Highly selective hydrogenation of furfural and levulinic acid over Ni0.09Zn/NC600 derived from ZIFW-8

Article abstract of DOI:10.1016/j.mcat.2019.110651

Highly selective hydrogenation of furfural and levulinic acid (LA) was studied over Ni_0.09Zn/NC₆₀₀ derived from zeolitic imidazolate frameworks. The existence of active Ni₃ZnC_0.7 particles in Ni_0.09Zn/NC₆₀₀ was confirmed by multiple characterizations. As a result, over Ni_0.09Zn/NC₆₀₀, 99.7% of furfural conversion (FC) and 100% of furan-2-ylmethanol selectivity (FMS) were achieved in isopropanol (IP) at 170 °C for 2 h, while FC and (tetrahydrofuran-2-yl)methanol (THFM) selectivity are 97.5% and 86.4% in water at 150 °C for 1 h. Over the same catalyst, LA was completely converted to γ-valerolactone in water at 95 °C for 0.5 h. The catalyst is still highly active after 6 cycles of recycling with 92.8% of FC and 100% of FMS in IP at 170 °C for 1.5 h and 90.1% of LA conversion and 100% of γ-valerolactone selectivity in water at 80 °C for 0.5 h.

Full text of DOI:10.1016/j.mcat.2019.110651

Molecular Catalysis 480 (2020) 110651
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Highly selective hydrogenation of furfural and levulinic acid over Ni0.09Zn/
NC
derived from ZIFW-8
6
00
a
a,b,
a
a
a
a
Zhi-Xin Li , Xian-Yong Wei ⁎, Guang-Hui Liu , Xing-Long Meng , Zheng Yang , Shuo Niu ,
a
a
a
a
Di Zhang , Hua-Shuai Gao , Zhi-Hao Ma , Zhi-Min Zong
a
b
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou, 221116, Jiangsu, China
State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, Ningxia University, Yinchuan, 750021, Ningxia, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Highly selective hydrogenation of furfural and levulinic acid (LA) was studied over Ni0.09Zn/NC600 derived from
Furfural
zeolitic imidazolate frameworks. The existence of active Ni ZnC particles in Ni Zn/NC
was confirmed by
3
0.7
0.09
600
Levulinic acid
multiple characterizations. As a result, over Ni0.09Zn/NC600, 99.7% of furfural conversion (FC) and 100% of
furan-2-ylmethanol selectivity (FMS) were achieved in isopropanol (IP) at 170 °C for 2 h, while FC and (tetra-
hydrofuran-2-yl)methanol (THFM) selectivity are 97.5% and 86.4% in water at 150 °C for 1 h. Over the same
catalyst, LA was completely converted to γ-valerolactone in water at 95 °C for 0.5 h. The catalyst is still highly
active after 6 cycles of recycling with 92.8% of FC and 100% of FMS in IP at 170 °C for 1.5 h and 90.1% of LA
conversion and 100% of γ-valerolactone selectivity in water at 80 °C for 0.5 h.
Selective hydrogenation
Zeolitic imidazolate frameworks
Ni0.09Zn/NC600
1
. Introduction
only a food additive but also a potentially ideal green solvent [25,26].
Furthermore, VL has attractive applications as a versatile intermediate
Nowadays, the research for upgrading bio-derivates, especially bio-
for producing renewable fuels and chemicals [27–29]. However, al-
though a variety of catalysts, such as Ni [30], Cu [31], and Ru [32],
were widely used in LA hydrogenation (LAH) to VL, they have many
disadvantages, such as low activity, poor selectivity, and need of rela-
tively harsh reaction conditions. Selectively LAH to VL under mild
conditions still faces challenges. With these in mind, developing a
catalyst with highly selective FH and LAH is still insistent demands.
Bimetallic Ni catalysts have been widely used in energy and biomass
upgrading fields due to their low price and high hydrogenation activity
[33,34]. In addition, carbon-based metal nanoparticles derived from
newly emerging zeolitic imidazolate frameworks (ZIFWs) are ex-
tensively applied in many fields [35–39]. Notably, the metal center of
ZIFWs is partially reduced as metal nanoparticles under high-tem-
perature inert gas which is embedded in a ZIFWs-derived carbon ma-
terial [38,39]. In addition, the nitrogen contained in ZIFWs is also
embedded in the carbon material, which could interact with metal
nanoparticles to improve the catalytic performance [40,41]. Inspired by
these advances, developing a high performance catalyst derived from
ZIFWs is indispensable for FH to FM or THFM and LAH to VL.
derived furfural and levulinic acid (LA), to chemicals and fuels has
received considerable attention [1,2]. Furfural obtained from corncob
with a variety of reactive bonds could be selectively hydrogenated to
furan-2-ylmethanol (FM), (tetrahydrofuran-2-yl)methanol (THFM), 2-
methylfuran (2-MF), LA, γ-valerolactone (VL), and/or cyclopentanone
[
3–7]. However, highly selective hydrogenation of furfural is still a
problem. FM is used to produce alkyl levulinates, LA, VL, resins, bio-
fuels, and fuel additives [7,8], while the uses of THFM include as a
solvent for coating or resin and as a raw material to produce a variety of
chemicals, such as pentane-1,5-diol, succinic acid, pentaerythritol, and
pyranoid [9–11]. Furfural hydrogenation (FH) to FM was widely re-
ported over either non-noble metals in liquid phase, such as Cu [12], Co
[
[
13], Ni [14], Cu-Cr [15], and Cu-Co [16], or noble metals, such as Pd
17], Pt [18], and Pd-Cu [19]. In addition, FH to THFM was intensively
studied over various catalysts including Ru [10], Pd [10], Pt [11], and
Ni [20]. However, since activity, selectivity, and stability of these cat-
alysts cannot be simultaneously achieved at a low cost, there is no sa-
tisfactory catalyst for highly selective FH to FM or THFM.
LA is a basic raw material to produce VL, pentane-1,4-diol, 2-me-
thyltetrahydrofuran, and 5-nonanone [21–24]. Remarkably, VL is not
In this work, we prepare a Ni0.09Zn/NC by calcining Ni0.09/ZIFW-8.
The catalyst shows excellent catalytic performances for selective FH to
⁎
Corresponding author at: Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou,
2
21116, Jiangsu, China.
E-mail address: wei_xianyong@163.com (X.-Y. Wei).
https://doi.org/10.1016/j.mcat.2019.110651
Received 25 July 2019; Received in revised form 20 September 2019; Accepted 30 September 2019
2468-8231/ © 2019 Elsevier B.V. All rights reserved.

Z.-X. Li, et al.
Molecular Catalysis 480 (2020) 110651
Fig. 1. XRD patterns of the samples.
FM in isopropanol (IP) or to THFM in water and LAH to VL in water.
. Experimental
2.4. Catalytic reaction
A substrate (50 μL), a Ni
x
Zn/NC
y
(50 mg), and a solvent (10 mL) are
2
added to an 60 mL magnetically stirred autoclave. After replacing air in
the autoclave with N , a certain amount of hydrogen was filled into the
2
2.1. Materials
autoclave. Then, the autoclave was heated to a required temperature
and maintained at the temperature for an indicated period of time at
Furfural (99.0%), LA (99.0%), FM (99.0%), THFM (99.0%), VL
1
50 rpm.
(
(
99.0%), IP, hexane, ethanol, methanol, butanol, 2-methylimidazole, Ni
NO
3
)
2
•6H
2
O, and Zn(NO
3
)
2
•6H
2
O
were purchased from Aladdin
and
Industrial Inc., Shanghai, China and used without purification. N
2
3
. Results and discussion
H used are highly pure gases.
2
3.1. Catalyst characterization
2.2. Catalyst preparation
The diffraction peaks shown in Fig. 1 at 31.7°, 34.4°, 36.3°, 47.5°,
6.6°, 62.8°, 66.4°, 67.9°, and 69.7° are attributed to representative
2
.2.1. Preparation of ZIFW-8
5
Typically, 10.4 g Zn(NO
3
)
2
•6H O and 7.4 g 2-methylimidazole are
2
diffractions of planes (100), (002), (101), (102), (110), (103), (200),
dissolved in 65 mL and 50 mL water, respectively [38,41]. Then, the
former is quickly poured into the latter one with rapidly appearing
white precipitates. After being stirred at 30 °C for 12 h, ZIFW-8 is col-
lected by centrifugation, washed with water and ethanol sequentially,
and dried at 80 °C in vacuum for 12 h.
(
112), and (201) of crystalline ZnO, respectively (PDF#36-1451), while
the characteristic diffraction peaks located at 42.7°, 49.7°, 73.1°, and
8
8.5° can be attributed to representative diffraction of planes (111),
(
200), (220), and (311) of Ni
3
ZnC0.7 (PDF#28-0713), respectively. The
diffraction peaks of Ni
3
ZnC0.7 were significantly enhanced with in-
creasing Ni loading. Transmission electron microscopic images (Fig. S1)
2
.2.2. Preparation of Ni
Typically, 2.47 g Ni(NO
Then, 5.00 g ZIFW-8 is dispersed in the Ni(NO
tion followed by agitation at 30 °C for 12 h to obtain Ni0.09/ZIFW-8 by
x
/ZIFW-8
of Ni
x
Zn/NC600 also show that the number of Ni ZnC0.7 particles in-
3
3
)
2
•6H
2
O is dissolved in 70 mL ethanol.
creased significantly with increasing Ni content. As observed from TG
3
)
2
•6H O/ethanol solu-
2
curves, Ni0.09/ZIFW-8 rapidly decomposed with raising the temperature
to 320 °C under flow N
2
(Fig. S2). Hence, Ni0.09Zn/NC were prepared
y
subsequent filtration, washing, and drying. Other Ni /ZIFW-8 species
x
at 400, 500, 600, and 700 °C. The diffraction peaks of ZnO and
Ni ZnC0.7 increased with raising CT, indicating that the crystal sizes of
ZnO and Ni
were prepared in the same way, where x represents the molar ratio of Ni
to Zn (x = 0.01, 0.05, 0.09, and 0.13).
3
3
ZnC0.7 tend to increase at higher temperatures (Fig. 1).
Ni, Zn, N, C, O, NiO, and ZnO were confirmed to exist in Ni0.09Zn/
2
.2.3. Preparation of Ni
Typically, Ni0.09Zn/NC600 is prepared by calcining Ni0.09/ZIFW-8
under N at 600 °C for 5 h. Other Ni Zn/NC species were prepared in
the same way, where x represents the molar ratio of Ni to Zn (x = 0.01,
.05, 0.09, and 0.13) and y represents the calcination temperature (CT)
of Ni /ZIFW-8 (y = 400, 500, 600, and 700 °C).
x
Zn/NC
y
NC
(Table S1, Figs. 2 and S3). Peaks for Ni 2p1/2 at 870.1 eV and Ni
6
00
2p3/2 at 852.8 eV correspond to metallic Ni and peaks of Ni 2p1/2 at
871.6 and 873.0 eV and Ni 2p3/2 at 854.8, 855.8, 857.3, 858.9, and
861.2 eV could be attributed to NiO [42–44], while the peaks of Ni 2p3/
2 at 853.6 eV suggest the existence of the carbide phase in the carbon
composite [45,46] (Fig. 2). The peak at 1021.8 eV was also identified
corresponding to ZnO (Fig. S3) [47]. Ni0.09Zn/NC600 contains pyridine
2
x
y
0
x
2.2.4. Preparation of Zn/NC and Ni/NC
Zn/NC and Ni/NC were prepared by calcining ZIFW-8 and Ni-ZIFW,
respectively, under N at 600 °C for 5 h.
2
2.3. Characterization techniques
Each catalyst structure was characterized with a Hitachi S-3700 N
scanning electron microscope combined with an energy dispersive
spectrometer (EDS), a JEM-2100 microscope transmission electron
microscope, an ESCALAB 250 X-ray photoelectron spectroscope, a
Bruker Advance X-ray diffraction (XRD), a Nicolet Magna IR-560
Fourier transform infrared spectrometer, a TP-5000 multi-function NH
3
temperature-programmed desorption (NH -TPD) instrument, a TA SDT-
3
Q600 thermo gravimetric (TG) analyzer, and a laser ablation in-
ductively coupled plasma mass spectrometer (LA/ICPMS).
Fig. 2. X-ray photoelectron spectrum of Ni0.09Zn/NC600
.
2

Z.-X. Li, et al.
Molecular Catalysis 480 (2020) 110651
Fig. 3. Scanning electron microscopic images of ZIFW-8, Ni0.09/ZIFW-8, and Ni0.09Zn/NC600
.
nitrogen and graphite nitrogen, which could increase the metal dis-
persion in the catalyst (Fig. S2) [48,49].
CT, which is consistent with the XRD analysis (Fig. 4). The lattice
spacing (0.215 nm) corresponds to the d(111) in Ni ZnC0.7, confirming
the existence of Ni ZnC0.7 [41].
3
The formation of ZIFW-8 was confirmed in Fig. S4. ZIFW-8 with
clearly smooth surface and particle sizes of around 1.5 μm was observed
in Figs. 3 and S5. Ni0.09/ZIFW-8 was prepared by impregnating Ni with
ZIFW-8 in ethanol. Its rough surface is evenly distributed with holes,
facilitating better metal dispersion in the prepared Ni0.09Zn/NC600 by
subsequent calcination (Figs. 3 and 4). In addition, as Fig. 3 shows,
Ni0.09Zn/NC600 maintains the basic structure of Ni0.09/ZIFW-8, but its
surface obviously collapses partially and becomes rougher. The uniform
distribution of Ni, Zn, N, C, and O in Ni0.09Zn/NC600 shown in Fig. S6
indicates that the nitrogen element was successfully inset into Ni0.09Zn/
3
3.2. FH to FM over Ni0.09Zn/NC600
3.2.1. Effects of the molar ratio of Ni to Zn in Ni Zn/NC600, CT of Ni0.09
x
/
ZIFW-8, and solvent on FH over Ni Zn/NC
0
.09
600
Table S2 shows that FH did not proceed over Zn/NC, while Ni/NC
led to the excessive FH, resulting in low FM selectivity (FMS). In IP,
furfural was not hydrogenated over Ni Zn/NC . FM is the only
0
.01
600
product from FH over Ni Zn/NC , Ni Zn/NC , and Ni Zn/
0
.05
600
0.09
600
0.13
NC600. The uniform dispersion of Ni
3
ZnC0.7 particles was also observed
NC , and FC increased with increasing Ni/Zn molar ratio in the cat-
6
00
in Fig. 4. The particle size of Ni ZnC0.7 gradually increased with raising
3
alyst, since a lot of Ni ZnC was formed by the interaction between Ni
3
0.7
and Zn/NC. In water, both FC and THFM selectivity (THFMS) increased
with increasing Ni/Zn molar ratio up to 0.09 in Ni Zn/NC600, but fur-
x
ther increase in Ni/Zn molar ratio decreased THFMS (Table S3). Similar
tendancy for LA conversion (LAC) was also observed in Table S4, while
VL is the only product from LAH (Fig. 5).
As displayed in Fig. 6, FC increased to ca. 99% with raising the CT to
6
00 °C in IP. However, at higher CTs, FC dramatically dropped, perhaps
due to the increase in Ni
and 6a).
3
ZnC0.7 particle size in Ni0.09Zn/NC700 (Figs. 4
As shown in Fig. 7, relatively high FMSs were obtained in moder-
ately polar solvents over Ni0.09Zn/NC600. FH did not proceed in hexane
and is difficult in methanol and ethanol. Although FC is near 100% and
Fig. 4. Transmission electron microscopic images of the samples.
Fig. 5. Transmission electron microscopic images of Ni0.09Zn/NC600.
3

Z.-X. Li, et al.
Molecular Catalysis 480 (2020) 110651
3
.2.2. Effects of reaction parameters on FH to FM over Ni0.09Zn/NC600
As Fig. 9 displays, FC increased up to almost 100% with prolonging
time to 2 h, raising temperature to 170 °C, and increasing initial hy-
drogen pressure (IHP) to 2 MPa, while FM is the only product in FH.
Fig. 6. CT effect of Ni0.09/ZIF-8 on FH over Ni0.09Zn/NC under 2 MPa of IHP at
y
1
70 °C for 2 h in IP.
Fig. 7. Solvent effect on FH over Ni0.09Zn/NC600 under 2 MPa of IHP at 170 °C
for 2 h.
3
Fig. 8. NH -TPD of Ni0.09Zn/NC600.
FMS is very low in water, more THFM was produced. This could be
related to different activation capacities of active components to H in
2
different polar solvents and solvent-reactant interactions could also be
affected the hydrogenation activity [16,19]. In addition, tetra-
hydrofuran-2-carbaldehyde (THFC) was not found in all the products
(
Table S5). As shown in Fig. 8, Ni0.09Zn/NC600 has strong acidic sites,
+
facilitating both the formation of H from H
2
and furfural adsorption
on Ni0.09Zn/NC600 [50,51]. The > C=O group in furfural should be
+
more easily adsorbed, activated, and hydrogenated initiated by H
addition to the oxygen atom in > C=O [52,53]. Therefore, Ni0.09Zn/
NC600 was used to explore FC, FMS, and THFMS in IP or water.
Ni0.09Zn/NC is used to denote Ni0.09Zn/NC600 in the Figures and Tables
of the Supporting Material for convenience in typesetting.
Fig. 9. FH to FM over Ni Zn/NC
0
.09
600
in IP ((a) IHP 2 MPa, 2 h; (b) IHP 2 MPa,
1
70 °C (c) 170 °C, 2 h; (d) IHP 2 MPa, 170 °C, 1.5 h).
4

Z.-X. Li, et al.
Molecular Catalysis 480 (2020) 110651
3.3. FH to THFM over Ni0.09Zn/NC600 in water
abstraction from the catalyst surface, H…H transfers to the furan ring,
and > C–O– bond cleavage in tetrahydrofuran ring of THFM.
A high THFMS was achieved by adjusting the reaction conditions.
As shown in Fig. 10a, FH at lower temperatures (70 and 90 °C) has
higher FMSs up to 100%. Nevertheless, with raising temperature from
3.4. The leaching and reusability of Ni0.09Zn/NC600 for FH to FM in IP
9
0 to 150 °C, although FC increased, FMS decreased sharply, while
As summarized in Fig. S7, FC does not increase in IP after removing
Ni0.09Zn/NC600, suggesting that active sites of Ni0.09Zn/NC600 were not
lost. LA/ICPMS analysis also shows that Ni or Zn leaching is negligible
THFMS increased rapidly and then decreased with raising temperature
to 170 °C. In addition, the selectivity of other products shows a trend of
gradual increase due to gradual decomposition of THFM at high tem-
peratures.
By prolonging reaction time, THFMS first increased rapidly and then
decreased from 20 to 100 min, while the corresponding FMS decreased
sharply (Fig. 10b). Similarly, the selectivity of other products decreased
with prolonging time. These results also support the possibility that
other products were derived from THFM decomposition. The selective
hydrogenation of FM to THFM over Ni0.09Zn/NC600 was confirmed and
THFC was never detected (Table S5). As illustrated in Scheme 1, FH
proceeds via H addition to the oxygen atom in > C=O of furfural, H−
Fig. 11. XRD patterns of Ni0.09Zn/NC600 after 6 times of recycle.
+
Fig. 10. FH over Ni0.09Zn/NC600 in water under 2 MPa of IHP.
Fig. 12. LAH to VL over Ni0.09Zn/NC600 in water ((a) IHP 2 MPa, 65 °C; (b) IHP
Scheme 1. Possible mechanisms for the selective FH over Ni0.09Zn/NC600
.
2 MPa, 30 min; (c) IHP 2 MPa, 80 °C, 30 min).
5

Z.-X. Li, et al.
Molecular Catalysis 480 (2020) 110651
in the reaction solution (Table S1).
using Ni nanoparticle catalysts capped with organic molecules, J. Catal. 344 (2016)
6
09–615.
As exhibited in Fig. 9d and Table S7, FC only slightly decreased and
FMS remains at 92.8% over Ni0.09Zn/NC600 recycled 6 times. Ni0.09Zn/
NC600 is more stable than other catalysts reported (Table S7). XRD
analysis suggests that the structure of Ni0.09Zn/NC600 remains almost
no change after 6 cycles (Fig. 11).
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