydrogenation to octane,
finally giving heptane via dehydrogenation–decarbonylation.
Initially, the reaction was carried out at 250 °C for 12 h and
all results were collected as shown in Table 1. It is found that
the total yields of alkanes are similar, but the ratio of octane/
heptane is the highest over NiCu/Nb2O5 among all the
investigated catalysts, indicating its significant inhibition
effect for C–C bond cracking. Few oxygenated compounds
Scheme 1 The proposed reaction pathway for the
hydrodeoxygenation of FA.
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were detected, suggesting that all catalysts have good activity.
In order to clarify whether these catalysts have different
activities, the reaction time was shortened to 2 h and the
results are shown in Table 2. To further verify the effects of
the Nb2O5 support, we employed SiO2 and active carbon (AC)
as supports for comparison (Table S3†). In sharp contrast,
Ni–Cu/SiO2 and Ni–Cu/C gave low yields of alkanes and O/H,
much lower than those over Ni–Cu/Nb2O5, in agreement with
our previous results,20,25,46–48 further confirming the unique
properties of Nb2O5.
It can be seen from Table 2 that the three bimetallic Ni–
M/Nb2O5 (M = Fe, Co, Cu) catalysts have better HDO ability
with 35.5%, 37.4% and 59.5% yield of octane, respectively.
However over the monometallic Ni/Nb2O5 catalyst, the yield
of octane is only 19.3% with 64.2% oxygenated compounds.
More importantly, these Ni–M/Nb2O5 (M = Fe, Co, Cu)
bimetallic catalysts enable the significant suppression of the
C–C cleavage with O/H values of 4.7, 5.9, and 27.0, much
higher than that of Ni/Nb2O5 (O/H of 2.1). These results
indicate that the introduction of second metals indeed
improves the HDO ability, while restraining the C–C cracking.
In particular, the Ni–Cu/Nb2O5 catalyst shows obvious
advantages in promoting HDO and suppressing C–C
cracking.
The further reaction pathway was investigated through the
time course over the 10% Ni 10% Cu/Nb2O5 catalyst and the
results are presented in Fig. 1. During the first 1 hour,
unsaturated products decreased rapidly, and 2-hydroxy-butyl-
tetrahydrofuran (THFA) was produced as the main product,
indicating that hydrogenation is a fast process, which is in
agreement with our previous study.49 Then, the
dehydroxylation intermediate product BTHF accumulated
with the conversion of THFA in 2 hours, suggesting that the
dehydration/hydrogenation of the secondary hydroxy group is
also a facile reaction. After 2 hours, with the opening of the
tetrahydrofuran ring, the yield of 1-octanol increased which
then undergoes hydrogenolysis or dehydration/hydrogenation
to produce octane. For the production of heptane, we
proposed that 1-octanol is first dehydrogenated to 1-octanal,
and then heptane is produced by the decarbonylation of
1-octanal which always happened over metal sites.21
The above results reveal that the ring-opening of BTHF to
octanol and the further conversion of octanol are rate-
determining steps in the entire reaction. Therefore, we
performed the kinetic assessments of these two rate-
determining steps over the 20% Ni/Nb2O5 and 10% Ni 10%
Cu/Nb2O5 catalysts at conversions lower than 20% (Fig. 2). For
the ring-opening of BTHF to octanol, the apparent activation
energy Ea calculated by the Arrhenius equation over 10% Ni
10% Cu/Nb2O5 is 109.9 kJ mol−1, much lower than that over
20% Ni/Nb2O5 (187.8 kJ mol−1), clearly indicating that 10% Ni
10% Cu/Nb2O5 is kinetically more favorable for furan-ring
opening than 20% Ni/Nb2O5 and accordingly affords a higher
activity. Meanwhile for the hydrodeoxygenation of octanol to
octane, the apparent activation energy Ea values over these
two catalysts are really high, but similar, indicating that the
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Table 1 The HDO of FA over various Ni–M/Nb2O5 catalysts for 12 hours

Entry Cat. Yield of octane% Yield of heptane% Octane/heptane (O/H) Yield of DOE% CB.%
1 20% Ni/Nb2O5 62.5 20.1 3.1 1.2 94.6
2 10% Ni 10% Co/Nb2O5 77.1 10.1 7.6 0.4 93.3
3 10% Ni 10% Fe/Nb2O5 67.4 16.0 4.2 0.9 93.3
4 10% Ni 10% Cu/Nb2O5 86.5 5.1 16.7 0.1 94.4

Reaction conditions: 0.1 g catalyst, 0.2 g FA, 6.5 g cyclohexane, 4 MPa H2, 250 °C, 12 h.
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Table 2 HDO of FA over various NiM/Nb2O5 catalysts for 2 hours

Entry Cat. Yield of octane/% Yield of heptane/% Octane/heptane ratio/O/H Yield of oxygenated compoundsa/% CB.%
1 20% Ni/Nb2O5 19.3 9.2 2.1 64.2 93.1
2 10% Ni 10% Co/Nb2O5 35.5 6.0 5.9 44.6 90.2
3 10% Ni 10% Fe/Nb2O5 37.4 8.0 4.7 45.0 90.3
4 10% Ni 10% Cu/Nb2O5 59.5 2.2 27.0 28.3 91.2

Reaction conditions: 0.1 g catalyst, 0.2 g FA, 6.5 g cyclohexane, 4 MPa H2, 250 °C, 2 h. a
Oxygenated compounds including 1, 2, 3, 4, and 5 in
Scheme 1, detailed results in Table S1.†

conversion of octanol into octane is not influenced by
different active metal sites. Therefore, the conversion of
octanol into octane may not pass through hydrogenolysis, but
go through another route, i.e. dehydration following
hydrogenation, because Nb2O5 is a solid acid.
3.2 The alloy structure and its roles in the HDO reaction
To understand the origin of the excellent performance of 10%
Ni 10% Cu/Nb2O5, various techniques were used to identify its
structure and surface properties. X-ray powder diffraction was
carried out to detect the metal phases (Fig. 3). Firstly, the
diffraction peaks at 22.7°, 28.5°, 36.5°, 46.4°, 51.9° and 55.8°,
are clearly seen, which correspond to the (001), (180), (181),
(002), (380) and (182) facets of the orthorhombic T phase
Nb2O5 (JCPDS 30-0873). For 20% Ni/Nb2O5, an additional
diffraction peak at 2θ = 44.5° is observed and corresponds to
the Ni (111) plane (JCPDS 04-0850).
For 20% Cu/Nb2O5, the diffraction peak at 2θ = 43.3°
assigned to the Cu (111) facet (JCPDS 04-0836) can be seen.
Interestingly, the bimetallic 10%Ni10%Cu/Nb2O5 catalyst
exhibits only one single diffraction peak at 2θ = 43.9° besides
the peaks corresponding to orthorhombic T phase Nb2O5,
which is correlated to the alloyed Cu0.81Ni0.19 (111) plane
(JCPDS 47-1406). This XRD pattern clearly shows the
formation of Ni–Cu alloys, which may contribute to the high
HDO ability and high octane/heptane ratio.
HAADF-STEM (Fig. 4) was performed to investigate the
morphology and structural information of the 10% Ni 10%
Cu/Nb2O5 catalyst. The polyhedral nanoparticles are found
with an average particle size of about 24.4 nm, which is in
great agreement with the XRD result (20.0 nm). The EDS
elemental maps pronouncedly demonstrate that Cu and Ni
are uniformly mixed, strongly confirming the formation of
Ni–Cu alloys (Fig. 4).
Then we conducted the H2-temperature-programmed
reduction (H2-TPR) of 20% Ni/Nb2O5, 10% Ni 10% Cu/Nb2O5
and 20% Cu/Nb2O5. It can be seen from Fig. 5 that 20%Ni/
Nb2O5 has an obvious H2-consumption peak at 373 °C, which
was attributed to the reduction of NiO to metallic Ni.50 The
profile of 20% Cu/Nb2O5 shows two reduction features,

Fig. 1 Product distributions versus reaction time in the conversion of Fig. 2 Activation energies of 10% Ni 10% Cu/Nb2O5 and 20% Ni/
FA over the 10% Ni 10% Cu/Nb2O5 catalyst. Reaction conditions: 0.02 Nb2O5 in the conversion of (a) BTHF into octanol and (b) octanol into
g catalyst, 0.2 g FA, 6.5 g cyclohexane, 4 MPa H2, T = 250 °C. octane.

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Fig. 3 XRD patterns of 20% Ni/Nb2O5 and 10% Ni 10% Cu/Nb2O5.

concentrated at 181 °C and 195 °C, respectively. The former

one was assigned to the H2-consumption of reducing well-
dispersed CuO oxide crystallites to metallic Cu and the latter
was associated with the reduction of bulk CuO to Cu metal.51
However, on 10% Ni 10% Cu/Nb2O5, an additional peak
centered at 238 °C is observed and this peak can be ascribed
to the reduction of Cu–O–Ni species,52,53 giving strong
evidence for the formation of Ni–Cu alloy particles, which is
in accordance with the XRD patterns. Despite the presence of
monometallic Ni and Cu nanoparticles, the formation of Ni–
Cu alloys may be the reason for improved HDO ability.
To determine the origin of the high activity of the 10% Ni
10% Cu/Nb2O5 catalyst, we carried out H2 pulse
chemisorption and the results are summarized in Table 3.
For 10% Ni 10% Cu/Nb2O5, the H2 chemisorption amount
was higher than that of the monometallic 20% Ni/Nb2O5,
indicating that the dispersion of Ni over 10% Ni 10% Cu/
Nb2O5 was higher than that over 20% Ni/Nb2O5.54 Therefore,
the Ni–Cu alloy structure can effectively promote the
dispersion of metal Ni, leading to more active metal sites to
promote the HDO reaction.

3.3 Restrained decarbonylation over alloyed NiCu/Nb2O5

To explore the reason for the restrained decarbonylation over
10% Ni 10% Cu/Nb2O5, the adsorption and desorption of the
intermediate octanal over the two catalysts were conducted
with in situ DRIFTS. Fig. 6 shows the adsorption of octanal in
the region of 1600–1800 cm−1, and to exclude the effect of
Nb2O5, the carrier was operated under the same experimental
conditions. Peaks around 1690 cm−1 and 1740 cm−1 are
attributed to the vibration of carbonyl over the support
Nb2O5 (Fig. S3†), while the peak centered at 1712 cm−1 is
attributed to the vibration of carbonyl adsorbed on metal
sites. Strong adsorption of octanal was observed and
maintained at 160 °C on 20% Ni/Nb2O5, however the ad-
species completely desorbed over 10% Ni 10% Cu/Nb2O5
when the temperature reached 100 °C, indicating that the
adsorption of octanal on 10% Ni 10% Cu/Nb2O5 is weaker
than that on 20% Ni/Nb2O5.55 To the best of our knowledge,
Fig. 4 HAADF-STEM images and the corresponding elemental maps
of 10% Ni 10% Cu/Nb2O5.
the adsorption of a reactant could be a critical factor for the
reaction rate. Therefore, the stronger adsorption of octanal
on 20% Ni/Nb2O5 would weaken the C–C bond, resulting in
decarbonylation, whereas the weaker adsorption of octanal
on 20% Ni/Nb2O5 gives the significant inhibition to
decarbonylation. Moreover, on 10% Ni 10% Cu/Nb2O5, the
intensity of octanal adsorbed was higher than that on 20%
Ni/Nb2O5, indicating more exposed active sites on the surface
of 10% Ni 10% Cu/Nb2O5.
The kinetic assessment of the side reaction involving C–C
cleavage, namely octanol to heptane, was further investigated
and the results (Fig. 7) show that the apparent activation
energy Ea of 20% Ni/Nb2O5 (108.6 kJ mol−1) was really lower

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Fig. 7 Activation energies of 10% Ni 10% Cu/Nb2O5 and 20% Ni/

Fig. 5 H2-TPR profiles of the 20% Ni/Nb2O5, 10% Ni 10% Cu/Nb2O5 Nb2O5 in the conversion of octanol into heptane.
and 20% Cu/Nb2O5 catalysts.

3.4 Stability tests

Table 3 The metal content and H2 chemisorption on the 20% Ni/Nb2O5
and 10% Ni 10% Cu/Nb2O5 catalysts
The stability of 10% Ni 10% Cu/Nb2O5 in the conversion of FA
was tested under the selected conditions when the yield of
Metal octane was kept below 50%. After 3 consecutive runs, the yield
contenta
of octane has not changed significantly. However, in the fourth
(wt%) H2 chemi-sorption run, the yield of octane decreased rapidly (24.5%), accompanied
Entry Sample Ni Cu (μmol g−1)
by the generation of more oxygen-containing intermediates
1 20% Ni/Nb2O5 18.3 — 677.0 (73.6%). To find the reason for the deactivation, XRD and TG
2 10% Ni 10% Cu/Nb2O5 8.7 9.7 805.9
3 20% Cu/Nb2O5 — 19.0 101.3
analyses were conducted and the results are shown in Fig. S4
and S5,† respectively. It was found that there was no phase
a
Determined by ICP-OES analysis. change after the reaction, confirming that 10% Ni 10% Cu/
Nb2O5 was structurally stable. But 9% carbon deposition on the
used 10% Ni 10% Cu/Nb2O5 was detected (Fig. S5†), which may
than that of 10% Ni 10% Cu/Nb2O5 (161.0 kJ mol−1), which be the reason for the deactivation. To confirm this, the used
further manifested that the incorporation of Cu into Ni can 10% Ni 10% Cu/Nb2O5 catalyst was calcined under an air flow
inhibit dehydrogenation/decarbonylation. Consequently, the (450 °C, 3 h) and reduced (500 °C, 4 h) again. As expected, the
dramatic enhanced yield of octane over 10% Ni 10% Cu/ catalytic performance of 10% Ni 10% Cu/Nb2O5 was recovered.
Nb2O5 was not only affected by the improved activity for In short, the above results evidenced that 10% Ni 10% Cu/
furan ring-opening but also the significant suppression of Nb2O5 presented structural stability and excellent recyclability.
the side reaction of Ni–Cu alloys (Fig. 8).

Fig. 6 FTIR spectra of octanal adspecies at 30 °C and temperature Fig. 8 Reusability of the 10% Ni 10% Cu/Nb2O5 catalyst in the HDO of
programmed desorption of octanal over (a) 20% Ni/Nb2O5 and (b) 10% FA to octane. Reaction conditions: 0.1 g catalyst, 0.2 g FA, 6.5 g
Ni 10% Cu/Nb2O5. cyclohexane, 4 MPa H2, T = 250 °C, time: 1 h.

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4. Conclusions
In summary, 10% Ni 10% Cu/Nb2O5 was identified as the
most efficient catalyst in the HDO of biofuel precursor FA to
liquid alkanes (86.5% yield of octane and 5.1% yield of
heptane) among the investigated bimetallic Ni–M/Nb2O5
catalysts (M = Fe, Co, Cu) and monometallic Ni/Nb2O5.
Intensive characterization reveals the formation of Ni–Cu
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alloys on 10% Ni 10% Cu/Nb2O5. Detailed studies confirm
that the Ni–Cu alloys have high H2 chemisorption, affording
the high activity. Furthermore, Ni–Cu alloys significantly
restrained the undesirable decarbonylation due to the
weakening adsorption of carbonyl, preventing the carbon
loss. The excellent stability of 10% Ni 10% Cu/Nb2O5 made it
promising for the HDO process. This study adds a new
possibility for high-yield production of biofuels and opens
new insights into the roles of Ni–Cu alloys.
Conflicts of interest
The authors declare no competing financial interest.
Acknowledgements
This work was supported financially by the NSFC of China
(No. 21832002, 21872050, 21808063), the Fundamental
Research Funds for the Central Universities (222201718003),
and the Science and Technology Commission of Shanghai
Municipality (18ZR1408500, 10dz2220500). Additional support
was provided by the Feringa Nobel Prize Scientist Joint
Research Center.
References
1 Y. Jing, Y. Guo, Q. Xia, X. Liu and Y. Wang, Chem, 2019, 5,
2520–2546.
2 P. Sudarsanam, R. Zhong, S. Van den Bosch, S. M. Coman,
V. I. Parvulescu and B. F. Sels, Chem. Soc. Rev., 2018, 47,
8349–8402.
3 Z. Sun, G. Bottari, A. Afanasenko, M. C. A. Stuart, P. J. Deuss,
B. Fridrich and K. Barta, Nat. Catal., 2018, 1, 82–92.
4 S. Kim, E. E. Kwon, Y. T. Kim, S. Jung, H. J. Kim, G. W.
Huber and J. Lee, Green Chem., 2019, 21, 3715–3743.
5 H. Li, A. Riisager, S. Saravanamurugan, A. Pandey, R. S.
Sangwan, S. Yang and R. Luque, ACS Catal., 2017, 8, 148–187.
6 G. Li, B. Hou, A. Wang, X. Xin, Y. Cong, X. Wang, N. Li and
T. Zhang, Angew. Chem., Int. Ed., 2019, 58, 12154–12158.
7 Q. Han, M. U. Rehman, J. Wang, A. Rykov, O. Y. Gutierrez, Y.
Zhao, S. Wang, X. Ma and J. A. Lercher, Appl. Catal., B,
2019, 253, 348–358.
8 S. Liu, T. R. Josephson, A. Athaley, Q. P. Chen, A. Norton, M.
Ierapetritou, J. I. Siepmann, B. Saha and D. G. Vlachos, Sci.
Adv., 2019, 5, 5487–5495.
9 Y. Nakagawa, S. Liu, M. Tamura and K. Tomishige,
ChemSusChem, 2015, 8, 1114–1132.
10 G. W. Huber, J. N. Chheda, C. J. Barrett and J. A. Dumesic,
Science, 2005, 308, 1446–1450.
4262 | Catal. Sci. Technol., 2020, 10, 4256–4263
View Article Online
Catalysis Science & Technology
11 Y. Jing, Y. Zhang, Q. Lv, Y. Guo, X. Liu and Y. Wang, Green
Chem., 2019, 21, 6236–6240.
12 Y. Liu, G. Li, Y. Hu, A. Wang, F. Lu, J.-J. Zou, Y. Cong, N. Li
and T. Zhang, Joule, 2019, 3, 1028–1036.
13 A. Corma, O. de la Torre, M. Renz and N. Villandier, Angew.
Chem., Int. Ed., 2011, 50, 2375–2378.
14 S. Dutta, A. Bohre, W. Zheng, G. R. Jenness, M. Núñez, B.
Saha and D. G. Vlachos, ACS Catal., 2017, 7, 3905–3915.
15 G. Nie, Y. Dai, Y. Liu, J. Xie, S. Gong, N. Afzal, X. Zhang, L.
Pan and J. J. Zou, Chem. Eng. Sci., 2019, 207, 441–447.
16 Y.-B. Huang, Z. Yang, J.-J. Dai, Q.-X. Guo and Y. Fu, RSC Adv.,
2012, 2, 11211–11214.
17 Y. Jing, Q. Xia, X. Liu and Y. Wang, ChemSusChem, 2017, 10,
4817–4823.
18 Y. Jing, Q. Xia, J. Xie, X. Liu, Y. Guo, J.-J. Zou and Y. Wang,
ACS Catal., 2018, 8, 3280–3285.
19 S. Sitthisa, W. An and D. E. Resasco, J. Catal., 2011, 284,
90–101.
20 Q. N. Xia, Q. Cuan, X. H. Liu, X. Q. Gong, G. Z. Lu and Y. Q.
Wang, Angew. Chem., Int. Ed., 2014, 53, 9755–9760.
21 J. Yang, S. Li, L. Zhang, X. Liu, J. Wang, X. Pan, N. Li, A.
Wang, Y. Cong, X. Wang and T. Zhang, Appl. Catal., B,
2017, 201, 266–277.
22 B. Liu and Z. Zhang, ACS Catal., 2015, 6, 326–338.
23 G. Liu, A. W. Robertson, M. M. Li, W. C. H. Kuo, M. T.
Darby, M. H. Muhieddine, Y. C. Lin, K. Suenaga, M.
Stamatakis, J. H. Warner and S. C. E. Tsang, Nat. Chem.,
2017, 9, 810–816.
24 J. C. Serrano-Ruiz, D. J. Braden, R. M. West and J. A.
Dumesic, Appl. Catal., B, 2010, 100, 184–189.
25 Y. Jing, Y. Xin, Y. Guo, X. Liu and Y. Wang, Chin. J. Catal.,
2019, 40, 1168–1177.
26 G. N. Yun, S. J. Ahn, A. Takagaki, R. Kikuchi and S. T.
Oyama, J. Catal., 2017, 353, 141–151.
27 Y. Romero, F. Richard and S. Brunet, Appl. Catal., B,
2010, 98, 213–223.
28 C. Zhao, J. He, A. A. Lemonidou, X. Li and J. A. Lercher,
J. Catal., 2011, 280, 8–16.
29 R. N. Olcese, M. Bettahar, D. Petitjean, B. Malaman, F.
Giovanella and A. Dufour, Appl. Catal., B, 2012, 115–116,
63–73.
30 X. Qiao, T. She, H. Zhang, X. Wen, L. Niu, L. Ricardez-
Sandoval, J. Li and G. Bai, Appl. Catal., B, 2019, 259, 118111.
31 X. Zhang, P. Yan, B. Zhao, K. Liu, M. C. Kung, H. H. Kung, S.
Chen and Z. C. Zhang, ACS Catal., 2019, 9, 3551–3563.
32 M. Balakrishnan, G. E. Arab, O. B. Kunbargi, A. A. Gokhale,
A. M. Grippo, F. D. Toste and A. T. Bell, Green Chem.,
2016, 18, 3577–3581.
33 E. I. Gurbuz, D. D. Hibbitts and E. Iglesia, J. Am. Chem. Soc.,
2015, 137, 11984–11995.
34 Y. Lu, B. Ma and C. Zhao, Chem. Commun., 2018, 54,
9829–9832.
35 W. Yang, R. V. Solomon, J. Lu, O. Mamun, J. Q. Bond and A.
Heyden, J. Catal., 2020, 381, 547–560.
36 Y. Zheng, N. Zhao and J. X. Chen, Appl. Catal., B, 2019, 250,
280–291.
This journal is © The Royal Society of Chemistry 2020

Catalysis Science & Technology
37 F. Jalid, T. S. Khan, F. Q. Mir and M. A. Haider, J. Catal.,
2017, 353, 265–273.
38 F. Yang, N. J. Libretto, M. R. Komarneni, W. Zhou, J. T.
Miller, X. Zhu and D. E. Resasco, ACS Catal., 2019, 9,
7791–7800.
39 J. G. Dickinson and P. E. Savage, ACS Catal., 2014, 4,
2605–2615.
Published on 19 June 2020. Downloaded by Universidad Autonoma de Madrid on 12/13/2022 5:06:09 PM.
40 J. Luo, M. Monai, C. Wang, J. D. Lee, T. Duchoň, F. Dvořák,
V. Matolín, C. B. Murray, P. Fornasiero and R. J. Gorte, Catal.
Sci. Technol., 2017, 7, 1735–1743.
41 D. Raikwar, M. Munagala, S. Majumdar and D. Shee, Catal.
Today, 2019, 325, 117–130.
42 Y. Wang, S. Furukawa and N. Yan, ACS Catal., 2019, 9,
6681–6691.
43 F. F. Yang, D. Liu, H. Wang, X. Liu, J. Y. Han, Q. F. Ge and
X. L. Zhu, J. Catal., 2017, 349, 84–97.
44 J. J. Zhang and C. Zhao, ACS Catal., 2016, 6, 4512–4525.
45 S. Furukawa, M. Ieda and K. I. Shimizu, ACS Catal., 2019, 9,
5096–5103.
46 Y. Xin, L. Dong, Y. Guo, X. Liu, Y. Hu and Y. Wang, J. Catal.,
2019, 375, 202–212.
47 L. Li, L. Dong, X. Liu, Y. Guo and Y. Wang, Appl. Catal., B,
2020, 260, 118143.
48 Q. Xia, Z. Chen, Y. Shao, X. Gong, H. Wang, X. Liu, S. F.
Parker, X. Han, S. Yang and Y. Wang, Nat. Commun., 2016, 7,
11162.
This journal is © The Royal Society of Chemistry 2020
View Article Online
Paper
49 M. Gu, Q. Xia, X. Liu, Y. Guo and Y. Wang, ChemSusChem,
2017, 10, 4102–4108.
50 M. Xu, S. He, H. Chen, G. Q. Cui, L. R. Zheng, B. Wang and
M. Wei, ACS Catal., 2017, 7, 7600–7609.
51 J. J. Xue, X. Q. Wang, G. S. Qi, J. Wang, M. Q. Shen and W.
Li, J. Catal., 2013, 297, 56–64.
52 P. Li, J. Liu, N. Nag and P. A. Crozier, J. Catal., 2009, 262,
73–82.
53 B. C. Miranda, R. J. Chimentao, J. Szanyi, A. H. Braga,
J. B. O. Santos, F. Gispert-Guirado, J. Llorca and F. Medina,
Appl. Catal., B, 2015, 166, 166–180.
54 C. Zhu, H. Wang, H. Li, B. Cai, W. Lv, C. Cai, C. Wang, L.
Yan, Q. Liu and L. Ma, ACS Sustainable Chem. Eng., 2019, 7,
19556–19569.
55 Y. M. Xu, W. B. Zheng, Y. M. Hu, C. Tang, A. P. Jia and J. Q.
Lu, J. Catal., 2020, 381, 222–233.
56 Z. H. Zhang, Q. W. Yang, H. Chen, K. Q. Chen, X. Y. L, P. K.
Ouyang, J. Fu and J. G. G. Chen, Green Chem., 2018, 20, 197.
57 M. M. Ambursa, L. H. Voon, J. J. Ching, Y. Yahaya and J. N.
Appaturi, Fuel, 2019, 236, 236–243.
58 J. Ashok, Y. Kathiraser, M. L. Ang and S. Kawi, Catal. Sci.
Technol., 2015, 5, 4398.
59 B. Seemala, C. M. Cai, C. E. Wyman and P. Christopher, ACS
Catal., 2017, 7, 4070–4082.
60 V. Sanchez, P. Salagre, M. D. Gonzalez, J. Llorca and Y.
Cesteros, Mol. Catal., 2020, 490, 110956.
Catal. Sci. Technol., 2020, 10, 4256–4263 | 4263