ChemCatChem
10.1002/cctc.201700066
FULL PAPER
Synthesis of 1,5-pentanediol from the hydrogenolysis of furfuryl
alcohol over Ni-Y composite catalyst
2
O
3
Husni Wahyu Wijaya,[a], [b] Takashi Kojima, Takayoshi Hara, Nobuyuki Ichikuni, and Shogo
[a]
[a]
[a]
Shimazu*[a]
Abstract: We found that the addition of Y
2
O
3
into Ni formed a
Here, we report the simple preparation and characterization of a
Ni-Y composite as well as its catalytic performance in the
hydrogenolysis of FFA. The typical synthesis of Ni-Y O
3
composite catalyst that selectively produced 1-5-pentanediol (1,5-
PeD) rather than 1,2-pentanediol (1,2-PeD) in the hydrogenolysis of
2 3
O
2
furfuryl alcohol (FFA) at 2.0 MPa H
was produced over the Ni(0)-Y
the properties of Ni-Y , catalytic performance, and reaction route
2
and 423 K. Obviously, 1,5-PeD
composite used the co-precipitation of mixed nitrate salts in
alkaline solution followed by hydrothermal, calcination, and
hydrogen treatments. Appropriate parameters such as Ni/Y mole
ratio and calcination temperature were surveyed to obtain a well-
2
O boundary. This report highlights
3
2 3
O
in the synthesis of 1,5-PeD from FFA.
coupled Ni-Y
conditions (such as reaction temperature, initial H
2
O
3
catalyst. The optimum catalytic reaction
pressure, and
2
substrates dependency) were also examined and determined.
Introduction
The catalytic conversion of biomass-derived furfural (FFR) and
its derivatives to valuable chemicals and fuels by hydrogenation
and hydrogenolysis has received increasing attention in recent
years.[1] Upgrading FFA includes the hydrogenation of its furan
ring into tetrahydrofurfuryl alcohol (THFA),[2] reduction of its
hydroxyl group into 2-methylfuran (2MF),[3] and hydrogenolysis
of the C-O bond of the furan ring into pentanediols.[4,5] In the
case of FFA hydrogenolysis, 1,2-PeD was produced in higher
yield and selectivity over the formation of 1,5-PeD using a
Results and Discussion
2 3
Ni-Y O catalyst screening
2 3
In a typical preparation of Ni-Y O , nickel and yttrium hydroxides
were formed via co-precipitation and later hydrothermal
treatment (Figure S1). Calcination at 623 K, 773 K, 923 K, or
1
073 K for 5 h with 5 K/min elevation step from RT transformed
nickel and yttrium hydroxides into their oxides as shown in
Figure S2. The XRD patterns of calcined Ni-Y samples
2
O
3
supported Ru, Pt/HT, or Cu-based catalyst.[6–9] A Ru/MnO
catalyst system produced 1,2-PeD with 42.1% yield at 1.5 MPa
and 423 K.[6] Employing basic support on Pt, Pt/HT catalyst,
x
contained peaks at 2θ 37.2, 43.3, 62.9, 75.3, and 79.4, which
were identified as NiO (ICSD 53931). Cubic yttrium oxide also
formed according to ICSD 647653 after calcination at 923 K and
H
2
directly transformed FFR giving 1,2-PeD up to 73% yield with
small amount of 1,5-PeD (8% yield) at full conversion.[7] Ru
supported carbon catalyzed the aqueous solution of FFA with
1
073 K, although calcination at 623 K and 773 K produced
amorphous yttrium oxide. The crystallinity of Y decreased
with lower calcination temperatures. The results were consistent
2
O
3
2
0% selectivity to produce 1,2-PeD at 473 K and 1 MPa H
Cu-LDO with basic support also gave 1,2-PeD up to 51.2% yield
and 28.8 % yield of 1,5-PED (413 K and 6 MPa H
).[5] Another
reported work on using non-precious metal based, Cu-Al
catalyst, produced comparable selectivity of 1,2-PeD (48.6%)
and 1,5-PeD (22.7%) at 6 MPa H
and 413 K.[9] Therefore,
2
.[8]
with the experiment by Liu et al., where cubic Y
was formed after calcination at higher than 773 K.[
2
O
3
2 3
in Ni/Y O
11,12]
2
2
O
3
2
2 3
Table 1. Physico-chemical properties of Ni-Y O catalysts.
production of 1,5-PeD selectively from FFA hydrogenolysis is an
interesting and challenging route to renewable fine chemicals
production. 1,5-PeD with an uneven aliphatic carbon and
terminal diols has been used as a building block in producing
Catalyst [a]
Crystallite Size (nm) [b]
BET
(m /g)
2
Ni(0)
24.2
11.8
5.3
Y O
2
3
Ni-Y
Ni-Y
Ni-Y
Ni-Y
Ni-Y
2
2
2
2
2
3
O (2.5)-1073
3
O (2.5)-923
3
O (2.5)-773
3
O (2.5)-623
3
O (2.5)-623pm
23.9
10.3
7.2
17.57
37.53
88.99
71.39
20.39
polyesters, thermoplastics, polyurethanes, and as a plasticizer
4.5
5.6
monomer.[
10]
Employing Ni-based catalysts to transform the
[c]
15.0
93.3
biomass-based chemical FFA into 1,5-PeD via hydrogenolysis is
a worthwhile investigation.
[
a] After hydrogen treatment at 673 K. Catalyst is denoted as Ni-Y
indicates the Ni/Y mole ratio and is the calcination temperature. [b]
Determined by using the Scherrer equation. (pm = physical mixing).
2 3
O (x)-t; x
t
2 3
Figure 1 shows the calcined Ni-Y O (2.5) (the number in
parenthesis indicates the Ni/Y mole ratio) XRD patterns after
hydrogen treatment at 673 K. There are two kinds of peak series
[
[
a]
b]
Husni Wahyu Wijaya, Dr. Takashi Kojima, Dr. Takayoshi Hara, Dr.
Nobuyuki Ichikuni, Prof. Shogo Shimazu
Department of Applied Chemistry and Biotechnology, Graduate
School of Engineering, Chiba University, Japan
2 3
in the XRD patterns, which correspond to Ni(0) and Y O
1-33, Yayoi, Inage, Chiba, 263-8522 Japan
according to ICSD 646092 and ICSD 53931, respectively. The
hydrogen treatment only reduced NiO to Ni (0). It agrees with
previous studies that hydrogen treatment at 673 K was the
proper procedure for producing Ni(0). Sun et al. reported that the
Husni Wahyu Wijaya
Department of Chemistry, Faculty Mathematics and Science,
State University of Malang (Universitas Negeri Malang), Indonesia
Jl. Semarang 5 Malang 65145, East Java, Indonesia
TPR profile of Ni/Y
2
13]
O
3
showed a single peak at 658 K in the
The crystallite sizes of Ni(0) and Y
estimated from Scherrer equation decreased with decreasing
reduction of NiO.[
Supporting information for this article is given via a link at the end of
the document.
2 3
O
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